Materials for energyB
Battery and energy storage devices: from materials to eco-design
For future sustainable economic growth and environment protection, energy generated from renewable sources has to be stored in highly efficient and ecofriendly manner. Therefore, all over the world rechargeable batteries and supercapacitors are in the focal point for the development of efficient electrochemical energy storage systems from macroscale to microscale.
Electrochemical energy storage is a rapidly advancing field building on a continuous stream of innovative ideas. As renewable energy sources become increasingly prevalent the need for high energy-density, high-power storage devices with long cycle lives is greater than ever. The development of suitable materials for these devices begins with a complete understanding of the complex processes that govern energy storage and conversion spanning many orders of magnitude in length and time scales. Furthermore, new battery technologies have to be not only commercially and technically viable, but they should also deliver a lower environmental impact than the current state of the art. Therefore, a major challenge of modern battery technologies is to ensure that newly developed batteries are safe, efficient and follow the highest environmental and social standards at the level of production, use and disposal in a frame of a circular economy.
The focus of this meeting is to bring together all aspects of batteries and alternative electrochemical energy storage devices across the field, from modelling and nanoscale characterization to full-scale battery construction and testing regimes. An interdisciplinary selection of speakers will cover this broad range of topics to develop an overview of the current research and challenges in the battery field in a continuum from materials to eco-design. The intention is to bring together the international community working on the subjects and to enable effective interactions between research and engineering communities. Although a Europe-bound event, participation is invited from all continents. It provides an excellent opportunity for scientists, engineers and manufactures to present recent technical progress and products, to establish new contacts in the appreciated networking events and to exchange scientific and technical information. The symposium will be structured in ten different sections.
Hot topics to be covered by the symposium:
- lithium-ion cells and post-lithium ion technologies
- supercapacitors and metal-ion capacitors
- hybrid battery cells
- automotive and mobile application requirements
- stationary battery application requirements
- advanced manufacturing of batteries
- raw material supply / value chains
- recycling in battery storage technologies
- environmental challenges
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Solid State Battery : Dominic Bresser
Authors : Peter P. Molesworth, Wilhelm R. Glomm, Marius Sandru, Roberto Scipioni, Le T. Truong, Nils P. Wagner*
Affiliations : SINTEF Industry, Trondheim, Norway
Resume : There is a significant push within the Li-ion battery world to reach greater energy densities and safety characteristics. Solid polymer electrolyte (SPEs) Li-ion batteries offer enhanced safety via reduced material flammability and resistance to lithium metal dendrite formation in contrast to classical liquid electrolyte Li-batteries batteries. However, the safety benefits of SPEs are tempered by reduced Li conductivity when contrasted to liquid systems, and requires in most cases operation at elevated temperature to ensure the highest possible conductivity. To date, polyethylene oxide (PEO) is still the most studied system. However, despite significant effort, PEO cannot be easily used above 4 V, due to vulnerability to oxidation and degradation caused by Li salt and electrode by-products under operating conditions. This has led to many alternative polymers being tested, ranging from simple commercially available polymers to complex custom prepared systems. These include, but are not limited to polyesters, polycarbonates and polynitriles, with more exotic systems looking at co-polymers and composite SPEs. This study will look at the preparation of novel plasticiser free polyethyleneimine (PEI) co-polymers, from monomer to SPE, and subsequent testing and benchmarking against PEO systems. Performance will be studied using a flexible cell solution, that allows simultaneous, in operando measurement of SPE thickness under electrochemical characterisation, at a range of temperatures. This allows for accurate determination of SPE conductivity and Li transference number at different temperatures.
Authors : A.-S. Kelchtermans *(1), B. Joos (1)(2), A. Tesfaye (3), T. Thompson (3), M.K. Van Bael (1)(2), A. Hardy (1)(2)
Affiliations : (1) Hasselt University, Institute for materials research, DESINe, Martelarenlaan 42, 3500 Hasselt, Belgium (2) imo-imomec, division of imec, Wetenschapspark 1, 3590 Diepenbeek, Belgium (3) Umicore, Corporate Research & Development, Watertorenstraat 33, 2230 Olen, Belgium * Presenting Author
Resume : The need for sustainable mobility leads to a growth of the market of electric cars. At this moment, lithium-ion batteries are the most suitable technology due to their high gravimetric and volumetric energy density. In all roadmaps for battery development, solid-state batteries are the next step after advanced lithium-ion batteries. They offer the potential to significantly increase the energy density, combined with a higher safety due to the absence of a flammable liquid electrolyte. During the last years, research on solid-state batteries has significantly increased, but still faces many challenges, such as the development of a high performant solid electrolyte, the integration of the cathode active material with the solid electrolyte, and the integration of the lithium metal anode which is needed to obtain the predefined energy densities. The polymeric backbone eutectogel (P-ETG) is a hybrid solid-state electrolyte in which a Li-ion conducting deep eutectic solvent is confined within the polymeric backbone. Such an electrolyte allows the combination of the processability advantage of polymers with the high Li-ion conductivity of liquid electrolytes, thus overcoming the primary disadvantages of solid polymer electrolytes. We introduce a P-ETG compatible with high-voltage cathode materials. The (electro)chemical compatibility between the cathode and electrolyte is studied by means of (physico)chemical characterization methods, such as XRD, FT-IR, and ICP-OES. The electrochemical properties, such as ionic conductivity and stability window, are probed by electrochemical impedance spectroscopy and voltammetry experiments. The galvanostatic cycling behaviour of the Li|P-ETG|NMC-622 cell is assessed at several (dis)charge rates. This project receives financial support from VLAIO (Baekeland project) and Umicore. C. Sun, et al., Nano Energy, vol. 33, pp. 363?386, 2017 J. Janek, W. G. Zeier, Nature Energy, vol. 1, no. 9. pp. 1?4, 2016 A. Manthiram, et al., Nat. Publ. Gr., vol. 2, 2017 B. Joos et al., Chem. Mater., vol. 32, no. 9, pp. 3783?3793, 2020
Authors : Marine Soler, Céline Barchasz, Vasily Tarnopolskiy, Frédéric Le Cras
Affiliations : CEA, LITEN, 38000 Grenoble, France
Resume : The high demand for portable energy storage is driving the development of new, more efficient and safer portable energy storage systems. A lithium-sulfur battery is based on a lithium metal anode and an elemental sulfur cathode. It is a very promising system on paper as it has a very high theoretical energy density. In addition, sulfur is an inexpensive, abundant, non-critical and non-toxic raw material. On the other hand, lithium-sulfur batteries with conventional liquid electrolytes suffer from several problems preventing them from being commercialized today. The development of so-called "all-solid-state" lithium-sulfur batteries with the use of a highly conductive solid electrolyte (SE) could resolve these difficulties(1). In particular, solid sulfide electrolytes (SSEs) have received increasing interest in recent years due to their promising ionic conductivities around 10-2-10-3 S/cm(2) and their ductility. However, while it solves the problems associated with liquid electrolytes, the all-solid-state system also presents a number of specific challenges. One major challenge of the all-solid-state systems is the study and the control of the interfacial issues, in particular of the SE/Li metal anode interface. Indeed, stability issues of the sulfide-based electrolytes with Li metal may be encountered, as being thermodynamically unstable against lithium metal, as well as the possible growth of lithium dendrites through the solid electrolyte separator (3,4). Since both of these phenomena can severely impact the performance and safety of the battery (poor electrochemical stability of the SE against Li metal leads to decomposition of the SE thus increasing the impedance; growth of lithium dendrites leads to short-circuit of the battery), they must be understood and suppressed. In this work, we study two sulfide electrolytes: argyrodite-type crystalline Li6PS5Cl and glass-ceramic Li7P3S11. In order to assess and compare their stability against lithium metal, Electrochemical Impedance Spectroscopy measurements were carried out over time on symmetric Li/SSE/Li cells, as well as post mortem observations. While the impedance response is multiplied by a factor of 10 within 150h in the case of Li7P3S11, it remains relatively stable for argyrodite type cell. The nature of the decomposition products of the two electrolytes with lithium have been characterized post mortem, and allow a better understanding of this difference in stability. We demonstrate that in the case of argyrodite, the decomposition products limit the further reaction of electrolyte with lithium, whereas they promote the propagation of the decomposition reaction of Li7P3S11.  Wang, HangChao, Xin Cao, Wen Liu, et Xiaoming Sun. 2019. « Research Progress of the Solid State Lithium-Sulfur Batteries ». Frontiers in Energy Research 7: 112.  Busche, Martin R. et al. 2016. « In Situ Monitoring of Fast Li-Ion Conductor Li 7 P 3 S 11 Crystallization Inside a Hot-Press Setup ». Chemistry of Materials 28(17): 6152?65.  Yue, Junpei, Min Yan, Ya-Xia Yin, et Yu-Guo Guo. 2018. « Progress of the Interface Design in All-Solid-State Li-S Batteries ». Advanced Functional Materials 28(38): 1707533.  Wu, Bingbin et al. 2016. « Interfacial Behaviours between Lithium Ion Conductors and Electrode Materials in Various Battery Systems ». Journal of Materials Chemistry A 4(40): 15266?80.
Authors : Luca Porcarelli
Affiliations : 1 POLYMAT University of the Basque Country UPV/EHU, Donostia?San Sebastin, Spain 2 ARC Centre of Excellence for Electromaterials Science and Institute for Frontier Materials, Deakin University, Melbourne, Australia
Resume : In recent years, there has been growing interest in ionic liquids (ILs) electrolytes since their superior thermal and electrochemical stability with respect to conventional organic electrolytes . The need of incorporating ionic liquid into solid state energy storage applications has led to the development of iongels materials. This novel class of materials combines the unique electrolyte properties of ILs with the superior mechanical properties of polymers . In this work, a simple method to prepare a mechanically robust iongel films is demonstrated. Fast (< 1 min) UV photopolymerization of poly(ethylene glycol) diacrylate in the presence of a saturated 42%mol solution of sodium bis(fluorosulfonyl)imide in trimethyliso-butyl phosphonium bis(fluorosulfonyl)imide was employed to prepare versatile taskspecific iongel electrolytes for application in two emerging solid state energy storage devices: namely sodium metal batteries and sodium oxygen batteries. The iongel electrolytes showed high ionic conductivity at room temperature (?10?3 S cm?1) and tuneable storage modulus (104? 107 Pa). The high salt concentration of the gel electrolyte (42% mol) was beneficial for battery performance, Na/iongel/NaFePO4 full cells delivered a high specific capacity of 140 mAh g?1 at 0.1C and 120 mAh g?1 at 1C with good capacity retention after 300 cycles. In addition, preliminary results in sodium oxygen batteries showed remarkable capacity of 0.285 mAh cm?2 at a discharge current of 0.1 mA cm?2. These results suggest the feasibility of solid state design based on iongel materials for next?generation energy storage and conversion applications based on sodium metal electrodes. References:  A. Fdz De Anastro, L. Porcarelli, M. Hilder, C. Berlanga, M. Galceran, P. Howlett, M. Forsyth, D. Mecerreyes, ACS Applied Energy Materials 2019, 2 (10), 6960-6966.  M. Forsyth, L. Porcarelli, X. Wang, N. Goujon, D. Mecerreyes, Accounts of Chemical Research 2019, 52 (3), 686-694
Authors : S. G. Leonardi, M. Samperi, A. Brigandì, V. Antonucci, C. D?Urso
Affiliations : Consiglio Nazionale delle Ricerche Istituto di Tecnologie Avanzate per l'Energia ?Nicola Giordano? Via S. Lucia sopra Contesse, 5, Messina, Italy
Resume : Among the electrochemical storage technologies, sodium-metal-chloride batteries are currently of great interest from research. In this regard, one of the predominant activity concerns the reduction of the operating temperature, which is mainly affected by the limited ionic conductivity of the solid electrolytes typically used in these batteries (0.2 S/cm @ T > 250 °C). In this work, various electrolytic materials with different chemistry, have been successfully synthesized by solid-state reaction and tested as sodium-ion conducting electrolytes. In particular, all the samples are Nasicon-based powders prepared with excess of sodium Na3.3Zr2Si2PO12, or substituted with different metals characterized by ionic radius similar to that of zirconium Na3.3M0.5Zr1.5Si2PO12 (i.e. Mg, Cu, Zn, Co, Fe). Nasicon pellets were prepared from these powders by uniaxial pressing, then sintered at suitable temperature. The activity was aimed at understanding the impact of the composition of the electrolyte on sodium ion conductivity through in situ measurements, using diagnostic techniques such as electrochemical impedance spectroscopy (EIS). Moreover, structural, chemical and morphological characterizations were carried out on the prepared materials using various experimental techniques including X-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), spectroscopy photoelectronics (XPS).
Authors : George P. Demopoulos,, Hsien-chieh Chiu, Umer Farooq, Moohyun Woo, Senhao Wang
Affiliations : Materials Engineering, McGill University, Montreal, QC, Canada
Resume : The strong demand for advanced high-energy-density batteries for the fast-growing electromobility sector necessitates not only the design and development of new electrode/electrolyte materials but also their sustainable synthesis and fabrication. In this context our research focuses on electrode materials made of abundant elements and have high-energy density potential because of their either high theoretical capacity, high-charge voltage, or multi-ion activity as is the case of lithium iron orthosilicate (Li2FeSiO4/LFS) [1,2], lithium cobalt phosphate (LiCoPO4/LCP), and titanium niobate (TiNb2O7/TNO) . Despite however, the promise of these materials for high-energy density gains, there remain significant inherent structural limitations as is energy storage beyond one Li, poor Li-ion intercalation kinetics, electrode/electrolyte interfacial reactivity and complex phase transitions resulting in poor capacity retention. Herein, we report on controlled solution synthesis and deposition of the above nanostructured materials, their mechanochemical and thermal annealing, as well as their composition & interfacial engineering opening new pathways towards realization of their full high-energy density potential. Meanwhile, we have developed a low-temperature sustainable synthesis method allowing for production of cubic nanostructured garnet-type ceramic electrolyte for all-solid-state battery systems. Work is underway for low resistance interfacial integration of garnet with TNO anode and LCP cathode. Acknowledgments: This work is supported by NSERC Canada, Hydro-Québec, and McGill?s Sustainability Systems Initiative (MSSI). References:  Yan Zeng et al., Defect Engineering of Fe-Rich Orthosilicate Cathode Materials with Enhanced Li-Ion Intercalation Capacity and Kinetics, ACS Applied Energy Materials, 2020, 3, 675?686  Majid Rasool et al., PEDOT Encapsulated and Mechanochemically Engineered Silicate Nanocrystals for High Energy Density Cathodes, Advanced Materials Interfaces, 2020, 2000226; DOI: 10.1002/admi.202000226  Marianna Uceda et al., Nanoscale Assembling of Graphene Oxide with Electrophoretic Deposition Leads to Superior Percolation Network in Li-ion Electrodes: TiNb2O7/rGO Composite Anodes, Nanoscale, 2020, 12, 23092?23104
Authors : David Kitsche* (1), Yushu Tang (2), Yuan Ma (1), Damian Goonetilleke (1), Joachim Sann (3), Felix Walther (3), Matteo Bianchini (1,4), Jürgen Janek (1,3), Torsten Brezesinski (1)
Affiliations : (1) Battery and Electrochemistry Laboratory, Institute of Nanotechnology, Karlsruhe Institute for Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein- Leopoldshafen, Germany; (2) Institute of Nanotechnology, Karlsruhe Institute for Technology (KIT), Hermann-von- Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany; (3) Institute of Physical Chemistry & Center for Materials Science (ZfM/LaMa), Justus- Liebig-University Giessen, Heinrich-Buff-Ring 17, 35392 Giessen, Germany; (4) BASF SE, Carl-Bosch-Str. 38, 67056 Ludwigshafen, Germany
Resume : Inorganic solid-state batteries (SSBs) are promising candidates to replace liquid-electrolyte-based lithium-ion batteries (LIBs) for application in electric vehicles, mainly due to potential improvements in safety and energy density. Lithium thiophosphates stand out among the conceivable superionic solid electrolytes, as they show the highest room-temperature ionic conductivities achieved to date. However, their narrow stability windows makes them prone to degradation. Overall, thiophosphate-based SSBs have been reported to suffer from impedance growth and capacity fading due to side reactions at the interfaces during battery operation, thereby emphasizing the need for protective coatings. The beneficial effect of cathode materials coatings has been reported in a large number of studies, with the majority focusing on Li-containing ternary oxides applied by wet-chemical methods. While versatile, cost-efficient and easy to implement, such methods provide only limited control over the coating thickness and morphology. In contrast, atomic layer deposition (ALD) allows preparing conformal nanocoatings on substrates with complex surfaces. ALD has been widely applied in the field of LIBs, but few examples exist on the use of ALD-functionalized electrode materials in bulk-type SSBs. In this contribution, we report on the coating of LiNi0.85Co0.1Mn0.05O2 (NCM-851005) cathode material with HfO2. Specifically, we describe the preparation of HfO2-coated NCM-851005 by ALD of tetrakis(ethylmethylamido)hafnium(IV)/O3. In addition, the positive effect of the nanocoating, especially after annealing, on the cycling performance of NCM-851005 in high-loading SSB full cells with argyrodite Li6PS5Cl solid electrolyte is highlighted.
Na-Ion Battery : Alessandra Di Blasi
Authors : Yongil Kim and Stefano Passerini
Affiliations : Helmholtz Institute Ulm - Karlsruhe Institute of Technology
Resume : Sodium-seawater batteries (Na-SWB) are considered among the most promising electrochemical devices for large scale energy storage and the marine sector. In fact, by employing an open-structured cathode, they benefit from the unlimited supply of sodium from seawater. This means that the energy of such systems is intrinsically limited by the capacity of the anode, which, however, can also be stored outside the cell for seasonal/annual energy storage.
Authors : Enterría, M.*(1), Munuera, J.M (2), Villar-Rodil, S. (2), J.I. Paredes, J.I. (2), Ortiz-Vitoriano, N.*(1,3)
Affiliations : (1) Centre for Cooperative Research on Alternative Energies (CICenergiGUNE), Basque Research and Technology Alliance (BRTA), Alava Technology Park, Albert Einstein 48, 01510. (2) Instituto de Ciencia y Tecnología del Carbono, INCAR-CSIC, C/Francisco Pintado Fe 26, 33011 Oviedo, Spain. (3) Ikerbasque, Basque Foundation for Science, María Díaz de Haro 3, 48013 Bilbao, Spain.
Resume : Sodium-air batteries (SABs) are receiving interest as possible alternatives to Li-ion batteries because of their potential to provide high gravimetric energies. The use of suitable cathode materials is a point of major concern as they are responsible for achieving efficient deposition/redissolution of the solid discharge products formed during battery operation. Graphene has gained attention as a cathode material due to its superior electrical conductivity and highly accessible 2D area. Here, we have prepared high-quality graphene aerogels via electrochemical exfoliation using an innocuous biomolecule (adenosine monophosphate nucleotide) and tested them as SAB cathode using a glyme-based electrolyte. The assembled batteries delivered a discharge capacity as high as 9.64 mAh cm-2 and endured 95 cycles at a discharge depth of 0.5 mAh cm-2 with a high current density (0.2 mA cm-2). Such a good performance was attributed to the phosphate groups present in the nucleotide, which is adsorbed on the surface of the graphene sheets comprising the porous aerogel cathode. Therefore, the phosphate groups modify the nucleation mechanism of the discharge products by i) enhancing the interaction of the cathode with oxygen reactive species and ii) catalyzing the ORR/OER reactions during discharge/charge. This latter aspect is of paramount importance for the implementation of rechargeable SABs, as their reversible cycling is the major bottleneck for their commercialization.
Authors : Edouard Boivin, Robert A. House, Miguel A. Pérez-Osorio, John-Joseph Marie, Urmimala Maitra, Gregory J. Rees, Peter G. Bruce
Affiliations : Departments of Materials and Chemistry, University of Oxford, Parks Road, OX3 1PH, UK. The Faraday Institution, Quad One, Becquerel Avenue, Harwell Campus, Didcot, OX11 0RA, UK. The Henry Royce Institute, Oxford, Parks Road, OX1 3PH, UK.
Resume : Alkali metal (AM) intercalation compounds based on layered transition metal (TM) oxides and containing Li in the TM layers exhibit capacity in addition to that associated with TM redox by invoking redox reactions on the O2- ions. This O-redox is one of the very few options available to increase the energy density of Li-ion and Na-ion batteries. The nature of the ?oxidized oxide? formed has been widely debated with localized holes (O-), peroxo (O22-), peroxo-like (O2n-) and superoxo (O2-) species being proposed. 1?4 However, we have recently identified molecular O2 as the only species formed upon O2- oxidation in several materials such as Li[Li0.2Ni0.13Mn0.54Co0.13]O2, Na0.75[Li0.25Mn0.75]O2 as well as Li[Li0.33Ir0.33Sn0.33]O2. 5?7 In this presentation, I will show that a similar process takes place for Na0.67Mn0.72Mg0.28O2, containing Mg in the TM layers, and in which the molecular O2 has been identified by high resolution O K-edge RIXS and quantified by SQUID, showing that it equates to the charge passed. The O2 is trapped in clusters of vacancies which are formed by Mg out-of-plane displacement into the AM layer and Mn in-plane disordering within the TM layer, as evidenced by Mg K-edge EXAFS, neutron PDF and DFT. The Mg/Mn honeycomb ordering is therefore lost upon charge and O2 is reduced upon discharge, associated with a large voltage hysteresis. In contrast to compounds containing Li in the TM layer, in which the Li/TM honeycomb ordering and the voltage hysteresis are irreversibly lost after the 1st cycle, in Na0.67Mn0.72Mg0.28O2, this latter is retained upon few cycles due to the partial reversibility of Mn in-plane and Mg out-of-plane migration leading to the local reformation of the honeycomb ordering on discharge, as shown by neutron PDF. 1. Luo, K. et al. Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen. Nat. Chem. 8, 684?691 (2016). 2. Hong, J. et al. Metal?oxygen decoordination stabilizes anion redox in Li-rich oxides. Nat. Mater. 18, 256?265 (2019). 3. McCalla, E. et al. Visualization of O-O peroxo-like dimers in high-capacity layered oxides for Li-ion batteries. Science. 350, 1516?1521 (2015). 4. Chen, Z. et al. Unraveling Oxygen Evolution in Li-Rich Oxides: A Unified Modeling of the Intermediate Peroxo/Superoxo-like Dimers. J. Am. Chem. Soc. 141, 10751?10759 (2019). 5. House, R. A. et al. Superstructure control of first-cycle voltage hysteresis in oxygen-redox cathodes. Nature 577, 502?508 (2020). 6. House, R. A. et al. First cycle voltage hysteresis in Li-rich 3d cathodes associated with molecular O2 trapped in the bulk. Nat. Energy 5, 777?785 (2020). 7. House, R. A. et al. Covalency does not suppress O2 formation in 4d and 5d Li-rich O-redox cathodes. Nat. Commun. 1?7 (2021).
Authors : A. Quintela (1,2), L. Otaegui (1), M.C. Morant-Miñana (1), I.P. Gilbert (3), A. Villaverde (1)
Affiliations : 1 Centre for Cooperative Research on Alternative Energies (CIC energiGUNE), Basque Research and Technology Alliance (BRTA), Alava Technology Park, Albert Einstein 48, 01510 Vitoria-Gasteiz, Spain. 2 Fac. de Químicas, UPV/EHU, Apdo 1072, E-20080 San Sebastián, Spain 3 Ormazabal-Velatia, Boroa
Resume : Current lifestyles have increased energy consumption and as such, there is a need for increasing energy storage capability. Among the available energy storage systems, electrochemical energy storage, and more specifically batteries, are attracting growing attention. However, their autonomy, stability and safety characteristics still need to be improved, and it is anticipated that these features will be accomplished with solid-state batteries. (1) A solid-state battery is an evolution of currently available Li-ion batteries. In these batteries the liquid electrolyte is replaced by a solid electrolyte made of non-volatile and non-flammable components which improves the safety characteristics of the cells. Moreover, the presence of a solid electrolyte enables the use of metallic anodes which enhances energy density. (2) Since Li-based technologies are expected to be mostly used for portable and electric vehicle applications, there is a need to find other options such as Ca, Mg, Zn or Na-based systems for other applications.(3) In this work Na has been chosen as an alternative to Li-based batteries. Na is more abundant than Li, (thousand times higher) and is therefore expected to be less affected by market fluctuations. Although its kinetic and energy densities are slower than Li due to the smaller ionic radius of the Li molecules, Na based technologies could be a good alternative for applications in which the space and weight limitation is not a handicap, i.e. stationary storage systems.(4) This work is focused on the development of an all solid-state sodium battery. More specifically, a layered oxide is selected as the cathode active material, a PEO based polymer as the solid electrolyte and metallic Na as the anode. Electrolyte membranes and high active material-loading cathodes with different sodium salts in their composition were prepared and characterized with the aim of analyzing their suitability in a PEO based sodium solid state battery. 1. Manthiram, A., Yu, X. & Wang, S. Lithium battery chemistries enabled by solid-state electrolytes. Nat. Rev. Mater. 2, 1?16 (2017). 2. Varzi, A., Raccichini, R., Passerini, S. & Scrosati, B. Challenges and prospects of the role of solid electrolytes in the revitalization of lithium metal batteries. J. Mater. Chem. A 4, 17251?17259 (2016). 3. Biemolt, J., Jungbacker, P., van Teijlingen, T., Yan, N. & Rothenberg, G. Beyond lithium-based batteries. Materials 13, 425 (2020). 4. Kundu, D., Talaie, E., Duffort, V. & Nazar, L. F. The emerging chemistry of sodium ion batteries for electrochemical energy storage. Angew. Chemie - Int. Ed. 54, 3432?3448 (2015).
Authors : Concetta Busacca, Leone Frusteri, Orazio Di Blasi, Alessandra Di Blasi, Vincenzo Antonucci
Affiliations : CNR-ITAE, Via Salita Santa Lucia sopra Contesse 5, 98126 ? Messina, Italy
Resume : Sodium ion batteries (SIBs) can be considered a good alternative to Li-ion due to the abundance of sodium sources and the low cost. However, their development also faces challenges such as poor cycling stability and unsatisfying rate performance. Traditional electrodes use binders in such a way as to integrate the active phase within a matrix that gives mechanical stability and assists it during the charging and discharging processes. Unfortunately, binders are generally electrochemically inactive and insulating, which reduces the overall energy density and leads to poor cycling stability. Therefore, binder-free electrodes provide great opportunity for high-performance SIBs. This work is focused on the development of innovative cathode materials based on sodium-manganese-phosphate (NaMnPO4) homogeneously dispersed in carbon nanofibers (CNF) synthesized by electrospinning technique. The latter has allowed the synthesis of materials characterized by nanometric dimensions and the introduction of a carbonaceous matrix, this in order to improve the electrocatalytic activity and the electrical conductivity. The one-dimensional materials thus synthesized have a high specific surface and porosity, thus offering a good connection between active matter and electrolyte with a consequent advantage in terms of insertion and extraction of sodium ions. The technique allowed to obtain a flexible binder-free electrode having by an appropriate specific surface equal 150 m2 g? 1 NaMnPO4-CNF.
Authors : Arbizzani C.*, Bargnesi, L., Gigli, F.
Affiliations : Alma Mater Studiorum University of Bologna, Bologna, Italy
Resume : Among the different technologies, Na-ion batteries could play a role in substituting Li-ion batteries where the specific and volumetric energy and power are not the main requisites. Indeed, the cost per Wh of Na ion batteries with organic electrolyte is still comparable to that of Li ion batteries, despite the distributed availability and lower costs of sodium, given their lower specific energy . The way to decrease the cost is to use aqueous electrolytes that also contribute to increase safety . In addition, the adoption of water-based process to produce the electrodes is a suitable strategy toward sustainability . This study focus on the use of natural and sustainable polymers that can be processed in water and, nonetheless, guarantee the stability of the electrodes in aqueous electrolyte. The results of physico-chemical characterization of the materials and the electrochemical test on the Na-ion cell are here reported and discussed. Acknowledgments Ministry of Economic Development, and ENEA PAR 2019-2021 project are gratefully acknowledged for the research funding. References  S. F. Schneider, C. Bauer, P. Novák, E. J. Berg, ?A modeling framework to assess specific energy, costs and environmental impacts of Li-ion and Na-ion batteries,? Sustain. Energy Fuels, 2019, 3(11), 3061?3070.  D. Pahari, S.Puravankara, ?Greener, Safer, and Sustainable Batteries: An Insight into Aqueous Electrolytes for Sodium-Ion Batteries?, ACS Sustainable Chem. Eng., 2020, 8, 10613-10625.  D. Bresser, D. Buchholz, A. Moretti, A. Varzi, S. Passerini, ?Alternative Binders for Sustainable Electrochemical Energy Storage-the Transition to Aqueous Electrode Processing and Bio-Derived Polymers?, Energy and Environmental Science 2018, 11, 3096?3127.
Authors : A.Plewa, K. Kutukova, W. Zaj?c, E. Zschech, J. Molenda
Affiliations : A.Plewa; W. Zaj?c; J. Molenda (AGH University of Science and Technology, Faculty of Energy and Fuels, al. Mickiewicza 30, 30-059 Krakow, Poland) K. Kutukova; E. Zschech (Fraunhofer Institute for Ceramic Technologies and Systems, Dresden, Germany) K. Kutukova; E. Zschech (Brandenburg University of Technology Cottbus-Senftenberg, Institute of Physics, Germany)
Resume : Li-ion batteries are currently the most dynamically growing devices for electrical energy storage for portable electronics, electric and hybrid vehicles, and large-scale energy storage. Since resources of lithium and transition metals, particularly cobalt, are limited and expensive, cobalt-free Na-ion batteries have been recognized as one of the potential candidates for next-generation rechargeable batteries. They are characterized by a comparable energy density, significantly reduced costs, and practically unlimited resources of sodium. Currently, the major challenge in advancing Na-ion batteries technology is to find suitable cathode materials based on abundant, low-cost, safety and environmentally benign elements such as iron and sulphur. One of the most promising candidates from this group is Na2Fe2(SO4)3 which contains only low-cost and abundant elements. Na2Fe2(SO4)3 exhibits the highest Fe3+/Fe2+ redox potential found so far, equal to 3.7 V vs. Na+/Na. Such a high redox potential combined with a high capacity for sodium intercalation (x in Na2-xFe2(SO4)3 ranges from 0 to 1.7) leads to a particularly large theoretical energy density of 456 Wh kg?1. Until now, only some synthesis methods were used to obtain Na2Fe2(SO4)3 compounds. Moreover, these methods are characterized by a high degree of complexity and require a long synthesis time and a high energy input. Herein, we present a facile, low cost, green chemistry, low-temperature synthesis method yielding nanometric Na2Fe2(SO4)3 cathode material with very promising electrochemical properties. To optimize the 3D microstructure of the layered Na2Fe2(SO4)3 cathode material, X-ray microscopy and nano X-ray computed tomography were used for high-resolution imaging. The system Na/Na+/Na2Fe2(SO4)3 exhibited an energy density of 407 Wh kg?1. The capacity retention of the cell was above 90% and no microstructural changes were observed after 50 cycles, which points to exemptional stability of the electrode.
Organic Battery : Kristina Edstrom
Authors : J. Asenbauer,1,2 K. Shi,1,2 C. Marchiori,3 M. Araujo,3,4 R. Carvalho,4 D. Brandell,5 S. Pouget,7 L. Picard,8 S. Jestin,9 M. Völlmer,9 S. Bayle,10 D. Bresser 1,2
Affiliations : 1 Helmholtz Institute Ulm (HIU), Helmholtzstrasse 11, 89081 Ulm, Germany 2 Karlsruhe Institute of Technology (KIT), P.O. Box 3640, 76021 Karlsruhe, Germany 3 Department of Engineering and Physics, Karlstad University, 65188 Karlstad, Sweden 4 Materials Theory Division, Department of Physics and Astronomy, Ångstro?m Laboratory, Uppsala University, 75120 Uppsala, Sweden 5 Department of Chemistry-Ångström Laboratory, Uppsala University, Box 538, SE-75121, Uppsala, Sweden 7 University Grenoble Alpes, CEA, IRIG-MEM, 38000 Grenoble, France 8 Univ. Grenoble Alpes, CEA, Liten, 38000 Grenoble, France 9 Department of Fibers and Carbon, CANOE ? Platform for Composites and Advanced Materials, 16 Avenue Pey Berland, 33600 Pessac, France 10 Bernard Dumas, 2 rue de la papeteire, 24100 Creysse, France
Resume : Organic batteries have been attracting rapidly increasing interest in recent years owing to the great progress that has been achieved in the synthesis of advanced molecular structures, rendering the realization of truly sustainable high-performance batteries very well possible.[1?4] However, the path towards commercialization is still long and a series of challenges remains to be addressed, including amongst others improvable volumetric and gravimetric energy densities, the difficulties in synthesizing lithiated organic materials that can be reversibly release the lithium cations, the need for large amounts of conductive carbon in the electrodes, and, very generally, an in-depth understanding of the processes and reactions occurring.[1?4] In fact, one aspect that is frequently overlooked is that also organic active materials come as ?particles? rather than single molecules. Herein, a comprehensive analysis of tetra-lithium perylene-3,4,9,10-tetracarboxylate (PTCLi4) as an exemplary organic active material is provided, starting from an in-depth investigation of the de-/lithiation mechanism by merging theory and experiment towards an optimization of the electrode composition with the target to realize commercially relevant performance metrics. References  P. Poizot, F. Dolhem, J. Gaubicher, Current Opinion in Electrochemistry 2018, 9, 70.  B. Esser, F. Dolhem, M. Becuwe, P. Poizot, A. Vlad, D. Brandell, Journal of Power Sources 2021, 482, 228814.  P. Poizot, F. Dolhem, Energy Environ. Sci. 2011, 4, 2003.  Y. Lu, J. Chen, Nature Reviews Chemistry 2020, DOI 10.1038/s41570-020-0160-9.
Authors : Christina Toigo, Catia Arbizzani and Karl-Heinz Pettinger
Affiliations : Christina Toigo, Catia Arbizzani: Department of Chemistry ?Giacomo Ciamician?, Alma Mater Studiorum Universitá di Bologna, 40126 Bologna, Italy Karl-Heinz Pettinger: Technology Center for Energy, University of Applied Sciences Landshut, 94099 Ruhstorf, Germany
Resume : Due to the increasing demand of battery technology for applications in mobile and stationary devices, this is a fast-growing economic sector. Within the last decades, lithium ion batteries have been subjected to a continuous process of development and further improvement ? not only in terms of power and energy density, but also with focus on safety and sustainability. To overcome drawbacks concerning solvent-based manufacturing routes, new water-based routes are evaluated, using a variety of water-processable and therefore more sustainable materials. One promising alternative for fluoride-based binder polymers in battery electrodes is sodium alginate, which is a seaweed harvesting product. We have examined sodium alginate not only as bio-based binder for different applications in lithium and sodium ion battery electrodes, but also as an additive for the preparation of separators and as electrolyte in fuel cells. Sodium alginate offers a great bandwidth of possible engineering applications with high potential to improve existing systems both in terms of sustainability and biodegradability without cutting its performance. To conclude, bio-based sodium alginate is a suitable alternative for a big variety of applications in the battery sector. It is a polymer offering low environmental impact, good biocompatibility, and no negative influence on human health. Additionally, sodium alginate comes up with comparable results in terms of mechanic and electrochemical performance.
Authors : Rodrigo P. Carvalho, Cleber F. N. Marchiori, Daniel Brandell, C. Moyses Araujo
Affiliations : Department of Physics and Astronomy, Uppsala University; Department of Engineering and Physics, Karlstad University; Department of Chemistry, Uppsala University; Department of Engineering and Physics, Karlstad University
Resume : Electrical energy storage (EES) devices have staged important technological revolutions in the past years, with special attention given to Li-ion batteries (LIBs). However, novel socioeconomical paradigms have urged for environmentally friendly and sustainable alternatives regarding these technologies. In this context, organic materials have attracted attention as potential candidates to pave the way toward the achievement of truly green batteries. They offer several advantages like cost efficiency, sustainability, synthesis from renewable or feedstock and tunable properties. Nonetheless, hindrances related to cyclability and energy density need to be solved before the achievement of such alternative technologies. In this study, we present one possible way to accelerate the discovery of novel organic electrodes, with special focus given to LIBs positive electrodes. To explore the almost limitless organic universe, however, novel methodologies were needed. Based on a combination of density functional theory (DFT) and machine learning approaches we have developed an Artificial Intelligence (AI) algorithm capable of predicting the battery open circuit voltage (OCV) (V vs. Li/Li ). To fuel the AI, two different databases have been developed: a small set of predicted molecular crystals following an interplay between DFT and an evolutionary algorithm[3,4]; a larger set of more than 26000 unique molecules with redox properties extracted from DFT. The rendered AI-kernel relies solely on a textual representation of molecules to obtain the OCV, which allows a fast and efficient assessment of larger materials libraries. Thereafter, a high-throughput screening was performed in 20 million molecules following a capacity (mAh/g) ? OCV (V vs Li/Li ) selection to find suitable electrode candidates, resulting in about 1540 cathodes. As the final part of this screening, new DFT calculations were performed for the selected molecules with a two-fold goal: to validate the AI-kernel performance and to further filter the candidates list. This process led to the discovery of about 500 promising molecules for cathode compounds, with some exhibiting theoretical energy densities superior to 2000 Wh/kg. Moreover, the AI-kernel accurately identified common molecular characteristics that lead to such higher-voltage electrodes and pointed out an interesting donor-accepter-like effect that may drive the future design of cathode-active materials. References:  P. T. Brown and K. Caldeira, Nature, 2017, 552, 45?50.  S. E. Burkhardt, J. Bois, J. M. Tarascon, R. G. Hennig and H. D. Abruña, Chemistry of Materials, 2013, 25, 132?141.  R. P. Carvalho, C. F. N. Marchiori, D. Brandell and C. M. Araujo, ChemSusChem, 2020, 13, 2402?2409.  R. P. Carvalho, C. F. N. Marchiori, V.-A. Oltean, S. Renault, T. Willhammar, C. Pay Gómez, C. M. Araujo and D. Brandell, Materials Advances, 2021, 2, 1024?1034.
Authors : Rebecca Grieco* (1), Nagaraj Patil (1), Antonio Molina (1), Jesús Palma (1), Marta Liras (2), Jaime S. Sanchez (3) and Rebeca Marcilla (1)
Affiliations : Electrochemical Processes Unit, Photoactivated Processes Unit, IMDEA Energy, Avda. Ramón de la Sagra 3, 28935 Móstoles, Spain, Chalmers University of Technology, Chalmersplatsen 4, 412 96 Göteborg, Sweden
Resume : The development of sustainable batteries is becoming more and more important to accomplish clean energy goals. However, most of the current batteries, still based on inorganic electrodes that contain scarce and/or toxic elements, so hardly meet these sustainable requirements. In contrast, organic electrodes based on abundant elements are promising alternatives. Among them, conjugated microporous polymers (CMPs) have gained increasing attention due to their extended ?-conjugation and permanent microporosity. Recently, our group reported the advantages of anthraquinone-based CMPs (named IEP-11) as high performing cathode for Li-ion batteries . Being aware of the safety issues associated to Li-ion batteries and of the scarcity of Li resources, we went a step forward by applying our polymer electrodes in safer and more sustainable aqueous batteries. Here, we compare our porous IEP-11 polymer with the state-of the art linear polymer (PAQS) in a polymer || Ni(OH)2 battery configuration using alkaline electrolyte (1M and 10 M KOH). IEP-11 polymer exhibited much better performance over cycling due to its robust 3D porous structure which avoids the typical dissolution problem faced by linear polymers in low concentrated electrolytes. Due to the low cyclability of Ni(OH)2 in concentrated electrolytes, we substituted Ni(OH)2 by a novel NiCoMnSx cathode and the resultant battery outperformed most of the state-of-the-art alkaline batteries in terms of energy and power density . References: (1a) Adv. Funct. Mater. 2020, 30 (6), 1908074, (1b) ACS Energy Lett. 2020, 2945?2953, (2) Manuscript in preparation.
Authors : Marina Navarro-Segarra (1), Joseba M. Ormaetxea (1), Neus Sabaté (1,2) and Juan Pablo Esquivel (1,3,4)
Affiliations : (1)Instituto de Microelectrónica de Barcelona, IMB-CNM (CSIC), C/ dels Til?lers sn, Campus UAB, 08193 Bellaterra Barcelona, Spain; (2) Catalan Institution for Research and Advanced Studies (ICREA), Passeig Lluís Companys 23, 08010 Barcelona, Spain; (3)BCMaterials, Basque Centre for Materials, Applications and Nanostructures, UPV/EHU Science Park, 48940 Leioa, Spain; (4) IKERBASQUE, Basque Foundation for Science, 48009 Bilbao, Spain
Resume : Batteries have become an essential power source in many areas, due to their capability to deliver high energy densities in a portable manner. Furthermore, its demand is forecast to increase exponentially with the blooming of devices for the Internet-of-Things (IoT). Although secondary batteries seem to be the more suitable solution, many applications in which logistics requirements make battery recovery very unlikely, rely on the primary non-reusable option. In many of those cases, batteries must be adapted to the system size and form factors, making the recycling process even more challenging, thus aggravating the environmental impact associated with the generation of waste electrical and electronic equipment (WEEE). Furthermore, a close look at their life cycle reveals that they follow an obsolete linear model of production, consumption and disposal, which relies on scarce non-renewable resources and materials, contributing significantly to the ecosystem degradation. The current situation sets a great opportunity for re-thinking the battery paradigm by placing sustainability at the heart of the process. This talk will introduce a primary battery concept that turns around the typical battery life cycle. Eco-design principles have been applied since the device conception to explore new material applications, employ low energy consuming fabrication methods and customize energy supply while reducing environmental stress. The identification, optimization and application of new materials represented a pivotal step in this work. Abundant plastic-free, non-toxic materials are selected for all battery parts, from the substrate to the active redox species. Carbon-based current collectors are generated via Laser-Induced Graphene (LIG) over a pre-treated cardboard surface. Bio-polymer matrices synthesized from naturally occurring polymers, such as cellulose or alginate, are used to create hydrogels that retain the electrochemically active species and as ion exchange membrane. Their unique composition would allow batteries to follow alternative end-of-life scenarios, such as being recycled with paper/cardboard or being composted. This battery concept represents a feasible pathway to develop truly sustainable portable energy storage devices for application sectors such as smart packaging and precision agriculture.
Authors : Christiane Groher 1,3, Daniela Fontana 2, Marcus Jahn 1, Egon-Erwin Rosenberg 3, Jürgen Kahr 1
Affiliations : 1 AIT Austrian Institute of Technology GmbH, Center for Low-Emission Transport, Electric Drive Technologies, Giefinggasse 2, 1210 Vienna, Austria, firstname.lastname@example.org; 2 FAAM Research Center, R&D Electrochemical, FIB s.r.l., Area Sviluppo Industriale, S.S. Via Appia 7bis km 15400, 81030 Teverola (Ce), Italy; 3 Vienna University of Technology, Institute of Chemical Technologies and Analytics, Austria, Getreidemarkt 9/164 AC, 1060, Vienna, Austria, email@example.com
Resume : In recent years a growing demand for environmentally friendly transportation led well known car producers to introduce electric powered vehicles (EV) to their fleet. This development caused a growing demand for lithium-ion batteries (LIB) with high energy density and long cycle life, leading to the development of high voltage and high capacity electrode materials. However, their performance is still limited by fast decomposition of electrolyte components at high currents or beyond a defined voltage threshold, beyond 4.5V. There is a large number of researchers devoting their work to improve lifetime and safety of lithium ion battery (LIB) cells. One way to achieve these goals unfolds by adding functional organic compounds as additives to carbonate-based electrolytes. Vinylene carbonate (VC) and fluoroethylene carbonate (FEC) for SEI formation are common additives which are commercially used in state-of-the-art electrolytes. However, a new chemical class of additives has shown to address other aspects of cell degradation. Electrolyte decomposition stemming from harmful substances can be interrupted with scavenging additives. The conducting salt lithium hexafluorophosphate (LiPF6) for instance decomposes and reacts with water to yield hydrofluoric acid which further leads to the degradation of the SEI or causes damage to the cathode material. This reaction path can be interrupted at different stages by scavenging water, hydrofluoric acid or an intermediate species by adding additives, that prevent parasitic components from reacting and lead to an improvement of the state-of-health (SOH) in batteries. In this work, Tris-(Trimethylsilyl) phosphite (TMSP) was used as additive for the scavenging of hydrofluoric acid and together with a newly developed operando GC-MS method, the decomposition reactions during battery cycling were investigated. This was used to analyze the gas species evolving from NMC532/Li EL-Cells with and without TMSP during overcharge- and fast-charging-experiments. Gaseous decomposition products play a key role in understanding degradation reactions, therefore, the knowledge gained from these experiments assist in uncovering the mechanistic background of the additive impact and has a supporting role in finding new additives for LIBs. The author gratefully acknowledges the FFG (Austrian Research Promotion Agency) for funding this research within project No. 879613.
Authors : F. Lambert (1,2), Y. Danten (3), C. Gatti (4), M. Bécuwe (1,5,6), A.A. Franco (1,5,6,7) and C. Frayret (1,5,6)
Affiliations : 1) Université de Picardie Jules Verne, Laboratoire de Réactivité et Chimie des Solides, UMR 7314 (LRCS), 15, rue Baudelocque, 80000 Amiens, France; 2) French Environment and Energy Management Agency (ADEME), 20, avenue du Grésillé- BP 90406 49004 Angers Cedex 01, France; 3) Institut des Sciences Moléculaires, UMR CNRS 5255, 351, Cours de la Libération, 33405 Talence, France; 4) CNR SCITEC, CNR Istituto di Scienze e Tecnologie Chimiche "Giulio Natta", Sede Via C. Golgi, 19, 20133 Milano, Italy; 5) Réseau sur le Stockage Electrochimique de l?Energie (RS2E), FR CNRS 3459, HUB de l?Energie, 15, rue Baudelocque, 80000 Amiens, France; 6) ALISTORE-European Research Institute, FR CNRS 3104, HUB de l?Energie,15, rue Baudelocque, 80000 Amiens, France; 7) Institut Universitaire de France, 103, boulevard Saint Michel, 75005 Paris, France.
Resume : In recent years, interest in the development of organic electrodes for batteries with materials extracted from biomass rather than using synthetic routes has intensified, with the aim of making energy storage more environmentally friendly. To accelerate and simplify the search for promising compounds as potential electroactive materials in these sustainable batteries, computational procedures may be employed to complement the experimental approaches in view of guiding the selection of most promising backbones and functionalizing groups or to understand in detail the electrochemical mechanisms. The success of researches in this area relies on the discovery of performant compounds or materials, which can be assisted from both predictive power with atomic and mesoscale resolution and accurate scrutinization of structure property-relationships. With the aim of delivering unique insight and understanding of this class of materials, Density Functional Theory (DFT)  and Coarse-Grained Molecular Dynamics (CGMD) [2,3] can be partnered with experimental synthesis and characterization tools. In such a global approach, the panel of properties accessible encompass structure, slurry viscosity, evaporation, electrode calendering, diffusion and electrochemical features. Through molecular DFT calculations, the systematic exploration of modified or completely new compounds can be conducted either through screening of the effect of functionalization, isomerization or substitution inside a family or across several series of backbones or even through redox centers modulation. This tool can confirm or infirm chemical intuitions at a first glance, therefore helping to identify or even to engineer most suited candidates thanks to design and optimization considerations. Besides, based on the accurate electronic structure examination, structure?activity relationships can be established to unveil the origin of the redox potential magnitude as a function of both structural features and complexation effects. On the other hand, periodical DFT and CGMD calculations may assist in particular the comprehension of intercalation features and electrode manufacturing in the context of real-life experiments, respectively. A glimpse of the challenges and complementary approaches encountered in this research area will be presented through the consideration of a few case studies.  F. Lambert, Y. Danten, C. Gatti, C. Frayret, Phys. Chem. Chem. Phys., 2020, 22, 20212-20226.  A. A. Franco, A. Rucci, D. Brandell, C. Frayret, M. Gaberscek, P. Jankowski, P. Johansson, Chem. Rev. 2019, 119, 4569?4627.  M. Chouchane, A. Rucci, T. Lombardo, A. C. Ngandjong, A. A. Franco, Journal of Power Sources, 2019, 444, 227285.
Authors : Ashish Raj, Satyannarayana Panchireddy, Bruno Grignard, Christophe Detrembleur, Jean-Francois Gohy*
Affiliations : Institute of Condensed Matter and Nanoscience (IMCN), UCLouvain, Place L. Pasteur 1, 1348 Louvain-la-Neuve, Belgium. Center for Education and Research on Macromolecules (CERM), CESAM Research Unit, University of Liège, allée du 6 août, Building B6A, Agora Square, 4000 Liège, Belgium
Resume : The solid-state battery has drawn a huge interest with its motive to overcome the issues and challenges faced by batteries using conventional liquid electrolytes. The novel idea of using green approaches or bio-based sources for lithium batteries excites many researchers due to their eco-friendly, less carbon footprint in its synthesis and recycling at the end. In this work, we report a full bio-based solid-state electrolyte based on functionalized carbonated soybean oil (CSBO) obtained from the naturally occurring epoxidised soybean oil (ESBO) using CO2 and biomass. CSBO shows remarkable adhesive properties as characterized by rheological measurements owing to its bigger chains bearing multifunctional cyclic carbonates. LiTFSI salt reinforced CSBO was characterized following standard electrochemical measurements exhibiting ionic conductivity to ~10-3 S cm-1 at 100 oC and 10-5 S cm?1 at room temperature. The electrochemical window for this electrolyte was obtained to be 4.8 V (vs. Li/Li ) and transference number up to 0.31, allowing it to be explored for high voltage cathodes. CBSO shows stable stripping and plating behaviour for longer cycles making it a good candidate for higher coloumbic efficiency electrolyte batteries. We also demonstrated the galvanostatic charge-discharge of LiFePO4 (Lithium Ferrrophosphate, LFP) with CSBO electrolytes delivering the gravimetric capacity of 124 mAhg-1 and 150 mAhg-1 appx. at ambient room and higher temperature respectively. Therefore, our study provides a promising direction of developing bio-based solid electrolytes to facilitate progress in sustainability, cost-effective and safe manner to create a solid-state lithium-ion battery for global utilization.
Poster Session : Helmut Ehrenberg
Authors : N. Ohannessian* (1) (2), C. Schneider (1), T. Lippert (1) (2).
Affiliations : (1) Laboratory for Multiscale Materials Experiments, Paul Scherrer Institut, 5232 Villigen PSI, Switzerland; (2) Laboratory of Inorganic Chemistry, Department of Chemistry and Applied Biosciences, ETH Zürich, 8093 Zürich, Switzerland * lead presenter
Resume : The apparent ease to prepare films by pulsed laser deposition (PLD) with a complex stoichiometry hides the underlying complex and simultaneously occurring phenomena in the laser-induced plasma. Often the film growth suffers from the competition between light and heavy elements in the expanding plume with heavy species possessing a high kinetic energy as compare to lighter species. As a result, there are significant differences in the arrival time to the substrate causing compositional spatial deviation in both the plasma plume and the film. For a targeted growth of films with a complex composition, it would be therefore highly desirable to have a more detailed understanding of the scattering process and plasma chemistry that take place inside the laser-induced plume. The deposition of Li containing materials to prepare Li-ion battery thin films has been widely performed by PLD. Due to the small mass of lithium, Li-containing materials often undergo this competition with heavy elements detrimental to film growth and composition, respectively. The main goal of this research is to perform detailed elemental, spatially and time resolved optical and mass spectroscopic measurements of PLD processes of Li-containing materials such as LiMn2O4. Investigating the mechanisms involved such as the plasma plume formation, expansion, and subsequent film growth will benefit lithiated material manufacturing. Establishing more predictable deposition boundary conditions with respect to film growth will help to improve battery material performances.
Authors : George Zardalidis, Filippos Farmakis
Affiliations : Department of Electrical and Computer Engineering, Democritus University of Thrace, Greece
Resume : Li ion transport mechanisms in the bulk of electrolytes, for applications in Li ion batteries, however complex they might be, are well documented and dictated by the interactions between the solvent and each ionic species. However, when two different phases meet, namely the electrode material and the electrolyte, a plethora of different phenomena come into play. These phenomena set the limitations on the engineering for safety and efficiency of a Li ion battery. The trend towards solid state electrolytes is considered the most effective safety-wise but the solid to solid contact between the electrode and the electrolyte places a tremendous barrier in the smoothness and uniformity of Li diffusion through the interface. Low molecular weight poly(ethylene oxide) (PEO) based electrolytes offer remarkable conductivity of ~10-4 S/cm at room temperature but present no mechanical stability. On the other hand, solid polymer electrolytes (SPEs) present the necessary elastic properties but the contact with the electrodes is problematic, since they cannot comply to the roughness or porosity of the electrodes and the contact area is considerably reduced. Many ways to conformally comply the surface of the electrodes with that of the SPE have been studied, such as in situ polymerization, use of self-assembled block copolymer PEO molecular layers and high molecular weight PEO casting. A liquid or viscus electrolyte could mediate the interface between SPEs and electrodes optimizing the contact area. Especially in the case of lithium metal electrodes, when the electrolyte comes into contact with lithium, chemical or electrochemical reactions lead to the formation of an interphase (solid electrolyte interphase ? SEI) that passivates the electrode and protects the electrolyte from further consumption. This work is focused on the investigation of the behavior of PEO based liquid or viscus electrolytes in contact with lithium metal anodes. In this study we try to understand the formation of the composite layer and the evolution of SEI over time as well as the resultant change in conductivity. For this purpose, different electrolytes placed into contact with lithium electrodes and their behavior was monitored through impedance spectroscopy. All the systems studied, were prepared by solvation of bis(trifluoromethane) sulfonimide lithium, LiN(SO2CF3)2 (LiTFSI). The polymers used as solvents for the salt were the following: hydroxy poly(ethylene glycol) with molecular weight 550 g/mol (PEG550), dimethyl poly(ethylene glycol) with Mw 250 g/mol (PEG250-dME), a blend of 30% w/w poly(methyl methacrylate) PMMA (Mw 100 kg/mol) with 70% w/w PEG550 (PMMA/PEG550) and a blend of 30% w/w PMMA with 70% w/w dimethyl poly(ethylene glycol) with Mw 1000 g/mol (PMMA/PEG1k-dME). Al the electrolytes have been mixed with the salt in the same ratio of r = [Li ]:[EO] = 0.055 ([EO]:[Li ] = 18.2:1). For comparison a carbonate electrolyte of ethylene carbonate and diethyl carbonate LiTFSI 1M (EC/DEC) has also been studied. All the electrolytes were enclosed in symmetric cells with lithium electrodes, with the assembly performed in argon-filled glove box with levels of O2 under 100 ppm and ?2? under 1 ppm. The systems of low molecular weight, PEG electrolytes are in liquid state while the blends with PMMA are viscus at room temperature. By comparison of PEG550 and PEG250-dME it is seen that the formation of the SEI is a fast process which is completed during the first hours, from the first contact with the lithium metal electrodes. A second phase is observed that it is attributed to the formation of inorganic lithium salt compounds that evolve in a slower rate of days. The PEG550 shows a significant electrolyte decomposition, due to the formation of a weak SEI while at the same time a thick inorganic phase hiders Li ion transport. In contrast the PEG250-dME electrolytic system shows a stability sourcing from the formation of a SEI that is mechanically stable and a thinner inorganic layer. The comparison of the viscus electrolytes of blended PMMA and PEG follow a similar behavior. The PMMA/PEG550 electrolyte shows the characteristic reaction of PEG550 with the lithium metal leading to a SEI formation. The SEI dynamic behavior resembles that of PEG550 with the characteristic frequencies being very close for the two systems, indicating a similar SEI environment. The PMMA/PEG1k-dME shows a different dynamic behavior in comparison to the PEG250-dME system, with the characteristic frequency being more than an order of magnitude lower, probably due to the higher molecular weight of the PEG. It is interesting to note that by comparing the resistances of the SEI between the two blends there appears a remarkable similarity in their time evolution, which probably indicates that PMMA also contributes to the formation of the SEI. The low viscosity of low molecular weight PEG electrolytes allows for an effective electrode wetting and conformal matching of solid polymer electrolyte to electrode surfaces, while at the same time methoxy chain termination limits the molecule reactivity with lithium and promotes the formation of a stable SEI. The prospect of this work is to bridge electrode and SPE materials mechanically as well as electrically using low viscosity electrolytes. In order to determine the behavior of various PEO based electrolytes and their ability to passivate the anode materials, improve the solid to solid contact, achieve better diffusion for Li and extend cyclability of the lithium ion cells.
Authors : B. Sievert1, M. Nojabaee1, I. Nicotera2, A. Arenillas3, N. Wagner1, K. A. Friedrich1
Affiliations : 1. German Aerospace Center / Institute of Engineering Thermodynamics, Electrochemical Energy Technology, Stuttgart, Germany 2. University of Calabria, Calabria, Italy 3. Agencia Estatal Consejo Superior de Investigaciones Cientificas, Madrid, Spain
Resume : Within the BMBF-funded international collaborative project INNENERMAT, the partners are developing flexible batteries and supercapacitors and proof-of-concept for the hybridization of mentioned systems in a multidisciplinary approach. Safe and environmentally friendly high-performance cathodes and anodes, gel and polymer electrolytes and smart carbon textile electrodes for flexible energy storage cells are realized through the development of advanced functional materials. Here the primary results on the development of lithium sulfur battery component within INNENERMAT project are presented. Carbon xerogels with different size of feeder pores were developed and tailored with defined amount of microporosity to immobilize sulfur species within the cathode . Preparation and associated effect on the electrochemical performance of such electrodes is investigated. To this end, the influence of preparation method such as grinding, handling, stability and viscosity on the wet coating process as well as on the quality of cathode sheet in terms of defects and flexibility is discussed elaborately. Furthermore, the infiltration of sulfur into the carbon matrix is particularly studied for this innovative class of carbon materials . In order to immobilize the polysulfide anions, the strategy adopted in this work is that of employing innovative single ion conductor-solid polymer electrolytes (SLIC-SPEs), providing suppressed anion mobility. For this purpose, lithiated Nafion-based nanocomposite membranes were synthesized via dispersion of nano-additives bearing suitable functional groups . Two nanostructures have been investigated: graphene oxide (GO) and Nanoscale Ionic Materials (NIM) functionalized membrane. The presence of nanoparticles in the polymeric matrix is of great interest not only due to the significant gains in thermal and mechanical stability, but also the consequential barrier effect, hindering the diffusion of polysulfides and enhancing the cyclability of the cell. The implementation of these kinds of membranes have already been successfully demonstrated for lithium ion battery cathode and in the presented work the incorporation in the lithium sulfur system is showcased.
Authors : Anders Brennhagen, Carmen Cavallo, David S. Wragg, Ponniah Vajeeston, Anja O. Sjåstad and Helmer Fjellvåg
Affiliations : Centre for Material Science and Nanotechnology, Department of Chemistry, University of Oslo, PO Box 1033, Blindern, N-0315, Oslo, Norway
Resume : Na-ion batteries (NIBs) could be a good alternative to Li-ion batteries (LIBs) due to the large abundance and availability of sodium resources. The search for good anode materials is one of the big challenges since graphite, which is the most common anode material for LIB, does not work well in NIBs. We are developing Bi2MoO6 as an anode material for NIBs, and will explain the main cycling mechanism. By utilizing a combination of conversion and alloying reactions, the material achieves high capacity while still maintaining a decent cycling stability. The complex cycling mechanism also makes it an interesting and challenging material to characterize during cycling. In this poster, we present high quality operando XRD data of the material during several cycles, acquired in the home lab. The data clearly shows that the reversible alloying reaction of Bi-metal to cubic Na3Bi gives the main capacity contribution, after the initial conversion reaction. This indicates formation of nanocrystalline Bi-particles, as nanocrystalline Bi-metal has shown the same reaction mechanism while microcrystalline Bi instead forms the hexagonal phase of Na3Bi. The molybdenum goes into an amorphous matrix that is only partially electrochemically active. The phases formed with molybdenum during cycling are difficult to characterize, due to their amorphous nature, and remain an unsolved mystery.
Authors : TOSIN PAESE Lucas, CHATAIN Sylvie, GUENEAU Christine
Affiliations : Université Paris-Saclay, CEA, Service de la Corrosion et du Comportement des Matériaux dans leur Environnement, 91191, Gif-sur-Yvette, France
Resume : Lithium-ion batteries (LIBs) are one of the most promising technologies for electric energy storage. They have some advantages over conventional rechargeable systems, such as a high output voltage and low self-discharge. Being the bottleneck of its performance, the cathode of LIBs are of great interest of study, more specifically in reducing the cobalt content, a mineral expensive and toxic. Here, we use the CALPHAD (CALculation of PHAse Diagram) approach to obtain a thermodynamic description of typical cathode based on NMC materials (layered host compounds with nickel, manganese and cobalt). Combining crystallography, phase diagrams and thermodynamic information, we develop a model with Gibbs energy functions for every phase that can appear in the cathode during battery operation. This model allows us to calculate important properties such as cell voltage, release of oxygen and phase stability. At a first moment, we focus in the Li-Ni-O system, typical of LIBs that use LiNiO2 as host compound. Even though this compound provides a very high theoretical energy density and has no cobalt, there are issues regarding its synthesis and it usually presents a considerable loss of its capacity after the first charge due to irreversible changes in its crystalline structure. We propose an ionic model, where we can provide information on the oxidation degree of nickel atoms during battery operation. We also assess the system in temperatures higher than room temperature, where we accomplish a better comprehension on how the synthesis conditions affect the host compound. Finally, as a future work, we extend the model to systems representative of NMC cathodes. The NMCs with equal amounts of each transition metal are very stable as lithium deintercalates over battery charging. However, the automobile industry demands LIBs with increasingly higher capacity, which is possible by adding more nickel in the host structure and losing some structure stability as counterpart. We use the model to sweep over a wide range of NMC compositions in order to find optimal ones in terms of performance, safety and stability.
Authors : Mario Samperi, Gianluca Leonardi, Antonino Brigandì, Vincenzo Antonucci, Claudia D?Urso
Affiliations : For all authors: CNR-ITAE ? Via Santa Lucia sopra Contesse, 5 ? 98125 Messina
Resume : Ion conductive ceramics play an important role in industries and manufacturers due to their wide applications on energy storage devices. Many synthesis approaches to prepare ceramics have been developing rapidly in the few decades. One of the most simple and easy ways to prepare ceramics was using the solid-state reaction method and varying calcinated temperatures. In this works, we developed ion conductive ceramics, microstructure analysis by XRD and SEM, and conductivity measurements. Our important finding was an improvement in the performance of microstructures, crystallinities and conductivities by changing calcinated temperatures. The raw materials of Na3.3Zr2Si2PO12 were wetly mixed for 24 hours and were dried overnight. Na3.3Zr2Si2PO12 powders were then calcined at three different temperatures, that are 1150°C, 1175°C, 1200°C, and 1225°C for 12 hours. The calcined powders were compacted at 250 MPa and then were sintered at 1100°C for 10 hours. On the pellets obtained, EIS measurements were carried out to determine the ion conductivity.
Authors : F. Dumitrache 1, C. Fleaca* 1, D. Craciun1, L. Gavrila-Florescu 1, E. Goncearenco 1, I.P. Morjan1, M. Buga 2, A.Spinu-Zaulet 2, C.Ungureanu 2, G. Prodan 3
Affiliations : 1 - National Institute for Laser, Plasma and Radiation Physics -NILPRPR, Lasers Department, 409 Atomistilor Street, Magurele-Bucharest, Romania 2 - National Research and Development Institute for Cryogenic and Isotopic Technology - ICSI- Rm. Valcea, ICSI Energy Research Department, Uzinei Street No. 4, Post code 240050, Rm. Valcea, Romania 3 - "Ovidius University" of Constanta , Mamaia Bd, no. 124, Constanta, Romania
Resume : Laser pyrolysis in a flow reactor designated for silicon nanoparticles has been used to synthesize composite nanostructure having distinct Si and Sn nanocrystals, aiming to obtain a nanomaterial with potential high performances for Li intercalation in anodes for the corresponding rechargeable batteries. Particularly, silane gas act in these configuration with a double role: Si precursor and reaction sensitizer (laser energy absorber). In this study we intended to analyse the structural and morphological changes of resulted composite nanostructure by progressively increasing the Sn precursors (Sn(CH3)4 vapors) flow, up to 22 sccm in the reactive mixture containing a constant SiH4 flow, 20 sccm. Thus, to generate nanoparticles having a low degree of agglomeration, the laser beam was focused at 1.3 mm together with the reactive mixture dilution with Ar and its flow was adjusted in order to keep the same total mixture flow (120 sccm). The as synthesized powders show distinct Si and metallic Sn beta phase nano-crystallites after XRD analysis. Also, the crystalline domain of Sn phase tend to increase with Sn(CH3)4 flow increasing. TEM investigations revealed distinct nanocrystals in the same NPs agglomeration: The mean Si crystal size are the lower (10 nm mean size) and Sn are the bigger one (up to 30 nm). The elemental composition was evaluated with EDX and the specific surface area by BET analysis. These NPs and their RGO composite will be evaluated for their electrochemical performances, including charge/discharge cyclability for performant Li ion anodes.
Authors : C. Fleaca* 1, F. Dumitrache 1, M. Buga 2, A.Spinu-Zaulet 2, C.Ungureanu 2, S. Enache 2, A.-M. Banici 1, E. Dutu 1, M. Dumitru 1
Affiliations : 1 - National Institute for Laser, Plasma and Radiation Physics -NILPRPR, Lasers Department, 409 Atomistilor Street, Magurele-Bucharest, Romania 2 - National Research and Development Institute for Cryogenic and Isotopic Technology - ICSI- Rm. Valcea, ICSI Energy Research Department, Uzinei Street No. 4, Post code 240050, Rm. Valcea, Romania
Resume : We report the synthesis of two different batches of Si nanoparticles (NPs) using laser pyrolysis of silane, their crystallite and nanoparticle size decreasing with the increasing of precursor gas speed by narrowing the cylindrical injector diameter. Thus, the bigger NPs (named SiA1) have mean XRD diameter around 30.7 nm, whereas for the smaller ones (SiA4) the mean value is 21.7 nm, values confirmed also by SEM analyses. For the composite synthesis, the Si NPs were ultrasonicated in the presence of water-dispersed graphene oxide (obtained by graphite oxidation with KMnO4/H2SO4 using a modified Hummer recipe), continuated by the mixture reduction in lyophilized dry state under H2 flow in a furnace or in liquid suspension with ascorbic acid followed by washing and lyophilisation. The resulted Si NPs and their powdered nanocomposites with RGO were used for the Li-ion anodes fabrication by adding conductive carbon black support (only for those based on raw Si NPs) and binders: poly(vinylidene fluoride) (PVDF) in N-methyl pyrrolidone (NMP) or carboxymetylcellulose (CMC)/styrene-butadiene rubber (SBR) in water and deposed by spraying or roll-to-roll techniques, respectively. They were subsequently tested in CR 2032 half-cells (having a Li foil as cathode) two electrode configuration (and also half-cell with three electrodes configuration - PatCell testing system) using LiPF6 salt dissolved in organic carbonates mixture (EC : EMC : DEC 3wt.% FEC). Depending of employed recipe and deposition technique their performances after 200 cycles at 1C were greatly different, for example for an electrode containing 15 wt% SiA1 NPs deposed by roll-to-roll: 734 mAh/g, whereas for an electrode with 15 wt% SiA4 NPs and deposed by spraying presented a 475 mAh/g capacity (also at 1C) after the same number of cycles in the conditions of their relatively high C black content (68 wt% for those withSiA1 and 80 wt% fo those with SiA4) . Also, the electrodes fabricated with Si NPs-RGO nanocomposites are under testing for cyclability performances. Preliminary electrochemical impedance analyses showed internal resistances between 4 ? 36? , whereas the cyclic voltammetry tests which were performed at 0.001 ? 3V, at 0.1 mV·s-1 scanning rate presented the expected the oxidation/reduction peaks in the region up to 0.75 V.
Authors : Raul Rubio1*, Javier Durantini1, Daniel Heredia2, Edgardo Durantini2, Luis Otero1, Miguel Gervaldo1.
Affiliations : 1. IITEMA-CONICET Departamento de Química, Universidad Nacional de Río Cuarto-CONICET, Córdoba, Argentina; 2. IDAS-CONICET Departamento de Química, Universidad Nacional de Río Cuarto-CONICET, Córdoba, Argentina.
Resume : Renewable energy sources, such as solar radiation, are alternatives to supplant fossil fuels. However, because of the variability in time as well as geographic distribution, devices to store the generated energy are needed. Supercapacitors can store the energy generated by other energy sources and deliver it when necessary. There are two types of supercapacitors: electrostatic double layer (EDLC) and pseudocapacitors (PSC). PSC store energy by faradaic reversible redox processes (oxidation-reduction) that occur within the electrode material, being this phenomenon known as pseudocapacitance. Until now metal oxides, metal hydroxides and organic polymers have been used in PSC. Organic polymers present high specific energy and power, high conductivities and are flexible. However, most of these organic polymers are synthetized by complex chemical methods involving several steps which are expensive and also generate waste. A strategy that can be used in the deposition of organic polymers is the electropolymerization. Electropolymerization is a very versatile procedure to construct organic films over metallic contacts, or over transparent conducting oxides. By electing the correct polymerization group and the correct desired functionality, a significative number of monomers can be designed and synthetized to generate polymers. In this work we present the electrochemical formation and characterization of porphyrin films obtained by electrochemical polymerization. The used porphyrin monomers have two carbazole and two triphenylamine electroactive groups, which were chosen to undergo electrochemical initiated radical coupling that promotes the formation of polymeric structures. Also, two central hydrogen atoms were substituted with different central metals (Zn (II), Co (II), Cu (II)). The monomers and the electrogenerated films were characterized by cyclic voltammetry, UV-vis spectroscopy, AFM, SEM and Electrochemical Impedance Spectroscopy (EIS). Because of the reversible oxidation-reduction processes involving the porphyrin macrocycle, the dicarbazole and the tetraphenylbenzidine groups present in the polymeric structure, it was expected a pseudocapacitive behavior that would make the porphyrin films adequate for their use as active material in the construction of supecapacitors. The porphyrin films were characterized by charge-discharge cycles at different current densities. The discharge and charge curves were nearly mirror images, indicating a fast and reversible electron exchange. The pseudocapacitive electrode materials exhibited capacitances as high as 201 F/g at a current density of 2 A/g. These high capacitances demonstrate that the porphyrin films are promising materials for energy storage applications where a high discharge-recharge rate is needed.
Authors : Athanasia Kostopoulou , Konstantinos Brintakis , Dimitra Vernardou , Emmanuel Stratakis [1, 3]
Affiliations :  Institute of Electronic Structure and Laser, Foundation for Research and Technology - Hellas, Heraklion, 71110, Crete, Greece;  Department of Electrical & Computer Engineering, School of Engineering, Hellenic Mediterranean University, Heraklion, 710 04, Crete, Greece;  Physics Department, University of Crete, Heraklion, 710 03 Crete, Greece
Resume : Metal halide perovskites have been recently proposed as promising anode materials for energy storage applications.1,2 Despite their quite important electrochemical characteristics, all the perovskite-based anodes are synthesized at high temperatures (90?150 °C) and with reaction durations of the order of tens of hours. In this work, we present perovskite materials synthesized with room temperature, simple and fast approaches for high-performance and stable electrodes for Li-air batteries. Hexagonally-shaped nanocrystals capped with ligands3 and ligand- free microcubes4 synthesized with re-precipitation based protocols will be compared according to their storage capacity and stability. Specifically, it is shown that the electrodes incorporating the ligand-free microcubes present outstanding stability at the same time with high specific capacity compared to the ligand-capped nanoparticulate system. These could be attributed to the high crystal quality of the materials and thus enhanced electrical conductivity, even under operation with an aqueous electrolyte. The large interfacial area between the perovskite material and the electrolyte along with the increase of the active sites on the exposed microcubes facets favor the Li ion intercalation. In addition, the absence of capping ligands contributes further to the enlargement of contact area, and facilitates the ion penetration compared to ligand capped nanocrystals. The good crystallinity of the microcubes enhances the Li-ion intercalation and the electron transportation. The microcubes performance is the best among all the anodes utilizing metal halide perovskite nanostructures, reported to date. References 1) Kostopoulou et al., Journal of Materials Chemistry A 2018, 6, 9765. 2) Kostopoulou A., Nanophotonics 2019, 8, 1607. 3) Kostopoulou A., Nanoscale 2019, 11, 882. 4) Kostopoulou A., Journal of Power Sources Advances 2020, 3, 100015. Acknowledgments: ?.?. would like to acknowledge the Hellenic Foundation for Research and Innovation (HFRI) and the General Secretariat for Research and Technology (GSRT) (under grant agreement No 1179) and K.B. EU H2020 Research and Innovation Program under Grant Agreement N820677 and Greek State Scholarships Foundation (IKY) through the operational Program «Human Resources Development, Education and Lifelong Learning» in the context of the project ?Reinforcement of Postdoctoral Researchers - 2nd Cycle? (MIS-5033021), for the funding.
Authors : Jong Ho Won
Affiliations : Department of Chemistry, Kookmin University, 77 Jeongneung-ro, Seongbuk-gu, Seoul 02707, Republic of Korea
Resume : Since lithium-ion batteries have become the mainstream energy storage devices, they have been used in various fields from mobile devices to electric vehicles, ESSs, and smart grids. As energy storage devices are used rather than generators even in larger and harsh environments, the demand for new energy storage devices with superior performance and stability has increased. The ideal structure proposed to satisfy this requirement would be a form in which lithium metal is used for the anode, sulfur is used for the cathode, and a solid electrolyte is positioned between both electrodes. The sulfur electrode has a theoretical capacity of at least five times greater than that of the conventional cathode, and it is expected to improve the performance of the energy storage device. However, the sulfur electrode showed disappointing results in existing experiments. When the sulfur electrode is combined with lithium, it spreads to all parts of the cell through a shuttle effect, which is not easily controllable and reversible. Early studies tried to prevent the shuttle effect by enclosing the sulfur electrode in a certain structure, but the sulfur dissolved in the liquid electrolyte, passed through the structure, and spread all over the cell, also the corrosive nature of sulfur accelerated that operation. When lithium was removed from sulfur, poor conductive sulfur was irregularly precipitated inside the cell, which seriously obstructs repeated charging and discharging and stable operation. Thus, later studies attempted to improve the structural reversibility and conductivity of the sulfur electrode by composing most of the electrode with sulfur and then mixing little additives, rather than trying to confine sulfur in the structure. In this study, the performance of the sulfur electrode was greatly improved by using the nano additive. The nano additive was a material with a highly controlled internal structure and high surface areas, such as graphene pomegranate pockets and nitrogen-rich carbon nanotubes. For example, the graphene pomegranate pocket provides conductivity to the sulfur electrode and has low interfacial energy with the electrolyte-sulfur solution, which makes the sulfur solution stable around. In addition, when removing lithium from the sulfur electrode, a stable reaction was induced by allowing the sulfur to be precipitated around the graphene pomegranate pocket. In addition, in the case of nitrogen-rich carbon nanotubes, a structure extending in one direction was uniformly stacked to provide excellent conductivity, and a sulfur solution was accommodated in a large internal space. In addition, the low interfacial energy with the sulfur solution allowed the solution to stay in the vicinity of the nitrogen-sufficient nanotubes, and a structurally reversible reaction was induced during charging and discharging. We verified stability through over 3000 charge/discharge reactions and achieved over 95% coulombic efficiency and theoretical capacity.
Authors : T. Tite, M. Buga, G.E. Stan, E. Matei, C. C. Negril?, A.C. Galca, M-C. Bartha, M. Baibarac
Affiliations : National Institute of Materials Physics, RO-077125 Magurele, Romania
Resume : On the main trends that drive energy storage development in our daily life is the rise of electrical devices, Internet of Things and battery-powered medical devices and implants. Despite its great success and mature custom manufacturing market, lithium ion batteries (LIBs) still need improvements in energy power density, speed charge capabilities, cost, and cyclic durability. In this context, in recent years, extensive efforts have been devoted to either improve lithium ion batteries (LIBs) by replacing commercial cathodes and anodes, improve electrolyte properties or designing new batteries without Lithium (Li) (e.g. Al, Mg, Na and Zn batteries) responding to the concern raised by the limited Li resources. Among new materials investigated in the literature, graphene and vanadium oxides (e.g. V2O5, VO2) are outstanding materials due to their unique physico-chemistry properties and their promises in both fundamental research and industrial field. Moreover, vanadium and carbon are sustainable elements sparsely distributed in the Earth?s crust, therefore abundant. There are several advantages to synthesize those materials, such as the unique open-layered structure of vanadium oxides (VOx), which could allow the easy insertion of various cations (e.g. Li and beyond Li ) and the synergetic effect of graphene due to its unique properties (e.g. good electrical conductivity, high surface area) for enhancing electrochemical properties of various materials. Electrochemical electrodes are generally prepared by a conventional coating method following by a drying process for several hours. By introducing physical vapor deposition (PVD) coating of the conductive current collector, we shall be suppressing this time-consuming step. As PVD deposition method, magnetron sputtering (MS) and pulsed laser deposition (PLD) has great potential for construction of electrode materials. Advantages include high adherence of films (which could guarantee long-term durability of electrochemical electrode); purity; easy engineering of the film properties by tuning the deposition parameters; control to atomic level the film thickness in contrast to spin-coating or dip-coating; good reproducibility of source material stoichiometry; MS has been proven to be a scalable technique at industrial level. Meanwhile, PLD technique has been proof an efficient technique for the construction of micro-batteries. Although various approaches have been used to synthesize vanadium oxides and graphene, the use of physical vapor deposition (PVD) as alternative method for energy storage devices is still quite unexplored. In this work, we report the synthesis of undoped and doped vanadium oxide polymorphs (e.g. V2O5, VO2(B)) and graphene by magnetron sputtering and pulsed laser deposition. Various substrates, such as Silicon, Aluminium, Nickel foil and Nickel foam were employed to deposit the thin films. The physico-chemical properties of the thin films were multi-parametrically surveyed by SEM, EDXS, Raman, GIXRD and spectroscopic ellipsometry. The electrochemical properties have been evaluated by cyclic voltammetry, and impedance spectroscopy and galvanostatic discharge?charge cycling in various electrolytes. Compared with the bare vanadium oxides, VOx/graphene electrodes exhibited enhanced electrochemical properties. Furthermore, we show the tailoring of the electrodes properties with defect (e.g. doping) engineering represent an excellent strategy to boost even further their performances. This work provides alternative approach to prepare electrode materials based on vanadium oxides and graphene for application in electrochemical energy storage.
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LCA : Stefano Passerini
Authors : Roland Hischier, Eleonora Crenna, Marcel Gauch, Rolf Widmer, Patrick A. Wäger
Affiliations : Empa, Technology and Society Laboratory, Lerchenfeldstrasse 5, 9014 St. Gallen, Switzerland
Resume : Poor availability of information on a commercial production scale and the diversity in modelling choices from various LCA experts makes evaluating the environmental impacts of Lithium-ion batteries (LIB) so far difficult and uncertain. In the same time, electric vehicles are gaining increasing room in the global market, since they are seen amongst the most promising solutions to cope with the growing concerns related to climate change and environmental pollution. But a successful evolution of the transportation sector towards electro-mobility depends ? among others ? also on the battery chemistry and technology, and its related environmental impacts. Hence, our activities over the past years aimed at contributing to the creation of flexible and transparent life cycle inventories (LCI) of LIB for background databases by means of a consequently modular approach that will be applicable in the future as a common framework to model new generations of LIB as well. In a first step, we focused for this on (i) compiling modular LCI datasets of current and near-future market LIB chemistries (i.e. NMC111, NMC811 and NCA chemistries) by using the most recent data from existing sources, and (ii) exemplarily assessing the environmental impacts of these three chemistries. Our assessment takes into consideration a wide range of impact categories, with a focus on climate change and the comparison with available literature of this sector.
Authors : R.Cayzac*, I.Sourmey, V.Kokoh, S.Sanchez, C.Joannin, C.Lepiller
Affiliations : SAFT a TOTAL company, Connected Energy division, Poitiers site, DT
Resume : Primary lithium is used in different markets like meters applications. Within these primary technologies some provide very high energy density like liquid cathode systems as Li-SOCl2. These cells (produced by several hundreds of millions per year worldwide) are designed to work 20 years and more, at small rate of discharge. They are characterized by a constant voltage during all the discharge with a fast polarization at the end of life of the cell. These features, voltage stability and high voltage value, are particularly appreciated by electronic manufacturers. The drawback is that during the discharge it is impossible to know what the discharge level of the cell is. Management of the system is then complicated beside a very generic date of obsolescence that can be based by the simulation of the lifetime of the battery in the application but not only. Saft as developed a meter life analysis technique which is providing key information to determine the best metering asset management strategy to Saft and other manufacturers of batteries. The Meter life analysis technique is based on the evaluation of health and ageing process of the meters by measuring and testing a representative sample of batteries collected from the field enables to identity the parameters influencing the ageing process (temperature, location, humidity, type of metering device) and the possible technical solutions to optimize battery life. Comprehensive facts & figures leads to fully informed decision making for asset maintenance and/or renewal leading to maximize time in the field.
Authors : Mashael Kamran, Marco Raugei, Allan Hutchinson
Affiliations : Oxford Brookes University, UK
Resume : The UK transport sector is approaching three major transitions: (1) a rapid growth of electrical mobility, and specifically light duty electric vehicles (EVs); (2) the deep decarbonization of the electricity grid, and (3) a possible gradual shift to shared mobility. This presentation analyses the interplay of these three transitions through a dynamic material flow analysis of lithium-ion battery (LIB) metals for electric vehicles and grid storage in the UK, and a consequential life cycle assessment (C-LCA) of the evolution of the entire light duty vehicle (LDV) fleet in the UK over the next three decades. A gradual phase-out of internal combustion engine vehicles (ICEVs) is assumed to take place, consistently with the UK government?s target to ban their sale by 2030. Also, rapidly increasing collection and recycling rates for EoL EV LIBs are assumed, and the co-evolution of the UK grid mix is modelled on National Grid?s ?Leading the Way? future energy scenario (FES). Results indicate that the shift from ICEVs to EVs, coupled to grid decarbonization and efficient closed-loop recycling of EoL EV LIB metals, can be very effective at curbing the sector?s demand for non-renewable primary energy and greenhouse gas emissions, despite a steadily growing demand for personal mobility. At the same time, though, the growing demand for LIB metals points to a potentially critical increase in resource depletion and toxicity impacts. However, the adoption of shared mobility, leading to a smaller overall LDV fleet, could keep the total net demand for critical metals in check, and hence significantly reduce the associated depletion and toxicity impacts.
Authors : Eleonora Crenna1, Mohammad Abdelbaky2, Alessio Tommasi3, Lilian Schwich4, Seyedeh Narjes Fallah5, Colin Fitzpatrick5, Bernd Friedrich4, Roland Hischier1, Jef Peeters2
Affiliations : 1 Technology and Society Laboratory, Empa, St. Gallen (CH); 2 Department of Mechanical Engineering, KU Leuven, Leuven- Heverlee (BE); 3 Gemmate Technologies, Buttigliera Alta - Turin (IT); 4 Institute for Process Metallurgy and Metal Recycling, RWTH Aachen University, Aachen (DE); 5 Department of Electronic and Computer Engineering, University of Limerick, Limerick (IE)
Resume : To guarantee a broader access to electric vehicles and in order to cope with growing concerns for climate change and resource depletion, the economic viability and environmental sustainability of batteries must improve. The Horizon 2020 EU-funded project Si-DRIVE aims at developing a next generation of Li-ion batteries by combining innovative cobalt-free chemistries and increased recyclability, al-lowing to increase their cost competitiveness. To ensure the overall economic and environmental sustainability of these new batteries in the context of a circular economy, a holistic systems-thinking approach is applied. Life cycle assessment is used to evaluate actions and targets already in the development stage. Strategies are developed to better align the design of Li-ion batteries with the repair, reuse, repurpose and recycling options consistent with circular economy objectives. Smart de-manufacturing systems are investigated to enable fully automated dismantling that will increase the safety, material recovery and economic viability of the end-of-life treatment of discarded batteries. In parallel, innovative metallurgy-based recycling processes for the battery components are investigated and validated to increase the direct reapplication of recycled material in the production of new batteries, while ensuring minimal environmental impacts.
Authors : Imen Karaoud1, Yassine Ben Belgacem1, Youssef Dabaki1, Chokri Khaldi1, Omar ElKedim2, Nouredine Fenineche3, Jilani Lamloumi1
Affiliations : 1Université de Tunis, ENSIT, LR99ES05, 1008 Montfleury, Tunisia. 2FEMTO-ST, MN2S, UTBM, UBFC, Belfort, France 3ICB-PMDM/FR FCLAB, UTBM, UBFC, Belfort, France
Resume : In the present work, we have studied the electrochemical properties of CaNi4.8M0.2 (M=Mg and Zn) type alloy used as an anode in nickel metal hybrid batteries. The CaNi4.8Mn0.2 alloy produced by mechanical alloying under an argon atmosphere has been widely studiedfor different milling times and ball to powder weight ratio, Retsch PM400 type ball mill was used. The different results show that the most encouraging electrochemical properties are obtained for a milling time of 40 hours and a ball to powder weight ratio of 8:1. On the basis of this study, we continued to characterize the CaNi4.8M0.2 (M= Mg and Zn) electrode electrochemically for the same optimal processing parameters (40h and 8:1). Several methods are used such as galvanostatic polarization and potentiodynamic polarization. The CaNi4.8Mg0.2 and the CaNi4.8Zn0.2 electrode are activated, respectively, during the fourth and the third cycle. The maximum discharge capacity is about 30 and 60 mAhg-1 at ambient temperature. On the other hand, a good correlation is observed between the evolution of the discharge capacity and the kinetic property of the electrode during a long cycling.
Authors : Ersoy, H.*(1), Baumann, M.(1) & Weil, M.(2).
Affiliations : (1) Karlsruhe Institute of Technology (KIT), Institute for Technology Assessment and System Analysis, Karlsruhe ? Germany (2) Helmholtz Institute Ulm (HIU) for Electrochemical Energy Storage, Ulm ? Germany
Resume : Battery energy storage is considered as key element for the mitigation of short-term peaks and the electrification of mobility sector towards 2050. In this context, techno-economics of Li-ion batteries (LiBs) is of great interest especially for the Europe considering the large renewable energy installations, and the high market share of European automotive manufacturers. To this end, a material demand and cost estimation tool is developed for conducting a techno-economic investigation of the widely used LiB chemistries (NCA, NMC, LMO, LR-NMC, LMNO, and LFP). The model is developed using a bottom-up approach starting from the raw materials required for the cell manufacturing to the entire battery energy storage system. The materials required for the cell material production are determined and necessary material quantities are estimated using material stoichiometry. Based on the determined demand, the material cost and manufacturing cost of the required active, inactive, and secondary materials are estimated. Considering the estimated material demand and cost, taking the common cell manufacturing steps as an origin the manufacturing cost are estimated to determine the cell price for the selected chemistries. To do so, scale exponents are introduced into the process cost model thus the economy of scales impacts are also considered for varying manufacturing volumes. Accordingly, the cell manufacturing volume is used for estimating the pack manufacturing capacity. To have an appropriate comparison, 12.5 kWh pack capacity is selected and required capital and manufacturing expenses are estimated in the same way. Required battery energy storage equipment for the control and power conversion system is determined and a container system with a 1 MW power capacity is designed. All the expenses to constitute a battery energy storage system are included in the calculations to estimate the overall system cost and the levelized cost of electricity for the considered chemistries are estimated taking into account the technical performance metrics (cycle life, degradation, etc.). As a result, NMC chemistries with their large energy density and high cycle life have shown high techno-economic performance, especially for the mobility applications. However, a remarkable alternative with a high potential for stationary battery energy storage is found to be the LFP due to the material scarcity and price instability concerns of NMC based cells. Hence, an overview and comparison of the selected Li-ion chemistries from material and cost perspective will be presented based on the created model.
Authors : Author, Huiting Liu*(1), Second-Author, Marcel Weil (1)(2), Third, Niklas von der Aßen (3) & Manuel Baumann (1)
Affiliations : (1) Institute for Technology Assessment and Systems Analysis (ITAS), Karlsruhe Institute of Technology (KIT), Germany (2) Helmholtz Institute Ulm (HIU), Germany (3) Chair of Technical Thermodynamics (LTT), RWTH Aachen University, Germany
Resume : Lithium-ion batteries are facing the challenges of potential resource scarcity and insecure supply chain, which makes sodium-ion battery widely discussed as a promising alternative due to its low cost and use of abundant elements. Hard carbon, also called non-graphitizable carbon, is the most suitable anode for sodium-ion batteries so far. As the market of this emerging material has not been fully developed yet, it is important to identify its sustainability including environmental, economic and social impact in early development phases. Based on previous research on the life cycle assessment of hard carbon, we intend to evaluate economic and socio-technical aspects of the hard carbon supply chain in a preliminary and qualitative way. Firstly, market maturity level of hard carbon materials is identified by using approaches such as patent analysis, literature review and stakeholder interviews, with a specific emphasis on sustainable development. Literature research enables the identification of global research trends and provide knowledge of the technology itself. The results of stakeholder interview reveal existing global business relevant to hard carbon supply chain, for example in China, Japan, Europe, etc. A patent analysis model is applied to provide understanding of innovation processes, and based on this, to identify the stage of technological life cycle of hard carbon material. Consequentially, the sustainable development goals are taken into consideration, in order to exploit the opportunities and possibilities for sustainable hard carbon supply chain. As a result, this work is expected to offer information for decision-making in the development of hard carbon technology and thus support the early conceptual design of sustainable manufacturing systems.
Testing : Roland Hischier
Authors : F. Sergi, D. Aloisio, G.S. Leonardi, M. Ferraro, S. Micari, G. Brunaccini, V. Antonucci
Affiliations : Consiglio Nazionale delle Ricerche - Istituto di Tecnologie Avanzate per l'Energia "Nicola Giordano" - via Salita S. Lucia sopra Contesse,5 - 98126 - MESSINA, Italy
Resume : In recent years, li-ion batteries have been widely employed in stationary and automotive applications. While performance often meets the requirements of the applications for which they were developed, the degradation effect over time can limit their use in particular operating circumstances for both safety and cost reasons. Since the operating load profile has a strong impact on the degradation of lithium-ion cells, dedicated experimental tests can provide important information in this regard. In this work, a long test campaign was carried out on sixteen Nickel Cobalt Aluminum (NCA) cells to collect sufficient data for lifetime evaluation under different operative conditions. Cycling aging was applied in selected charge/discharge profiles and ambient temperature conditions to develop a methodology for accelerating the time needed for aging evaluation in laboratory environment. Applying different cycles depending on application at various c-rate and temperatures, it is possible to evaluate the influence of each parameter on ageing. Electrochemical characterization was periodically carried out to record the state of health in terms of capacity and efficiency reduction, and resistance growth. Calendar aging was also performed at different temperature conditions. A final assessment on the long-run test campaign allowed validating through experimental data the accelerated tests methodology.
Authors : Tengfei He1, 2, Teng Zhang3, Zhirong Wang1*, Qiong Cai2*
Affiliations : 1Jiangsu Key Laboratory of Urban and Industrial Safety, College of Safety Science and Engineering, Nanjing Tech University, Nanjing 210009, China 2Department of Chemical and Process Engineering, Faculty of Engineering and Physical Sciences, University of Surrey, Guildford GU2 7XH, United Kingdom 3Department of Mechanical Engineering Science, Faculty of Engineering and Physical Sciences, University of Surrey, Guildford GU2 7XH, United Kingdom
Resume : Modelling the electrochemical and thermal behaviours of cylindrical lithium-ion batteries (LIBs) is complicated by their multilayer jelly roll structure. To evaluate if a full-scale cylindrical LIB model can be simplified, eight electrochemical-thermal models (ECT) with different levels of fidelity and dimensionality (from one-dimensional (1D) to 3D electrochemical and thermal models) are established for a Li[Ni8Co1Mn1]O2/graphite 18650 type LIB. The effect of different levels of simplification on the predicted LIB thermal and electrochemical characteristics are compared under different discharge and cooling rates. The results show that the predication of battery temperature vary greatly with the fidelity of selected thermal model. On the other hand, the ECT models with different electrochemical models show little difference in the predicted LIB temperature, although the 3D ECT model is more accurate in predicting the uniformity of electrochemical reaction and heat generation of the cell. The non-uniform electrochemical reaction and heat generation of the battery is most significant on the inner and outer layers of the battery. The inhomogeneous electrochemical reaction of the battery increases with the increase of the heat transfer coefficient and the discharge rate, while the non-uniform heat generation increase with the increase of the discharge rate and change slightly with the heat transfer coefficient changes.
Authors : Sebastian Ohneseit, S.O.*(1), Philipp Finster, P.F. (1), Nils Uhlmann, N.U. (1), Carlos Ziebert, C.Z. (1), Hans J. Seifert, H.S. (1) * lead presenter
Affiliations : (1) Karlsruhe Institute of Technology (KIT), Institute of Applied Materials - Applied Materials Physics (IAM-AWP), Eggenstein-Leopoldshafen, Germany
Resume : Lithium-ion batteries (LIB) are experiencing a significantly increasing demand for consumer goods, as well as for battery electric and hybrid electric vehicles. The broad usage possibilities of medium sized cylindrical cells, e.g. of size 18650 and 21700, results in multifaceted requirements and usage conditions. In consequence, their safety and the conditions provoking a thermal runaway are of particular interest. In this ongoing study it is planned to evaluate the influence of calendar and cyclic aging on the safety. Therefore commercial lithium-ion cells of type 21700 with different cathode materials and in high power as well as in high energy versions were acquired. In this part of the study, the fresh cells are analyzed by means of an Accelerating Rate Calorimeter (ARC) and the differences in the thermal runaway behavior are compared for the different materials and versions. Later, this analysis will be repeated for aged cells and the data will be compared. Before conducting the experiments in the ARC, the cells were characterized by means of electrochemical impedance spectroscopy (EIS) and their capacity was verified. The cells were dismantled and the composition of the cathode and anode was analyzed by means of inductive coupled plasma optical emission spectroscopy (ICP-OES). For assessing and comparing the safety, the cells are thermally abused at different state of charge using the Heat-Wait-Seek (HWS) test in an ARC. The exothermal behavior was determined and the self-heat rate as well as other safety relevant factors such as the onset, vent opening, current interruption device (CID) triggering and start of thermal runaway temperature were obtained and compared for all types and states of charge. A different thermal runaway behavior and reactivity was observed for NMC, NCA and LFP cathodes, as well as between high power and high energy cells. Additionally, the state of charge showed a significant influence on the reactivity for NCA cells. Further analysis by means of Accelerating Rate Calorimetry (ARC) will consist of nail penetration test at different SOC and for different cathode materials. In addition, more analytical investigations after disassembling of the cell will be done by means of x-ray diffraction (XRD) to reveal detailed structural data. Scanning electron microscopy (SEM) will be performed to work out highly resolved images of the interesting areas. Moreover, isothermal calorimetry will be conducted to compare the heat generation during cycling of the new cells.
Authors : V. Palomba(a), D. Aloisio(a), M. Ferraro(a), F. Muzio(b), D. Rebora(b), G. Brunaccini(a), A. Frazzica(a), F. Sergi(a)
Affiliations : (a) National Council of Research of Italy, Institute for Advanced Energy Technologies (CNR-ITAE), Salita S.Lucia sopra Contesse 5, 98126, Messina, Italy (b) Toshiba Transmission & Distribution Europe S.p.A., Via de Marini 1, 16149, Genova, Italy
Resume : This paper presents a hybrid thermal management system (TMS) for lithium-titanate oxide (LTO) batteries, which includes a passive element, i.e. Phase Change Materials (PCM) and an active one, i.e. a liquid cooling system. Several research efforts have been devoted in the past to the improvement of thermal management of lithium-ion batteries, but still dedicated focus towards the implementation in full-scale battery pack is needed. In particular, optimization of power density of batteries requires their reliable and continuous operation in a temperature range < 60°C, while minimizing the cost of the TMS and maximizing its efficiency. Safety issues and stable operation under unfavorable ambient conditions are further reasons that call for the optimization of the thermal management of the battery pack. In the present paper, COMSOL Multiphysics® is used for the simulation of different TMS. Results under natural convection are validated against experimental data and used as benchmark for the evaluation of different techniques: (a) passive system with PCM only; (b) active system with liquid cooling; (c) hybrid PCM-liquid cooling system. A parametric analysis is carried out to identify the best operating parameters in terms of reduction of the cell temperature and increase of electrical efficiency of the cell. In order to further progress towards the full-scale application of the proposed TMS, two main differences compared to the other systems proposed in the literature are considered: the use of solid-solid PCMs, which avoid the presence of flammable liquids within the battery cell, and the evaluation of the thermal response of the system under realistic operating conditions and multiple cycles. The results indicate that the proposed hybrid thermal management system can provide more benefits than traditional cooling systems in some particular applications and, accordingly, recommendation for future activities on its development are given.
Authors : Chi Nguyen Van
Affiliations : Institute of High-Technology Research and Development for Industry (RIAT), Thai Nguyen University of Technology (TNUT), 666, 3/2 Street, Tich Luong Ward, Thai Nguyen City 251750, Vietnam
Resume : This paper presents a energy equalizing control method for Lithium-Ion battery pack formed by many cells connected in series. Using the active cell equalizing method with a cell-to-cell equalizing circuit configuration, the energy levels of two adjacent cells will be equalized by a equalizing circuit based on the principle of a bidirectional Cuk converter circuit with the PWM pulse width control variables The control strategy to determine the control variables is based on the solution of nonlinear optimal problem with the state of charge feedback satisfying the constraint of the energy levels, the amplitude of charge/discharge current, the equalizing currents in order to maintain the safe operation state of cells. Experimental results for Lithium-Ion battery pack with 7 SAMSUNG 22P battery cells connected in series with charge/discharge alternately scenarios show that the energy equalizing control proposed is quite effective in the practice.
Authors : Davide Aloisio (a), Maria Grazia Fadda (b), Gianluca Leonardi (a), Salvatore Micari (a), Giovanni Brunaccini (a), Marco Ferraro (a), Vincenzo Antonucci (a), Marco Pietrucci (b), Domenica Maria Conenna (b), Francesco Sergi (a)
Affiliations : (a) - National Council of Research of Italy, Institute for Advanced Energy Technologies (CNR-ITAE), Salita S.Lucia sopra Contesse 5, 98126, Messina, Italy (b) - Terna S.P.A., registered office Viale Egidio Galbani, 70, 00156 Roma, Italy
Resume : This paper presents the results of a wide test campaign carried out on a commercial EDLC (Electric Double Layer Capacitor) supercapacitor used by Terna, the Italian TSO (Transmission System Operator), to provide ancillary services to support the electric grid. It is well known that in the last time the study of different storage systems for stationary applications is underway. These are used to balance the energy flow in the electric grid, helping the continuous increase in renewable energy sources while reducing grid unreliability, although these are not always suitable to meet all the required purposes. Among them, supercapacitors are becoming one of the most important technologies for ensuring grid power quality, thanks to very fast response, high cyclability and strong reliability. A lot of study was done in these years to improve the knowledge on this kind of electrochemical devices and several electrochemical phenomena related to super-capacitive behavior were investigated. In this study has been investigated the behavior of an EDLC in terms of electrical and thermal response when subject different tests (performance tests at different temperatures, ageing test at high temperature, i.e. 65 °C, response to high current pulse, overcharge, etc). In particular, the effect of temperature on their life was evaluated, due to strong impact of this parameter on it. The study suggests the importance of thermal management of this kind of devices, in particular when several modules work together, as in stationary applications.
LIC and alternatives : Francesco Sergi
Authors : Carmen Cavallo*, Giulio Calcagno, Rodrigo Pereira de Carvalho, Alan Dang, Matthew Sadd, Bruno Gonano, C. Moyses Araujo, Anders E.C. Palmqvist, and Aleksandar Matic*
Affiliations : Centre for Materials Science and Nanotechnology (SMN)/Battery Division, Department of Chemistry, Oslo University, OSLO, Norway; Department of Chemistry and Chemical Engineering, Chalmers University of Technology, 412 96 Gothenburg, Sweden; Materials Theory Division, Department of Physics and Astronomy, Ångström Laboratory, Uppsala University, 751 20 Uppsala, Sweden; University of California Santa Barbara, CA, 93106, USA; Department of Physics, Chalmers University of Technology, GOTEBORG, Sweden; Centre for Materials Science and Nanotechnology (SMN), Department of Chemistry, Oslo University, OSLO, Norway; Materials Theory Division, Department of Physics and Astronomy, Ångström Laboratory, Uppsala University, 751 20 Uppsala, Sweden; Department of Chemistry and Chemical Engineering, Chalmers University of Technology, 412 96 Gothenburg, Sweden; Department of Physics, Chalmers University of Technology, 412 96 Gothenburg, Sweden;
Resume : Short-term accumulation for rapid reuse forces the development of a new style of supercapacitors. Hybrid Asymmetric Super Capacitors, or simply Li-ion capacitors, are designed to achieve both high power and energy densities using a carbon-based EDL material as a positive electrode coupled with a Li-ion intercalation negative electrode (or vice-versa). The challenge is finding sustainable materials as fast charging negative electrodes, characterized by high capacity retention. TiO2-based nanomaterials and, in particular, the polymorphs anatase and TiO2(B) are promising as negative electrodes due to their high structural stability, thanks to the low volume change during cycling (?4%). Unfortunately, the poor electronic conductivity and the low ionic diffusivity, which influence the Li insertion/desertion in Ti, are affecting their use in practice. Herein, we aim at overcoming the low electronic conductivity, the low ion diffusivity, and the capacity fading of anatase by introducing pentavalent niobium ion doping and directly using our microbeads as anodes for fast rechargeable Li-ion batteries. Mesoporous niobium-doped anatase beads (Nb-doped TiO2) with different Nb5+ doping (n-type) concentrations (0.0 Pure, 0.1, 1.0, and 10% at.) were synthesized via an improved template approach followed by hydrothermal treatment. The formation of intrinsic n-type defects and oxygen vacancies under RT conditions gives rise to metallic-type conduction due to a shift of the Fermi energy level. The increase in the metallic character, confirmed by electrochemical impedance spectroscopy, enhances the performance of the anatase bead electrodes in terms of rate capability and provides higher capacities both at low and fast charging rates. The experimental data were supported by density functional theory (DFT) calculations showing how different n-type doping can be correlated to the same electrochemical effect on the final device. The Nb-doped TiO2 electrode materials exhibit improved cycling stability at all the doping concentrations by overcoming the capacity fade shown in the case of pure TiO2 beads. The 0.1% Nb-doped TiO2-based electrodes exhibit the highest reversible capacities of 180 mAh g?1 at 1C (330 mA g?1) after 500 cycles and 110 mAh g?1 at 10C (3300 mA g?1) after 1000 cycles. Our experimental and computational results highlight the real possibility of using n-type doped TiO2 materials as anodes in high-rate Li-ion batteries and Li-ion capacitors. Indeed, the pure phase was properly paired with a commercial activated carbon cathode to form a Li-ion capacitor. The titania electrode exhibits high capacity and rate performance. The device shows extremely stable performance with an energy density of 27mWh g-1 at a specific current of 2.5 A g-1 for 10,000 cycles. The remarkable stability is associated with a gradual shift of the potential during cycling as a result of the formation of cubic LiTiO2 on the surface of the beads. This phenomenon renews the interest in using TiO2 as a negative electrode for high-rate Li-ion batteries and capacitors.
Authors : Baptista, J. M.(1,2), Gaspar, G.(1), Wijayantha, U. K. G.(2) & Lobato, K.(1)
Affiliations : (1) Instituto Dom Luiz, Faculdade de Ciências, Universidade de Lisboa, 1749-016 Lisboa, Portugal; (2) Energy Research Laboratory (ERL), Department of Chemistry, Loughborough University, Loughborough, Leicester LE11 3TU, UK
Resume : Commercial supercapacitors typically employ organic solvents, due to their wider operational potential range (ca. 2.7V), which grants them a higher energy density. However, this type of electrolytes is expensive, flammable, toxic  and typically renders lower capacitances. Devices with aqueous electrolytes are considerably better in these aspects, but they present a narrow range of stable potentials (?V?1V), which severely limits their energy density. To solve this issue, a thin coating of an insulating polymer - poly(phenylene oxide)  ? was electrodeposited on the surface of activated carbon electrodes. This passivating layer should be thick enough to prevent electron transfer between the electrode and the electrolyte (>2 nm)  whilst simultaneously thin enough (< 30 nm) to preserve the electrode?s high surface area, indispensable for a high capacitance. Several electrodeposition potentials have been studied (1.15V to 1.9V vs Ag wire, which acted as a pseudo-reference) and preliminary results suggest a trade-off between capacitance and the degree of passivation: a decrease in both oxidation and reduction currents (respectively associated to the oxygen and hydrogen evolution reactions) comes at the expense of some capacitance loss. However, for the best conditions, the ca. 33% increase in the potential range seems to compensate the ca. 40% capacitance loss and render a ca. 6% increase in the overall energy density. This study was complemented with X-ray Photoelectron Spectroscopy measurements to assess the elemental composition of the surfaces after polymerization under different potentials. The authors acknowledge the financial support given by the UK EPSRC JUICED Hub project EP/R023662/1, by national funds FCT/MCTES (PIDDAC) and by Fundação para a Ciência e a Tecnologia (FCT): projects UIDB/50019/2020 ? IDL - Instituto Dom Luiz and PhD grant PD/BD/128169/2016  González et al., Renew. Sust. Energ. Rev. 58 (2016) 1189?1206  Deheryan et al., Carbon 88 (2015) 42 ?50  Fletcher et al., J. Phys. Chem. C 120 (2016) 8014?8022
Authors : a,b-Nurzhan Baikalov; a-Almagul Mentbayeva; a-Aishuak Konarov, c-Yongguang Zhang; a,b-Zhumabay Bakenov
Affiliations : a ? School of Engineering and Digital Sciences, Nazarbayev University, Nur-Sultan 010000, Kazakhstan b ? National Laboratory Astana, Nazarbayev University, Nur-Sultan 010000, Kazakhstan c ? School of Materials Science and Engineering, Hebei University of Technology, Tianjin 300130, China
Resume : Lithium-ion batteries (LIBs) opened new opportunities for rapid development of modern portable devices. LIBs use mainly the intercalation cathodes represented by transition metal oxides and phosphates as cathodes, which are incapable of fulfilling the requirements of electric vehicles and high energy storage systems due to their limited energy density (less than 400 W h kg-1). Moreover, intercalation type cathodes have several drawbacks associated with high cost of materials and safety issues which also limit their use in electric vehicles and large scale power systems. Therefore, implementation of alternative systems with higher specific capacity, energy density and inexpensive sources is required in order to meet high demands. In this regard, lithium sulfur (Li-S) batteries are considered as one of the most promising energy systems due to high theoretical specific capacity, which results in a theoretical energy density of 2600 Wh kg?1.1 Moreover, sulfur has low cost, considerably less environmentally impact and abundant resources.2 However, the implementation of Li-S batteries is hindered due to a number of drawbacks such as low conductivity of sulfur, complicated redox reactions, shuttle of soluble intermediates (polysulfides, LiPS), dendrite growth on lithium anode and volumetric expansion of cathode upon reduction to Li2S2/Li2S which leads to structural degradation and lower the cycle life of batteries.3 The shuttle effect can be suppressed via encapsulation of sulfur into carbon matrices, synthesis of conductive sulfur composites with polymers, etc. In our recent works we reported on carbon materials with metal -oxides, -sulfides and -nitrides as sulfur immobilizers exhibiting strong affinity to LiPSs. Despite such strong immobilization effect of metal compounds, the conversion of sulfur to the end products needs to be enhanced by introduction of electrocatalysts. In this work, the synergistic effect of heterostructures with double functions, titanium dioxide as LiPSs immobilizer with Ni, Co metals as electrocatalysts were prepared and analyzed as an effective sulfur host material. Acknowledgement: This work was supported by the project AP09259764 ?Engineering of Multifunctional Materials of Next Generation Batteries? from the Ministry of Education and Science of the Republic of Kazakhstan. References: (1) Xu, Z.-L.; Kim, J.-K.; Kang, K. Carbon Nanomaterials for Advanced Lithium Sulfur Batteries. Nano Today 2018, 19, 84?107. https://doi.org/10.1016/j.nantod.2018.02.006. (2) Kim, S. J.; Kim, K.; Park, J.; Sung, Y. E. Role and Potential of Metal Sulfide Catalysts in Lithium-Sulfur Battery Applications. ChemCatChem 2019, 11 (10), 2373?2387. https://doi.org/10.1002/cctc.201900184. (3) Ould Ely, T.; Kamzabek, D.; Chakraborty, D.; Doherty, M. F. Lithium?Sulfur Batteries: State of the Art and Future Directions. ACS Appl. Energy Mater. 2018, 1 (5), 1783?1814. https://doi.org/10.1021/acsaem.7b00153.
Authors : Usman Zubair*, Carlotta Francia, Silvia Bodoardo
Affiliations : *School of Engineering and Technology, National Textile University, Sheikhupura Road, 37610, Faisalabad, Pakistan & Department of Applied Science and Technology, (DISAT), Politecnico di Torino, C.so Duca degli Abruzzi 24 - 10129 Torino ? (ITALY); Department of Applied Science and Technology, (DISAT), Politecnico di Torino, C.so Duca degli Abruzzi 24 - 10129 Torino ? (ITALY); Department of Applied Science and Technology, (DISAT), Politecnico di Torino, C.so Duca degli Abruzzi 24 - 10129 Torino ? (ITALY) *Corresponding Author (contact details): firstname.lastname@example.org, +92 333 83 65 135
Resume : Various metal oxides have been widely investigated to catalyse lithium polysulfides (LiPS) conversion to promote the surface-bound insoluble intermediates and limit the LiPS shuttle, but further enhancement of their activities is a growing challenge. Herein, an effective methodology has been reported to enhance LiPS catalytic conversion by electrodepositing mixed phases composite films of various manganese oxides (MnOx) on carbonized cotton cloth. Synergistic effects of porous carbon cotton fabric with remnant lumen and high interfacial MnOx composite films comprised of nanoflakes greatly contribute towards high-loading freestanding sulfur cathodes. Various MnOx phases have been achieved by controlled annealing of MnOOH electrodeposited nanoflakes on carbon cloth. Oxygen deficient phases especially active interfaces among various phases have been proposed to accelerate the LiPS oxidation to polythionate complexes that can interact with LiPS to assist their onsite conversion into lithium sulfide. The composition of pristine and LiPS interacted deposited films have been evaluated by X-ray photoelectron spectra (XPS) and X-ray absorption spectra (XAS). The cathodes bearing high oxygen-deficient manganese oxide nanoflakes achieve high initial discharge capacity of 1083 mAh/g and high reversible capacity of 815 mAh/g at 0.5 C over 300 cycles at loading of 5 mg/cm2, while only initial discharge capacity of 918 mAh/g and reversible capacity of 567 mAh/g are obtained for MnO2 dominated deposit films. This study reveals a new strategy to prepare free-standing binder free sulfur cathodes at higher sulfur loadings.
Authors : V. Baglio1, C. Busacca1, A. Di Blasi1, O. Di Blasi1, E. Modica1, O. Barbera1, V. Antonucci1, M.J. Lázaro2, C. Alegre2
Affiliations : 1 Istituto di Tecnologie Avanzate per l?Energia ?Nicola Giordano? (ITAE), Consiglio Nazionale delle Ricerche (CNR), Via Salita S. Lucia sopra Contesse 5, 98126 Messina (Italy) 2 CSIC-Instituto de Carboquímica (ICB), C/Miguel Luesma Castan 4, 50018 Zaragoza (Spain)
Resume : Rechargeable alkaline Zn?air batteries are envisaged as promising post-lithium energy storage technologies due to their environmental friendliness, safety, affordability and high theoretical energy density. However, they do not still offer adequate practical energy density and life cycle due to critical problems arising from the positive electrode, such as slow kinetics of the oxygen reduction (ORR) and oxygen evolution (OER) reactions. In previous works, our group employed electrospinning to prepare bifunctional ORR/OER catalysts based on carbon nanofibers (CNF) loaded with spinel-type FeCo2O4 or NiCo2O4 [1-2]. Using this technique, highly active oxides supported on a graphitic carbon support, CNFs, also doped with N coming from the carbon precursor (Polyacrylonitrile), were obtained. The as-prepared CNFs were characterized by a high interaction with the metal, porosity and good resistance to corrosion, due to their graphitic character. In the present work, MnCo2O4/CNF catalysts are synthesized and physico-chemically studied in terms of structure, morphology, and surface properties; these features have been correlated to the electro-chemical behavior for the ORR and OER in comparison with previously developed catalysts and state-of-the-art materials reported in the literature. A preliminary investigation in an alkaline Zn-air battery is presented. Acknowledgements: The research leading to these results has received funding from the ?Accordo di Programma CNR-MiSE, RdS PTR 2019-2021 - "Progetto 1.2 Sistemi di accumulo, compresi elettrochimico e power to gas, e relative interfacce con le reti?. References  C. Alegre, C. Busacca, A. Di Blasi, O. Di Blasi, A.S. Aricò, V. Antonucci, V. Baglio, Materials Today Energy 2020, 18, 100508.  C. Alegre, C. Busacca, A. Di Blasi, O. Di Blasi, A.S. Aricò, V. Antonucci, V. Baglio, ChemElectroChem 2020, 7, 124.
Authors : L. Frusteri, G. Leonardi, V. Antonucci, C. D?Urso
Affiliations : CNR-ITAE ? Via Santa Lucia sopra Contesse, 5 ? 98125 Messina
Resume : Solid metal halides are used as optimal active cathode component to produce Na-NiCl2 batteries. These cells require a fused secondary electrolyte, sodium tetrachloraluminate (NaAlCl4), that facilitates the migration of the Na+ ions into the cathode. The sodium-nickel chloride (Na - NiCl2) battery has been extensively investigated as a promising system for large-scale energy storage applications. The growth of Ni and NaCl particles in the cathode is one of the most important factors that affects the performance of the Na-NiCl2 battery. The presence of large Ni and NaCl particles, inside the active phase, can lead to an increase in cell polarization resulting from a reduction in surface utilization. A higher current density, a higher state of charge (SOC) at the end of the charge (EOC) and a lower Ni / NaCl ratio are the main parameters that favour a rapid growth of Ni particles. In light of these problems, innovative nano-structured materials with important electrochemical properties have been produced and studied to simultaneously improve battery performance without neglecting the economic aspect and environmental sustainability. Starting from the well-known cathodic material (Na-NiCl2), the new electrolytic materials have been prepared replacing nickel with iron (substitution ranging from 10 to 90wt%). The advantages of this choice are: - lower cost of cathode material compared to the state of the art; - cheaper assembling materials (stainless steels could be used for cell components, including cathode current collectors and cell housings). The study on the particle size of the cathode and the physic-chemical characterization of the cathode was carried out in the test cell using, where possible, the GITT method (galvanostatic technique of intermittent titration). Furthermore, the impact of temperature on the different cathode compositions of the positive electrode was being studied.
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Organic Battery : Vincenzo Antonucci
Authors : Di Noto, V.* (1); Pagot, G. (1); Vezzù, K. (1); Negro, E. (1); Greenbaum, S.G. (2); * lead presenter
Affiliations : (1) Section of Chemistry for the Technology (ChemTech), Department of Industrial Engineering, University of Padova, Via Marzolo 9, I-35131 Padova (PD), Italy (2) Department of Physics & Astronomy, Hunter College of the City University of New York, 695 Park Avenue, 10065 New York (NY), United States
Resume : The development of stable and high-performing electrolyte materials is one of the main bottlenecks in the field of ?beyond Li-ion? secondary battery technology. In particular, electrolytes able to reversibly deposit and strip multivalent metals seem to be the answer to the growing energy demand set by the Electric Vehicles market. In this concern, Ionic Liquids (ILs) are considered attractive materials thanks to their low volatility, negligible flammability and good electrochemical performance in the metal reversible deposition processes [1-3]. Indeed, it was recently demonstrated how electrolytes based on ILs are able to deposit and strip a magnesium/metal alloy with Coulombic efficiencies higher than 99 %, overpotentials lower than 50 mV vs. Mg/Mg2+, remarkable current densities and a stability for over 70 cycles. In this talk, an overview on the most recent progresses in IL-based electrolytes for hybrid multivalent metals secondary batteries will be given. A detailed description of the interplay between structure, coordination and conductivity of ionic species will be presented. Thus, the relationships among metal ion speciation, long-range charge migration processes and electrochemical performances of these materials will be described. References:  G. Pagot, V. Di Noto et al., J. Power Sourc. 2021, 493, 229681.  G. Pagot, V. Di Noto et al., Electrochim. Acta 2017, 246, 914-923.  F. Bertasi, V. Di Noto et al., ChemSusChem 2015, 8, 3069-3076.
Authors : Jan Bitenc1, Klemen Pirnat1, Alen Vizintin1, Anna Randon-Vitanova2, Robert Dominko1
Affiliations : 1National Institute of Chemistry, Hajdrihova 19, 1000 Ljubljana, Slovenia 2 Honda R&D Europe GmbH, Carl-Legien Strasse 30, 63703 Offenbach, Germany
Resume : Rechargeable multivalent batteries are highly interesting future battery technology. Their application is envisioned through use of metallic anode (Mg, Ca and Al) and high-energy density cathodes, both of these electrodes present a specific challenge. Metallic multivalent metals are typically incompatible with conventional electrolytes known from Li-ion batteriesdue to the fact that solid electrolyte interphases do not allow transport of multivalent ions, unlike in case of Li passive layer. On the field of cathodes tendency towards irreversible conversion reactions, slow solid-state diffusion and energy demanding desolvation of multivalent ions present a major challenge in the development of cathode materials. Rapid development of new multivalent electrolytes in the last years, especially on the field of Mg and Ca electrolytes, has opened a path towards exploration of new types of cathode materials such as organic compounds, sulfur? Organic active materials offer a possibility to circumvent most of the limitations of inorganic ones. However, organics typically contain electrophilic centers inside organic electroactive groups. Hence, they need to be combined with non-nucleophilic electrolytes. Simple organic active materials often suffer from dissolution of active material into electrolyte, which leads to rapid capacity fade. Dissolution can be effectively mitigated through preparation of insoluble polymers. In our work we have shown that anthraquinone based polymers can be utilized as cathodes in Mg, Ca and Al rechargeable batteries.[1?3] Furthermore, we have shown that combination of suitable organic polymers and non-nucleophilic electrolytes can offer a long-term stability of organic batteries with capacity retention of more than 65% after 500 cycles. Electrochemical mechanism of organic materials is investigated through combination of ex-situ EDS and both operando&ex situ ATR-IR. References  J. Bitenc, K. Pirnat, T. Ban?i?, M. Gaber??ek, B. Genorio, A. Randon-Vitanova, R. Dominko, ChemSusChem 2015, 8, 4128.  J. Bitenc, A. Scafuri, K. Pirnat, M. Lozin?ek, I. Jerman, J. Grdadolnik, B. Fraisse, R. Berthelot, L. Stievano, R. Dominko, Batter. Supercaps 2020, batt. 202000197.  J. Bitenc, N. Lindahl, A. Vizintin, M. E. Abdelhamid, R. Dominko, P. Johansson, Energy Storage Mater. 2020, 24, 379.  J. Bitenc, K. Pirnat, E. ?agar, A. Randon-Vitanova, R. Dominko, J. Power Sources 2019, 430, 90.
Authors : Zhirong Zhao-Karger, Zhenyou Li and Maximilian Fichtner
Affiliations : Helmholtz Institute Ulm (HIU), Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT)
Resume : Rechargeable battery technologies based on the use of a metal anode and multivalent charge carrier ions (such as Mg2+, Ca2+) have the potential to provide high volumetric energy densities. The sustainable resource availability and safety advantages of these so-called ?beyond lithium-ion? battery systems could offer possibility for economic energy storage solutions, which are in particular promising for large-scale applications. However, the fundamental chemical and electrochemical properties associated with the doubly charged ions also generate inherent material design challenges for both Mg and Ca batteries. For instance, the strong ion association and solvation energy limit the ionic conductivity, as well as the electrode?electrolyte interfacial kinetics; the high charge density of the divalent ions induces strong electrostatic interactions between the working ion and cathode host, leading to sluggish ion diffusion in many common intercalation cathodes. In this talk, we will discuss some latest research and advanced design concepts to address the specific issues in formulating electrolytes, identifying suitable cathodes and understanding interfacial chemistries for Mg and Ca batteries.
Authors : Joachim Häcker (1), Tobias Rommel (1), Maryam Nojabaee (1), Zhirong Zhao-Karger (2), Norbert Wagner (1), K. Andreas Friedrich (1 3)
Affiliations : (1) Institute of Engineering Thermodynamics, German Aerospace Center (DLR), Pfaffenwaldring 38-40, 70569 Stuttgart, Germany; (2) Helmholtz Institute Ulm (HIU) Electrochemical Energy Storage, Helmholtzstrasse 11, 89081 Ulm, Germany; (3) Institute of Building Energetics, Thermal Engineering and Energy Storage (IGTE), University of Stuttgart, Pfaffenwaldring 6, 70569 Stuttgart, Germany
Resume : The magnesium-sulfur battery is a promising candidate as post-lithium battery system due to its high energy density, improved safety and abundance of the applied raw materials. Its underlying mechanism is comparable to the lithium-sulfur system also facing the challenge of sulfur retention in the cathode to mitigate the polysulfide shuttle. In contrast to Li-S cells, reactions at the metal anode in Mg-S batteries ? i.e. reduction of sulfur or electrolyte species at the Mg surface ? might lead to anode passivation and localized stripping/plating behavior inducing high overpotentials and dendrite formation, respectively. An artificial solid electrolyte interphase (SEI) represents a popular approach to solve many of these problems at once. It aims to inhibit inadvertent reactions and detrimental in situ SEI formation at the Mg surface, and might enable uniform Mg deposition as well as stable cycling with less active material loss and mitigated self-discharge. Therefore, a thin, homogenous and mechanically stable surface coating is desired, which features high ionic and negligible electrical conductivity while being electrochemically stable in a wide potential range. In this study, different ionomers and preparation methods were applied in an attempt to meet all requirements. The gained coatings were analyzed by polarization experiments in symmetrical Mg-Mg as well as galvanostatic cycling in Mg-S cells. Electrochemical impedance spectroscopy was applied to gain deeper insights and revealed the limitations of such coatings. Nevertheless, an ionomeric artificial SEI is capable to enhance the Coulombic efficiency as well as the discharge capacity gain, which confirms the artificial SEI to be an important component in the attainment of high-energy magnesium-sulfur batteries.
Authors : D.Snihirova, L.Wang, C.Wang, D.Min, B.Vaghefinazari, D.Höche, S.V.Lamaka, M.L.Zheludkevich
Affiliations : Institute of Surface Science, Helmholtz-Zentrum Hereon, 21502, Germany; Faculty of Engineering, Kiel University, Kaiserstrasse 2, Kiel, 24143, Germany
Resume : Magnesium and its alloys are actively explored in energy sector due to the high electrochemical reactivity, environmental compatibility and relatively low costs. However, when Mg is used as anode, in contact with water the Mg reactivity increases during the battery discharge. That is why it is crucial to control degradation of magnesium electrode by using advance alloys or effective electrolyte additives. An efficient way of using Fe3 complexing agents in electrolyte was shown previously. It significantly inhibits parasitic self-corrosion and improves the Mg behavior during discharge. However, in many cases, hydrogen evolution reaction is not completely suppressed. The relevant method to thoroughly control hydrogen evolution reaction is to use combination of different additives. Herein we combined Fe3 -complexing agents, that prevent detrimental iron re-deposition, with efficient magnesium inhibitors (sodium nitrate and nitrite) that reduce parasitic hydrogen evolution reaction. The combination of additives was chosen based on knowledge of magnesium corrosion mechanism and experience with corrosion inhibitors of Mg. In this work, the effect of single additives and their combination was studied under galvanostatic polarization. Additionally, localized measurements of pH and dissolved oxygen above magnesium surface during discharge were done in order to give insights on the additives mechanism. The results show that use of combination of additives reduce significantly the hydrogen evolution and in addition prevent formation of Mg(OH)2. The most effective was the mixture of sodium salicylate-sodium nitrate . This work is a step further to the improvement of the Mg-air battery performance.  D. Snihirova, L. Wang, S.V. Lamaka, C. Wang, M. Deng, B. Vaghefinazari, D. Höche, M.L. Zheludkevich, Synergistic Mixture of Electrolyte Additives: A Route to a High-Efficiency Mg?Air Battery, The Journal of Physical Chemistry Letters, (2020) 8790-8798.
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Flow Battery : Carmen Cavallo
Authors : Hannes Radinger (1), Adrian Lindner (1), Vanessa Trouillet (1), Jessica Pfisterer (1), Ahmad Ghamlouche (1), Helmut Ehrenberg (1) & Frieder Scheiba (1)
Affiliations : (1) Institute for Applied Materials, Karlsruhe Institute of Technology, Germany
Resume : Large-scale storage of renewable energy requires alternative battery technologies with high energy density, such as vanadium flow batteries. However, the interfacial processes controlling charge transfer at the carbon-based electrode are still poorly understood and need to be improved to increase the power density, which is considered the main obstacle for commercialization. Many studies report various surface modifications to enhance the electrocatalytic activity of graphite felts based on the introduction of surface-active oxygen functional groups. This work relies on a 30-year-old mechanism to which our group has recently formulated a counter-thesis. Consequently, the charge transfer and thus the effectiveness of the electrode is rather limited by these groups. Contrary to the prevailing opinion, the activity of the electrode is enhanced by the removal of surface oxygen. We identified microstructural defects such as edge sites and carbon vacancies as the actual origin of the activity. To clarify why the literature on this topic is so contradictory and to investigate the influence of defects in more detail, common thermal activation is used and compared with respect to its influence on the surface chemistry and microstructure of graphite felts. In addition, polycyclic aromatic hydrocarbons exposing zigzag and armchair edge sites and possibly containing additional functional groups were used as a model to mimic graphitic defects. These modified electrodes were then tested for their electrocatalytic activity. By using various advanced surface sensitive techniques in combination with (operando) Raman spectroscopy, further insights into the influence of graphitic defects, the interplay of micro- and electronic structure, and the mechanism of the vanadium redox reaction is obtained.
Authors : C. Busacca, O. Di Blasi, V. Antonucci, A. Di Blasi
Affiliations : CNR-ITAE
Resume : Alternative redox flow batteries to all Vanadium redox flow are attracting great attention thanks to the interesting reached results. Recently, Zn-Br battery recorded an EE of about 70% at 80 mA/cm2, while another kind of redox battery known as Zn-I recorded an EE of about 82% at 80 mA/cm2. In this work, vanadium alternative redox couples not yet investigated or poorly investigated, such as Ti/Ce, Ni / Ce and Ni/Mn were chosen as being for the interesting cell voltage, readily available and low cost, and the added benefit of relatively low toxicity and ease of disposal. Electrochemical tests such as cyclic voltammetry (CV), complex impedance spectroscopy (EIS) and charge-discharge tests were carried out to establish the feasibility of the proposed redox systems both in terms of developed potential and results relating to the main electrochemical parameters such as coulomb efficiency (CE), voltage efficiency (VE) and energy efficiency (EE).
Authors : Akhmetov N.O., Ovsyannikov N.A., Pogosova M.A., Krasnikova I.V., Gvozdik N.A., Stevenson K.J.
Affiliations : Skolkovo Institute of Science and Technology
Resume : Non-aqueous hybrid redox flow batteries (HFBs) based on metallic lithium anode and liquid catholyte are considered as prospective energy storage devices. Accumulating the energy from various sources, HFBs can either compensate energy drawbacks or overtake energy excess issues. Comparing with traditional Li-ion batteries, HFBs store energy in a separate tank enabling an independent control of battery?s power and energy capacity. Moreover, lithium anode and non-aqueous media allow operating at high voltage (above 4 V) that significantly enhances the power density of conventional flow batteries. The main challenge retarding the HFBs development is the absence of an effective ion-conductive membrane. This membrane is responsible for the cell?s charge balance and influences the battery?s cyclability, power, and efficiency. The ceramic-polymer fabrication approach was applied recently to membranes for solid-state batteries. Integration of ion-conductive Li1.3Al0.3Ti1.7(PO4)3 (LATP) ceramics into the stable poly(vinylidene fluoride) (PVdF) matrix provided the final membranes with the best characteristics of initial components: high ionic conductivity, good cyclability, stability, and flexibility. In this report, we studied the LATP+PVdF membranes (tape casting fabrication) suitable for the hybrid lithium (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) flow batteries. The various physical (XRD, FTIR, SEM, EDX) and electrochemical (impedance spectroscopy, cyclic voltammetry, galvanostatic cycling) techniques were used to analyze critical membranes? properties for the effective operation of Li-TEMPO HFBs. The most promising 45 wt.% LATP PVdF membrane demonstrated high ionic conductivity (3.4?10-4 S/cm), TEMPO permeability of 6.6?10-7 cm2/min, and outstanding stability towards metallic lithium (400 cycles) that substantially outperforms the commercially available membranes (Nafion, Neosepta). During galvanostatic tests, the Li-TEMPO cell with LATP PVdF) showed excellent cyclability, stable columbic efficiency of over 95%, and an initial capacity about 2.5 Ah/L (state of charge of about 93%), which then decreased to 1.4 Ah/L due to the crossover. Nevertheless, the LATP PVdF cycling performance (100 charge/discharge cycles) exceeds that of commercial analogues. There are also several pathways to suppress the crossover of LATP PVdF. Thus, the composite membrane is promising for non-aqueous Li-TEMPO HFBs due to the high lithium-ion conductivity, outstanding stability to the battery?s media, and cyclability. We hope these results will be useful for the further development of HFBs as well as other energy storage devices.
Authors : S. Kunz (1,3), M. Janse van Rensburg (2), D.S. Pietruschka (1,3), D. Emmel (1,3), D. Mollenhauer (1,3), H.A. Wegner (2,3), D.Schröder (4)
Affiliations : (1) Institute of Physical Chemistry, Justus Liebig University Giessen, Heinrich-Buff-Ring 17, 35392 Giessen, Germany; (2) Institute of Organic Chemistry and Center for Materials research, Justus Liebig University Giessen, Heinrich-Buff-Ring 17, 35392 Giessen, Germany; (3) Center for Materials research, Justus Liebig University Giessen, Heinrich-Buff-Ring 16, 35392 Giessen, Germany; (4) Institute of Energy and Process Systems Engineering, Technische Universität Braunschweig, Langer Kamp 19B, D-38106 Braunschweig, Germany
Resume : Organic active materials for redox flow batteries (RFBs) are intensively studied due to their potential low costs and adjustable electrochemical parameters. Verdazyl radicals belong to the class of stable organic radicals and upcoming RFB active materials. These radicals can be either oxidized or reduced electrochemically at a potential difference of ? 1 V. The presence of three redox states along with the potential difference makes them interesting candidates for the design for symmetric RFBs. First small-scale applications of Verdazyl radicals in symmetrical RFBs were shown recently. Besides these first RFB applications, there are still open questions regarding the fundamental impact on the performance of Verdazyl radicals in RFBs. The electrolyte, consisting of solvent and conductive salt, can have a remarkable influence on the electrochemical parameters of an organic active material. Electrochemical potential, rate constant, diffusion coefficient and mechanism of organic active materials can be easily varied for a certain molecule class. We aim to increase the understanding of the Verdazyl radicals by studying the impact of the electrolyte on the behavior of the Triphenylverdazyl radical by electrochemical characterization (cyclovoltammetry, hydrodynamic linear sweep voltammetry and square wave voltammetry). We show with the gathered electrochemical data, connected with computational data, that the redox mechanism of Verdazyl radicals differs fundamentally in organic and water-based solvents. This difference is revealed by identifying the number of transferred protons and electrons at different pH values and evaluating the resulting pourbaix diagram. Furthermore, we investigate differences in redox mechanism and involved species with UV/Vis spectroscopy and mass spectrometry in connection with electrochemical data. The Triphenylverdazyl radical, with a very basic structure, is used to gain representative results for the entire molecule class of Verdazyl radicals. With the gained knowledge about the electrolyte impact on the redox mechanism, we can compare it to state-of-the-art organic electrolytes and novel water-based electrolytes. In the end, the basic knowledge about the reactivity of the class of Verdazyl radicals is revealed and leads towards their application in full-scale RFBs.  Y. Ding, C. Zhang, L. Zhang, Y. Zhou, G. Yu, Chemical Society reviews 2018, 47, 69.  J. B. Gilroy, S. D. J. McKinnon, B. D. Koivisto, R. G. Hicks, Organic letters 2007, 9, 4837.  a) G. D. Charlton, S. M. Barbon, J. B. Gilroy, C. A. Dyker, Journal of Energy Chemistry 2019, 34, 52; b) A. Korshunov, M. J. Milner, M. Grünebaum, A. Studer, M. Winter, I. Cekic-Laskovic, J. Mater. Chem. A 2020, 8, 22280.  J. D. Hofmann, F. L. Pfanschilling, N. Krawczyk, P. Geigle, L. Hong, S. Schmalisch, H. A. Wegner, D. Mollenhauer, J. Janek, D. Schröder, Chem. Mater. 2018, 30, 762.  a) C. Batchelor-McAuley, Q. Li, S. M. Dapin, R. G. Compton, The journal of physical chemistry. B 2010, 114, 4094; b) H. Wang, R. Emanuelsson, A. Banerjee, R. Ahuja, M. Strømme, M. Sjödin, J. Phys. Chem. C 2020, 124, 13609.
Authors : M. Chakraborty1,2, S. Murcia-López1, J.R. Morante1,3, T. Andreu1,3
Affiliations : 1Catalonia Institute for Energy Research (IREC), Jardins de les Dones de Negre 1, Sant Adrià de Besós, 08930, Spain 2Universitat Autonoma de Barcelona (UAB), Plaça Cívica, Bellaterra, 08193, Spain 3University of Barcelona (UB), Martí i Franquès 1, Barcelona, 08020, Spain e-mail address: email@example.com
Resume : Redox flow batteries offer a reliable solution for future grid-scale energy storage due to its flexible design in decoupling energy and power independently. In comparison with mostly investigated and commercialized all vanadium redox flow batteries, aqueous zinc-iodide flow battery (ZIFB) is a highly promising contender due to its cost-effectiveness, environment friendliness, safety, and high energy density. Currently, it is possible to achieve a ZIFB with high energy density based on aqueous ZnI2 as an electrolyte. However, there are still obstacles to overcome before utilizing its full potential. Therefore, various research is ongoing to improve the battery design by optimizing its components towards the development of high-performance batteries. The electrolyte has a major contribution in scaling up the battery performance. Due to an imbalance of concentration of solutes between the anode and cathode compartments during charge-discharge cycling, the differential osmotic pressure results in water migration through the ion-permeable membrane from the compartment with lower ionic strength to the compartment with higher ionic strength, which is usually overlooked by using a static positive compartment, limiting its capacity. The addition of extra solute to the electrolyte solution is a way out to resolve this issue and reach an ionically balanced situation between two compartments. In this work, we have carried out the experimental analysis of a lab-scale ZIFB based on the theoretical ionic strength calculations to reach an overall balanced system. From the theoretical calculation, it has been proven that by adding extra potassium iodide (KI) to an electrolyte of 1:1 ZnI2:KI, the ionic balance between the compartments could be achieved. We have performed electrochemical impedance spectroscopy (EIS) as a tool to study the solution resistance and ionic conductivity of the half-cell compartments. Further, full cell cycling following post-mortem analysis of the half-cell electrolytes ensured no water migration between compartments during cycling of 60 hours, also exhibiting excellent voltage efficiencies. Moreover, low cost salt has been added to the electrolyte as an additive, for the purpose of longer cycling by improving the discharge capacity and reaction kinetics as well as suppressing improper zinc plating/stripping. Overall, the mechanisms of optimizing the electrolyte design, show a promising path to enhance the performance Zn-I2 flow batteries, which enlighten a step forward to the research in the next-generation aqueous flow batteries.
Anodes and SEI : Concetta Busacca
Authors : Solomon T. Oyakhire, William Huang, Yi Cui, Stacey F. Bent
Affiliations : Department of Chemical Engineering, Stanford University; Department of Materials Science and Engineering, Stanford University; Department of Materials Science and Engineering, Stanford University; Department of Chemical Engineering, Stanford University
Resume : The implementation of lithium metal batteries is hindered by the difficulty in controlling the Li metal plating microstructure. Ex-situ solid-electrolyte interphases (SEIs) have been shown to curtail the electrochemical instabilities of lithium, and atomic layer deposition (ALD) is useful for the synthesis of ex-situ thin-film SEIs such as alumina and alucone. However, these ALD-grown SEIs become delaminated as a result of their innate resistance to the cyclic shuttling of Li ions, resulting in marginal performance benefits. Herein, we report the use of ALD-grown titania as a nucleation layer, rather than as an artificial SEI. We show that by depositing titania directly on the Cu current collector, we can control the deposition morphology of Li in the widely studied ether-based electrolyte - 1M LiTFSi in an equal volume mixture of 1,3 dioxolane and 1,2 dimethoxyethane, with 1 weight percent of lithium nitrate as an additive. By optimizing the thickness of titania, we show that lithium nucleates into large deposits under reduced overpotential, resulting in a reduction in contact surface area with the electrolyte and an increase in cell performance. Furthermore, we report substantial improvements in cycling reversibility with an average Coulombic efficiency of 96% after 150 cycles at 1mA/cm^2 in Li/Cu cells. The performance of the titania film, and the origin of its effects as established by spectroscopy and microscopy techniques, will be reported and discussed.
Authors : Saravanan Karuppiah,1,2 Caroline Keller,1,2 Praveen Kumar,3 Gérard Lapertot,4 Pierre-Henri Jouneau,3 Peter Reiss,1 Cédric Haon,2 Pascale Chenevier1
Affiliations : 1 University Grenoble Alpes, CEA, CNRS, IRIG, SYMMES lab, 38000 Grenoble, France 2 University Grenoble Alpes, CEA, LITEN, DEHT, 38000 Grenoble, France 3 University Grenoble Alpes, CEA, IRIG, MEM, 38000 Grenoble, France 4 University Grenoble Alpes, CEA, IRIG, PHELIQS, 38000 Grenoble, France
Resume : Silicon is a promising anode material for increasing energy density in lithium-ion batteries that allows increasing the capacity of the anode by up to a factor of 10, and the overall energy density of the battery by up to 30%, as compared to standard graphite anodes. Absorption of high amounts of lithium in alloying induces a considerable volume change of silicon in lithiation, followed by pulverization of bulk silicon and fast decay of battery performance. Nanostructuration brings a valuable solution to this problem, since nanosized silicon appears to withstand lithiation and delithiation without fracturing. However, volume changes at the nanoscale can entail microscopic swelling and delamination of the anode. Our team proposes a composite of silicon nanowires (SiNW) and graphite obtained by direct growth of the SiNW on the graphite surface. Our compact androbust process  allows for the preparation of grams of composite containing up to 40wt% Si in a single step. This micropowder can directly enter in the slurry for the preparation of lithium battery anodes  following standard procedures. The composite was optimized for a specific capacity of 1000mAh/g, and holds more than 500 cycles at 2C (30 minute charge, 30 minute discharge). Full cells with NMC-622 cathode display a capacity retention of 70% over 300 cycles. The specific capacity retention is unusually high for silicon-rich anodes, thanks to the remarkably low swelling rate of our silicon-rich electrode in cycling, as was shown by FIB-SEM analysis. On-going work deals with optimization of SiNW size and shape  to lower the initial irreversible capacity, and with the replacement of the metal catalyst needed for SiNW growth from the classical gold nanoparticles to low-cost metals such as tin.  C. Keller et al., Nanomaterials 2021, 11, 307, 10.3390/nano11020307  S. Karuppiah et al., ACS Nano 2020, 14, 12006, 10.1021/acsnano.0c05198
Authors : Nurbol Ibadulla, Arailym Nurpeissova, Gulnur Kalimuldina, Zhumabay Bakenov
Affiliations : Nurbol Ibadulla & Arailym Nurpeissova - National Laboratory Astana, Nazarbayev University Gulnur Kalimuldina - Department of Mechanical and Aerospace Engineering, School of Engineering and Digital Sciences, Nazarbayev University Zhumabay Bakenov - Department of Chemical and Materials Engineering, School of Engineering and Digital Sciences, Nazarbayev University
Resume : As the portable electronics are high in demand, so are their characteristics such as battery life, speed, camera, storage, etc. Specifically, the battery is arguably the most important feature for most people as it is the one that keeps the piece of electronics on. Li-ion batteries (LIB) first commercialized in the early 1990s are still the market leaders, being the absolute life-saver nowadays. Although, these batteries also have several problems in terms of theoretical capacity, safety, cost, ageing, etc. The commercial graphite and Li4Ti5O12 anodes utilized in LIBs possess theoretical capacities of ~372 mAh/g and ~350 mAh/g, respectively, which is considerably low in comparison to other available anode materials . Other alternatives such as Sn (994 mAh/g), Si (4200 mAh/g), Sb (660 mAh/g), P (2596 mAh/g), Bi (667.3 mAh/g) show relatively high theoretical capacities, although they own other issues as well . The cons of the above-listed electrochemically active elements include high irreversible capacity, large capacity fading, poor cycling among other known issues. These issues are due to the considerable volume expansion of the anode that leads to the burst of the electrode, resulting in the death of the cell. In order to overcome the expansion, many suggestions have been offered. One of the common ways undertaken to prevent the volume expansion is enclosing the anode with another material. This has been realized in many ways such as encapsulation in hollow-shell, yolk-shell, core-shell spheres, core-shell nanotubes/nanofibers, suspension in carbon matrix, etc . In this work, the well-known method of electrospinning was employed to get Ni-Sn alloy-type anode enclosed by carbon nanofibers. Ni-Sn alloys obtained in this work, namely Ni1.6Sn and Ni3Sn, possess a theoretical capacity of ~554.6 mAh/g and ~400 mAh/g, respectively. Here, Ni-Sn intermetallic alloy acts as a buffering matrix against the volume expansion of Sn, i.e. Ni particles surrounding the Sn particles will stop the pulverization of the anode. SEM images and TEM images clearly show the encapsulation of the Ni-Sn particles inside the carbon nanofibers, while XRD confirms the formation of the NiSn alloy.
Authors : Manuel Schnabel (1), Terri C. Lin (1), Elisabetta Arca (1), Insun Yoon (1), Gabriel M. Veith (2), Xin He (1), and Robert Kostecki (1)
Affiliations : (1) Energy Storage and Distributed Resources Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA; (2) Oak Ridge National Laboratory, Oak Ridge, TN 37830, USA
Resume : Increasing the energy density of lithium-ion batteries (LIBs) is of great commercial interest, and one approach is to replace the standard graphitic intercalation anode with a material that alloys Li, such as silicon, since this promises nearly ten times greater energy density within the anode. While silicon is abundant and non-toxic, the durability of batteries with high silicon content is limited due to the unstable solid-electrolyte interphase (SEI) on silicon and its large volume change upon lithiation and delithiation which leads to cracking and pulverization. Among alloying anodes, amorphous materials generally outperform crystalline materials. The absence of grain boundaries can improve passivity, and amorphous materials generally lithiate in a continuous manner rather than as discrete lithiated phases, which eliminates strains at phase boundaries. In addition, amorphous metallic glasses have been shown to exhibit exceptional hardness, yield strength, and fracture toughness due to the absence of easy slip systems. This study explores an Al-Si-Mn glass as an alternative LIB anode. Si-based metallic glasses are appealing because they embed a significant and homogeneously distributed content of Si, which can alloy with up to 3.75 Li, within a matrix of other elements. A dense amorphous Al64Si25Mn11 metallic glass (a-AlSiMn) was successfully produced via splat quenching, a rapid cooling technique that is scalable and commonly used to produce amorphous materials for a variety of applications. The a-AlSiMn glass exhibits greater specific capacity (>800 mAh/g) than graphite and a low lithiation potential, making it suitable for high-energy density LIBs. XRD indicates that the material remains amorphous throughout cycling. A stable SEI was observed, with lower parasitic electrolyte decomposition currents than those observed on Al or Si anodes. The SEI is very thin, and rich in fluorinated species such as LiF, F-P-O groups, and fluorinated oxides of silicon and aluminum, whereas very few organic species are present. Most notably, no LiEDC is formed, resulting in a thinner and more stable SEI. This study demonstrates that metallic glasses provide a pathway to resolve both the interfacial instability and mechanical degradation issues that have traditionally plagued alloying anodes for LIBs.
Authors : Samson Y. Lai, Carl Erik L. Foss, Annette Thøgersen, Ingvild T. Jensen, Ola Nilsen, Jan Petter Mæhlen, Alexey Y. Koposov
Affiliations : Battery Technology Department, Institutt For Energiteknikk, Kjeller, Norway; Battery Technology Department, Institutt For Energiteknikk, Kjeller, Norway; SINTEF Industry, Oslo, Norway; SINTEF Industry, Oslo, Norway; Department of Chemistry/Centre for Materials Science and Nanotechnology, University of Oslo, Oslo, Norway; Battery Technology Department, Institutt For Energiteknikk, Kjeller, Norway; Department of Chemistry/Centre for Materials Science and Nanotechnology, University of Oslo, Oslo, Norway
Resume : Coating of silicon has been an active area of pursuit in research for advanced lithium-ion battery (LIB) anodes. Such surface modifications can serve different purposes to varying degrees, such as constraining the volumetric expansion of Si during lithiation, enhancing electronic conductivity, and/or establishing a more stable solid-electrolyte interface (SEI). Among various techniques used to create conformal coatings of the battery materials, atomic layer deposition (ALD) is a unique method, which allows precisely controlling the coating thickness. This property allows one to balance between the interplay of SEI stability and increased resistivity from thicker coatings. It also can conformally coat complex substrate geometries, including high aspect ratios, such as casted porous electrodes with high tortuosity. The key question remains: how the electrochemical performance, stability, and degradation pathways are altered as a function of the thickness for different types of coatings delivered by ALD. In this study, several types of coating have been explored in view of their stabilization effects for Si-based anodes. TiO2, perylene, and UiO-66 (a metal-organic framework) of varying thicknesses (2 nm, 5 nm, 10 nm, and 20 nm) were deposited by ALD as thin film coatings on 40-, 60-, and 80-nm thin film Si electrodes. The thin film model was chosen as a model system to understand the performance viability, degradation pathways, and thickness or size effect of the Si substrate. TiO2 is a well-known, state-of-the-art ALD coating and active material for LIB, which has high SEI stability and offers ionically conductive pathways for Li+ transport. Perylene is a polycyclic aromatic hydrocarbon which can be deposited by ALD and potentially offers high stability due to this polycyclic structure. Lastly, UiO-66 is a metal-organic framework, which has attracted significant attention due to its material properties, including a stable Zr cation which is redox inactive and potential flexibility. The thin film electrodes prepared through such deposition were electrochemically evaluated in half cells, followed by extensive post-mortem characterization by cross-section SEM and XPS. The thickness of the Si thin film electrode had a strong effect on the stability enhancement of the ALD coating: most of the TiO2 coatings enhanced 40-nm Si electrodes while only the 20-nm TiO2 significantly enhanced the capacity of the 80-nm Si electrode. However, even a 2-nm TiO2 coating was beneficial for any Si thin film thickness. Post-mortem cross-section SEM and XPS revealed the structural degradation of the Si electrode and increased density of fluorine-containing surface deposits for thicker TiO2 coatings. Perylene coatings of 3 nm and 10 nm slightly reduced the lithiation capacity with no significant effect on lifetime. UiO-66 also reduced the lithiation capacity of 40-nm Si, but it had less of an effect on 80-nm Si.
Authors : Maresca, G.* (1,2), Di Schiavi, A. (3), Simonetti, E. (1), Brutti, S. (3,4), Paolone, A. (4), Palumbo, O. (4), Fantini, S. (5), Lin, R. (5), Martin, P.A. (5), Falgayrat, A. (5), Choi, H. (6,7), Kuenzel, M. (6,7), Passerini, S. (6,7), Sankaran, A. (1), Geaney, H. (8), Ryan, K.M. (8), Appetecchi, G.B. (1).
Affiliations : (1) ENEA, Materials and Physicochemical Processes Technical Unit (SSPT-PROMAS-MATPRO), Via Anguillarese 301, 00123, Rome, Italy; (2) La Sapienza University of Rome, Department of Basic and Applied Sciences of Engineering, Piazzale Aldo Moro 5, 00185, Rome, Italy; (3) La Sapienza University of Rome, Department of Chemistry, Piazzale Aldo Moro 5, 00185, Rome, Italy; (4) Consiglio Nazionale delle Ricerche, Istituto dei Sistemi Complessi Piazzale Aldo Moro 5, 00185, Rome, Italy; (5) Solvionic SA, Site Bioparc Sanofi, 195 Route d?Espagne, BP1169, 31036, Toulouse Cedex 1, France (6) Helmholtz Institute Ulm (HIU), Helmholtzstrasse 11, 89081, Ulm, Germany (7) Karlsruhe Institute of Technology (KIT), P.O. Box 3640, 76021, Karlsruhe, Germany (8) Materials and Surface Science Institute and the Department of Chemical and Environmental Sciences, University of Limerick, V94 T9PX Limerick, Ireland
Resume : The increasing demand of high-energy density electrochemical energy storage systems is pushing up the development of new materials for lithium-ion batteries . The research is focusing on large-capacity anodes  and high-voltage cathodes (above 4 V vs. Li+/Li°) . In the meantime, safer and more reliable electrolyte systems are required for overcoming the safety issue of the organic electrolytes. A promising strategy is represented by the use of ionic liquids (ILs) as electrolyte components . In this work different IL families, combining imidazolium and tetra-alkyl-ammonium cations with per(fluoroalkylsulfonyl)imide anions, were specifically designed and investigated as electrolyte materials for safer high-energy density and high-voltage (> 4.5 V) Li-ion batteries. The compatibility of the developed electrolyte formulations towards silicon nanowire anodes and lithium-rich layered oxide (Li1.2Ni0.2Mn0.6O2) cathodes were studied (in Li half-cells) through charge-discharge cycling, cyclic voltammetry and impedance spectroscopy. Acknowledgements The authors would like to acknowledge the financial support from the European Union within the Si-DRIVE project. This project has received funding from the European Union?s Horizon 2020 research and innovation program under grant agreement No. 814464.  M. Armand, J. M. Tarascon, Nature 2008, 451, 652?657.  R. A. Huggins, J. Power Sources 1999, 81?82, 13?19.  N. Rapulenyane, E. Ferg, H. Luo, J. Alloys Compd. 2018, 762, 272?281.
Other : Gianluca Leonardi
Authors : Tsuyoshi Hoshino
Affiliations : Breeding Functional Materials Development Group, Department of Blanket Systems Research, Rokkasho Fusion Institute, Fusion Energy Directorate, National Institutes for Quantum and Radiological Science and Technology (QST), 2-166, Obuchi, Omotedate, Rokkasho-mura, Kamikita-gun, Aomori, 039-3212, Japan
Resume : In recent years, the industrial importance of Li has increased due to its use in Li ion batteries. I propose new method for recovering Li from used Li-ion batteries by using Li separation method by ionic conductor; LiSMIC. Li ionic conductor is functioned as a Li separation membrane. This innovative LiSMIC involves the use of an Li separation membrane whereby only Li ions in a solution of used Li-ion batteries permeate from the positive electrode side to the negative electrode side during electrodialysis; the other ions, including Co, Al, and F, do not permeate the membrane. Li ionic conductor is functioned as a Li separation membrane. Li0.29La0.57TiO3 (LLTO) was selected as the Li separation membrane. However, Li permeation speed is low. Therefore, I developed the advanced LLTO for the Li recovery from used Li-ion batteries. To develop the LLTO with Li adsorptive performance, the surface of LLTO was dipped in 2 M HCl for 5 days at 333 K. After dipping, LLTO was changed to HxLa0.57TiO3 (HLTO) with Li adsorptive performance. The applied dialysis voltage was 5 V, and the electrode area was 16 cm2. Measurements of the Li ion concentration at the negative electrode side showed that the Li recovery ratio increased to approximately 90% after 72 h. The lithium recovery speed has improved from the conventional 0.01 mg / hour to 1.8 mg / hour, and the recovery rate has been successfully increased 200 times. Thus, LiSMIC is most suitable for the Li recycling of used Li-ion batteries, and we have established a Li separation membrane technology that can recycle used Li-ion batteries that require mass processing in the future. This technology contributes to the recycling of Li resources in Li-ion batteries and is a major achievement that opens up prospects for the construction of a sustainable Li recycling society for Li, for which demand is expected to grow further in the future.
Authors : Maribel Touron, Leslie Castillo Iracheta, Caroline Celle, Jérôme Faure-Vincent, David Aradilla, Jean-Pierre Simonato
Affiliations : Univ. Grenoble Alpes, CEA, LITEN/DTNM, F-38054 Grenoble; France; Univ. Grenoble Alpes, CEA, INAC/SYMMES; Univ. Grenoble Alpes, CEA, LITEN/DTNM, F-38054 Grenoble; Univ. Grenoble Alpes, CEA, INAC/SYMMES, F-38054 Grenoble, France; Univ. Grenoble Alpes, CEA, LITEN/DTNM, F-38054 Grenoble; University of Göttingen, UGOE Institut of Inorganic Chemistry, Göttingen, Germany; Univ. Grenoble Alpes, CEA, LITEN/DTNM, F-38054 Grenoble
Resume : Due to their very low density and high porosity therefore high specific area, porous structures such as aerogels have attracted significant attention. The first applications explored in the seventies were for sound and heat insulation. After, other applications emerged from the literature for catalysis, filtration and sensors. Lately, the interest for a new class of materials that exhibits very light-weighed and electrical conductive properties has grown to attend the demand of storage energy and sensors. Electrically conductive aerogels can be synthetized from conductive polymers, conductive particles or insulant polymers loaded with conductive particles. Particles with high aspects ratios (trade-off between length and diameter) can form percolated networks at lower loadings. Which results in aerogels with lower densities. The percolated network of particles formed is a three-dimensional (3D) and highly porous. Herein new aerogels made by pure silver nanowires (AgNW) and by AgNW-based nanocomposites with high electrical conductivity and high porosity are studied. Silver is the most conductive metal and has been widely reported in the literature for nanowires synthesis. Our laboratory has a strong knowledge of synthesis and integration of nanomaterials, especially metallic nanowires with high aspects ratios. The method presented is based on the assembly of 1D AgNW into a 3D networks from concentrated suspensions in water by a simple freeze-drying process. Aerogels made of AgNWs and AgNWs embedded into polymers were compared to improve the electrochemical and mechanical properties of the electrodes. The unique structures obtained are defined by their very high porosity (>99%), very low densities (< 40 mg/cm3) and high electrical conductivities (hundreds of S/cm). These properties coupled with the ability of Ag to form very Li-rich alloys (up to Li33Ag) could make AgNW-based aerogels new promising 3D structures for efficient battery electrodes. Solid state batteries with Li-metal as negative electrodes present high energy density and power density. But their broad commercialization is limited by safety issues due to short circuits induced by Li dendritic growth. The porosity of AgNW-based aerogels allows a better homogeneity of the potentials in the electrode and therefore prevent the dendritic growth. First, we will present the AgNW synthesis and the fabrication process of the aerogels. Then, the link between structure and physical properties (density, electrical and mechanical properties) will be studied to bring a better understanding of the effect of the network density. Post-curing treatment and hybridation with polymers will also presented. Finally, the first electrochemical characterisations will be shown in order to present the interest of such 3D nano-networks for high efficiency Li-ion batteries electrodes.
Authors : Grageda Mario, Llusco Aleksei, Rojas Luis
Affiliations : Departamento de Ingeniería Química y Procesos de Minerales and Center for Advanced Study of Lithium and Industrial Minerals (CELiMIN), Universidad de Antofagasta, Campus Coloso, Av Universidad de Antofagasta 02800 Antofagasta (Chile)
Resume : In this work, Mg(OH)2 purified from waste generated in the production of Li2CO3 using natural brines from the Salar de Atacama, Chile, was used as a doping agent for the synthesis of LiMn2O4 nanoparticles co-doped with excess Li and Mg. Mg insertion decreased the thermal conductivity of prepared precursors; this resulted in the formation of an oxocarbonate phase instead of a pure spinel phase. CO2 desorption was achieved with a prolonged calcination process and the crystallization of a pure cubic spinel phase (Fd-3m) took place at 500 °C. The spinel powders obtained were sintered at 580 °C and 750 °C. The effect of the heat treatment schedules on elemental composition and the structural, morphological and electrochemical properties of synthesized samples were studied in detail. Primary particles from all synthesized samples exhibited a truncated octahedral crystal habit defined by the low index surfaces (111), (110) and (100). Optimum electrochemical performance at room temperature was obtained for Li1.03Mg0.05Mn1.92O4 spinel sintered at 750 °C with an initial discharge capacity of 121.3 mAh g-1 and a retention capacity of 94.0 % after 100 cycles at C/3. A locally ordered spinel structure was obtained at 750 °C, and Mg doping improved the structural rigidity; synergy between both effects resulted in a high Li+ diffusion rate (1.29 x 10-9 cm2 s-1) that significantly improved the cycling performance at high C-rates and 50 °C.
Authors : Pengfei Yan, Tao Ying
Affiliations : Shanghaijiaotong university
Resume : Magnesium alloy is a promising material for light-weight bipolar plates of proton exchange membrane fuel cell (PEMFC) owing to its low density, but high susceptibility to corrosion limits the application. In this paper, a novel hydrophobic Polytetrafluoroethylene (PTFE)/Carbon cloth/Ag multilayer coating is fabricated on Mg substrate. Potentiodynamic polarization results reveal that the multilayer coating decreases the corrosion current density of bare Mg dramatically from 17.24 ?A/cm2 to 0.058 ?A/cm2, meanwhile, the interfacial contact resistance (ICR) between carbon paper and coated magnesium drops from 100.6 m? cm2 to 27.28 m? cm2 at 1.4 MPa. The mechanism of the superior corrosion resistance and electrical property of coated Mg is discussed, which may shed light on the development of the novel light-weight magnesium bipolar plates of PEMFC.
Institute for Energy Technology, Instituttveien 18, 2007 Kjeller, NorwayAlexey.Koposov@ife.no
Via Salita Santa Lucia Sopra Contesse, 5-98126 Messina, Italydurso@itae.cnr.it
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