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Functional materials

E

Sustainable materials for chemical and electrochemical energy storage

Sustainable technologies for energy storage such as batteries, hydrogen storage, thermal storage or power-to-X solutions are dependent on advanced functional materials. Dwindling resources and increased focus on sustainability put new requirements on the functional materials.

Scope:

The transition from fossil-fuel based energy towards renewable energy technologies have brought a strong urge for energy storage materials offering efficient, long-lived, safe and environmentally benign energy storage. This task requires advanced materials, and their development entails detailed understanding of the chemical and physical properties over multiple length-scales, i.e. form the atomic to the micron scale. Furthermore, to truly offer sustainable energy storage solutions, the functional materials themselves must also be sustainable. This set new requirements for the material design in terms on the abundancy of the required resources, the environmental impact of the material production and the potential for material recycling and disposal within a frame of circular economy. 

This symposium will bring together various fields within energy storage materials, e.g. batteries, hydrogen storage, thermal storage and power-to-X solutions. The symposium will span theoretical modeling, material preparation and recycling routes, structural characterization, property analysis and device fabrication. The overarching focus will be on material sustainability from cradle to grave and hereunder routes for material recycling.   

The proposed symposium is highly interdisciplinary and aspires to bring together ambitious young and established scientists from around the world to not only present the latest advances of the intense worldwide research but also exchange ideas as well as identify major challenges and hot-topics for future developments towards efficient solutions. We envision that bringing together researcher across the field of energy storage material will seed new research directions.

Hot topics to be covered by the symposium:

  • Environmentally benign battery materials
  • Post-lithium ion battery technologies
  • Flow-batteries
  • Hydrogen storage
  • Thermal energy storage
  • Materials for power-to-x technologies
  • Supercapacitors and metal-ion capacitors
  • Raw material supply / value chains
  • Advanced manufacturing of batteries
  • Recycling of batteries
  • Material regeneration/refurbishment

Confirmed invited speakers:

  • Christian Masquelier, Universite de Picardie Jules Verne, France
  • Rosa Palacin, Institute of Materials Science of Barcelona, Spain
  • Petra De Jongh, Utrecht University, Holland
  • Yuanzheng Yue, Aalborg University, Denmark
  • Montse Casas-Cabanas, CIC Energigune, Spain
  • Elie-Elisee Georges Paillard, Politecnico di Milano, Italy
  • Magda Tirici, Imperial College London, United Kingdom
  • Marek Polanski, Military University of Technology, Poland
  • Michele Remo Chierotti, University of Turin, Italy
  • Francesca Toma, Lawrence Berkeley National Laboratory, USA
  • Sally Brooker, University of Otago, New Zealand
  • Yoon Seok Jung, Yonsei University, Seoul, Korea

Scientific committee:

  • William Brant, Uppsala University, Sweden,
  • Sondre Schnell, NTNU, Norway
  • Fermin Cuevas, ICMPE, France
  • Kasper Møller, Aarhus University, Denmark
  • Chiara Malanese, University of Pavia, Italy
  • Inga Burger, German Aerospace Center, Germany
  • Erika Michela Dematteis, University of Turin, Italy

Publication:

Symposium proceedings will be pulbished in a special issue of Journal of Materials Science.

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09:05
Authors : S. Park, [1,2,3], Z. Wang [4], Z. Deng [4], P. Canepa [4], F. Fauth [5], D. Carlier [2], L. Croguennec [2], J.N. Chotard [1], C. Masquelier [1]
Affiliations : [1] LRCS Amiens, France; [2] ICMCB Bordeaux, France; [3] TIAMAT Energy; [4] NUS Singapore; [5] ALBA Synchrotron, Spain

Resume : Polyanionic materials (phosphates in particular) are of special interest as positive electrodes for Li-Ion or Na-ion batteries since they offer competitive performances compared to sodiated or lithiated transition metal oxides[1,2]. They are based upon stable 3D frameworks, which provide long-term structural stability thanks to a unique variety of atomic arrangements. Recent electrochemical and structural investigations of vanadium-based compounds (LiVPO4O-LiVPO4F, Na3V2(PO4)2F3, Na3V2(PO4)3 …..) revealed promising perspectives[3-5]. The NASICON structural family with its large panel of compositions, NaxMM’(PO4)3 (0

E.1.1
09:45
Authors : Thomas Thersleff (1), Jordi Biendicho (2), Kunkanado Prakasha (2), Evgeniya Khomyakova (3), Jekabs Grins (1), Aleksander Jaworski (1), Gunnar Svensson (1)
Affiliations : (1) Department of Materials and Environmental Chemistry, Arrhenius Laboratory, Stockholm University, SE – 10691 Stockholm, Sweden; (2) Catalonia Institute for Energy Research-IREC, Sant Adrià de Besòs, 08930 Barcelona, Spain; (3) Cerpotech, Kvenildmyra 6, 7093 Heimdal, Norway

Resume : Due to high toxicity and controversial mining practices, energy storage materials such as high capacity battery cathodes containing cobalt are increasingly becoming unviable in the sustainable economy. This is particularly true of the layered manganese oxides such as LiNi(1/3)Mn(1/3)Co(1/3)O2 which, with their high capacity, would otherwise be ideal. While Co-free layered manganese oxides such as Li1.1Mn0.55Ni0.35O2 (LMNO) exist, these currently suffer from poor cycling stability and sluggish kinetics, reducing their longevity and, consequently, competitive edge. A route to improve the performance of these Co-free materials is thus of paramount importance. Key to the high performance of the layered manganese oxides is their ability to maximize the energy density of the cathode via nanoscale mixing of two structurally compatible components: a monoclinic C2/m Li2MnO3-like phase (M-phase) and a rhombohedral R-3m LiMn(1/2)Ni(1/2)O3-like phase (R-phase). Recently, we demonstrated that we can influence the morphology and distribution of these phases in Co-free LMNO on a particle-level scale through use of a spray-pyrolysis synthesis approach combined with targeted thermal calcination [1]. This approach segregates the Ni-rich R-phase to the outer surface of the LMNO nanoparticles, reducing structural degradation over the cyclic lifetime and ultimately delivering 160 mAhg-1 and 100 mAhg-1 at C/3 and 1C, respectively, with 80% capacity retention after 150 cycles. In this work, we further explore the potential performance improvements to LMNO that can be achieved by complementing the previous synthesis engineering approach with chemical doping with Al and Sn. We observe that low amounts of Al doping can increase the discharge capacity up to 187 mAhg-1 with a capacity retention in the same batch of 94.3% after 150 cycles. By studying a series of dopant concentrations from both species with a wide range of advanced characterization techniques, with a heavy emphasis on state-of-the-art advanced transmission electron microscopy methods, we are able to piece together a more comprehensive picture for the nanoscale structural and chemical origins of this performance increase, which we currently attribute to the dopant-dependent size distribution and composition of the two structural phases via the emergence of nanodomains. We conclude by exploring the prospects that this approach can be generalized to customize the nanoscale landscape and, subsequently, tune the electrochemical performance of all layered manganese oxide systems. [1] K. Rajappa Prakasha, J. Grins, A. Jaworski, T. Thersleff, G. Svensson, L.O. Jøsang, A.D. Dyrli, A. Paulus, D. De Sloovere, J. D’Haen, M.K. Van Bael, A. Hardy, H. Avireddy, J.R. Morante, J. Jacas Biendicho, Temperature-Driven Chemical Segregation in Co-Free Li-Rich-Layered Oxides and Its Influence on Electrochemical Performance, Chem. Mater. (2022). https://doi.org/10.1021/acs.chemmater.1c04150.

E.1.2
10:00
Authors : Morten Johansen, Dorthe B. Ravnsbæk
Affiliations : Department of Chemistry, Aarhus University, Langelandsgade 140, 8000 Aarhus C, Denmark

Resume : Traditional materials for rechargeable Li-ion battery electrodes are based on well-ordered crystalline materials containing scarce elements such as lithium and cobalt [1]. The strong focus on crystalline electrode materials have caused disordered/amorphous electrode materials to be overlooked in the past [2]. Thus, a number of well-performing, cheap and environmentally friendly materials may have been missed as candidates for rechargeable Li-ion battery electrodes. In this study, we have synthesized a monoclinic vanadium oxide, VO2(M), via thermal treatment of a non-distorted rutile VO2 phase and employed it as a cathode against a Li-metal anode. VO2(M) displays an irreversible broadening and loss of scattered intensity in the Bragg reflections when Li-ions are intercalated into the structure. This behavior is very similar to the disordering behavior of closely related rutile TiO2 electrodes, as reported by Christensen, et al. [3]. Similar to the TiO2 structure, VO2(M) has channels for Li migration along one crystallographic axis [4]. To investigate the irreversible order-disorder transformation in VO2(M), we collect operando powder x-ray diffraction and total scattering data during charge and discharge, i.e. Li-ion insertion and extraction, using an AMPIX battery test cell [5]. The data is analyzed using Rietveld refinement and pair distribution function analysis (PDF), respectively. The irreversible phase transformation begins after inserting 0.17 Li/V or approximately two hours into the first discharge at C/12. The broadening of the Bragg reflections increases with continuous intercalation of Li-ions. The subsequent complete charge and discharge look similar from the scattering, which indicate that after the irreversible disordering process, a reversible phase transition occurs in the disordered state. References [1] D. Larcher, et al., Nat Chem 2015, 7 (1), 19-29. [2] C. K. Christensen, et al., Journal of Physics: Energy, 3 (2021). [3] C. K. Christensen, et al., Nanoscale 2019, 11 (25), 12347-12357. [4] W. Li, et al., Journal of Alloys and Compounds, (2020), 812. [5] O. J. Borkiewicz, et. al., Journal of Applied Crystallography 2012, 45 (6), 1261-1269

E.1.3
10:15
Authors : Yang Xu, Runzhe Wei, Xingwu Zhai, Gopinathan Sankar, Min Zhou
Affiliations : Dr Yang Xu; Runzhe Wei; Prof. Gopinathan Sankar; Department of Chemistry, University College London, London WC1H 0AJ, UK Xingwu Zhai; Prof. Min Zhou; Hefei National Laboratory for Physical Sciences at the Microscale, School of Chemistry and Materials Science, University of Science and Technology of China, Hefei, Anhui 230026, China

Resume : Potassium Prussian blue analogue (K-PBA) KxFeFe(CN)6 is a sustainable and high-performance cathode material for K-ion batteries (KIBs), because K-PBA is non-toxic, based on earth-abundant elements, and has the structural remits to allow fast migration of large-sized ions. Interestingly, K-PBA has been recently demonstrated to be an appealing cathode for Na-ion batteries (NIBs). In such a hybrid NIB cell, where Na+ is in the electrolyte and K+ is in the cathode, although ion intercalation in K-PBA has been proven feasible, it can be significantly affected by the [Fe(CN)6]4- anion vacancies present in K-PBA. In this regard, two K-PBAs were synthesized via a precipitation method, and their anion vacancy levels were adjusted by changing the precipitation temperature. Electrochemical tests indicated that K-PBA with 25% anion vacancies exhibited two ion intercalation steps, and both steps were dominated by K+, displaying a ~0.2 V increase in the intercalation voltage compared with the voltage of Na-PBA in a NIB cell. In contrast, K-PBA with 7% anion vacancies exhibited a split intercalation at the lower voltage range (<3.2 V vs. Na+/Na), showing a K+ dominating intercalation above 2.8 V and a Na+ dominating intercalation below 2.8 V. Electrode characterizations and theoretical calculations suggested that the different ion intercalation processes are caused by the K+ kinetics regulated by [Fe(CN)6]4- anion vacancies. A higher vacancy level enhances K+ diffusion in the PBA framework, which facilitates K+ intercalation and suppresses Na+ intercalation. A lower vacancy level deteriorates K+ diffusion and thus enhances Na+ intercalation. As a result, in the NIB cell, the K-PBA cathode with a higher vacancy level delivered the capacities of 120 and 63 mAh g-1 at 50 and 500 mA g-1, respectively, as well as retained 87% capacity after 100 cycles at 25 mAh g-1, which completely outperformed the K-PBA cathode with a lower vacancy level. This work demonstrates that hybrid battery systems could have the promise in improving electrochemical performance, and vacancy regulation is crucial for cathode materials to deliver the performance improvement.

E.1.4
10:30 Coffee break    
11:00
Authors : D. Saurel1, M. Reynaud1, M. Galceran1, C. Berlanga1,2, E. Gucciardi1, J. Carrasco1, A. Wizner1,2, M. Casas-Cabanas1,3
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 Science and technology faculty, Basque Country University (UPV/EHU), 48940 Leioa, Bilbao, Spain; 3 Ikerbasque, The Basque Foundation for Science, 48013 Bilbao, Spain

Resume : The global rise of Li-ion battery (LIB) production is linked with a number of challenges, and in particular the growing risks of demand-supply mismatch and supply constraints of the raw materials. Within this scenario, Na-based batteries are rising as potential complementary technology to Li-ion batteries, as the combination of attractive properties potentially NIBs offer (i.e., low cost, sustainable precursors and secure raw material supplies), could represent an important step forward towards beyond Li technologies. Na-ion chemistry suffers however from some intrinsic drawbacks compared to Li-ion (heavier and larger alkali ion, 0.33V larger standard potential) which tend to lower cell voltage and capacity. Nevertheless, with ongoing development, materials available for Na-ion cells are approaching the energy density of the present generation of Li-ion commercial cells. In this talk, the potential of Na-ion batteries will be thoroughly analyzed and our recent research regarding positive and negative electrode materials will be reviewed. Results related to several phosphate-based families of cathode materials will be shown, together with the challenges of developing competitive anode materials. Finally, the use of high-throughput approaches applied to the screening and design of electrode materials for NIBs will also be discussed.

E.2.1
11:30
Authors : Srikanth Mateti, Baozhi Yu, Ye Fan, Qiran Cai, Ying Chen*
Affiliations : Institute for Frontier Materials, Deakin University, 3216, Victoria, Australia.

Resume : Current energy technologies rely on producing more than one billion lithium-ion batteries every year to power consumer electronics alone. The major challenge we face is the unsatisfactory energy density and slow charging performance of current lithium-ion batteries; they cannot meet the increasing demands from widespread and emerging applications, including electric vehicles, portable devices (i.e., smartphones), and many industry tools. One main goal is to develop new safe, efficient, and sustainable energy storage and conversion technologies to eliminate the severe fire risk and environmental issues caused by current technologies. This talk covers our research to address the above issues mentioned. We provide a new configuration strategy for the modification of conventional polyolefin separators by simply incorporation of appropriately engineered long and fine boron nitride nanotubes (BNNTs) without blocking the porous channels of the conventional separator for Li+ ion diffusion. This new BNNT separator exhibits improved thermal stability up to 150 °C, ensuring the safe operation of LIB cells at elevated temperatures [1]. Further Ion gel electrolytes show great potential in solid-state batteries attributed to their outstanding characteristics. However, because of the strong ionic nature of ionic liquids, ion gel electrolytes generally exhibit low lithium-ion transference number, limiting its practical application. Amine-functionalized boron nitride (BN) nanosheets (AFBNNSs) are used as an additive into ion gel electrolytes for improving their ion transport properties [2]. Moreover, migration of cycling intermediates (polysulfides) from the cathode to anode through a separator is one of the main problems in current lithium–sulfur batteries that deteriorates cycling performance of the cell. Here we report a multifunctional separator, which is constructed by incorporation of functionalized boron nitride nanosheets with negatively charged groups onto a commercial Celgard separator. The boron nitride separator is capable to prevent polysulfide migration through the separator effectively due to strong ion repelling of negatively charged polysulfides by the negatively charged boron nitride nanosheets. The lithium–sulfur cell with a boron nitride separator exhibits an excellent long-term cycling stability up to 1000 cycles and a high capacity of 718 mA h g–1 at a very high current of 7 C (1.18 A g–1) [3]. References: 1. M.M. Rahman, S. Mateti, Q. Cai, I. Sultana, Y. Fan, X. Wang, C. Hou, Y. Chen, “High temperature and high-rate lithium-ion batteries with boron nitride nanotubes coated polypropylene separators”, Energy Storage Materials, 19, 2019, 352-359. 2. D. Kim, X. Liu, B. Yu, S. Mateti, L. A. O’Dell, Q. Rong, Y. Chen, “Amine-functionalised boron nitride nanosheets: A new functional additive for robust, flexible ion gel electrolyte with high lithium-ion transfer number”, Advanced Functional Materials, 30, 2020, 1910813. 3. Y. Fan, M. M. Rahman, T. Tao, W. Li, S. Mateti, B. Yu, J. Wang, C. Yang, Y. Chen, “Repelling polysulfide ions by boron nitride nanosheet coated separators in lithum-sulfur batteries”, ACS Applied Energy Materials, 2, 2019, 2620-2628.

E.2.2
11:45
Authors : Jie Zheng, Rui Xia, Najma Yaqoob, Qianyuan Qiu, Yongdan Li, Kangning Zhao, Payam Kaghazchi, John E ten elshof and Mark Huijben
Affiliations : Jie Zheng, Rui Xia, Payam Kaghazchi, John E ten elshof and Mark huijben: MESA Institute for Nanotechnology, P. O. Box 217, Enschede 7500AE, University of Twente, Netherlands; Najma Yaqoob and Payam Kaghazchi: Forschungszentrum Jülich GmbH, Institute of Energy and Climate Research, Materials Synthesis and Processing (IEK-1), Jülich 52425, Germany; Qianyuan Qiu and Yongdan Li: Department of Chemical and Metallurgical Engineering, Aalto University, Kemistintie 1, FI-00076, Aalto, Finland; Kangning Zhao: State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, International School of Materials Science and Engineering, Wuhan University of Technology, Wuhan, 430070, China.

Resume : Wadsley-Roth phase titanoniobate is proposed to be one of the attractive anodes for fast-charging lithium-ion batteries due to its high theoretical capacity as well as the suitable channels for Li diffusion. Cation substitution is one of the most common used strategies for improving fast-charging ability of Wadsley-Roth phase titanoniobate anodes. In our work, the effect of iron substitution in Ti2Nb10O29 is uncovered from the novel aspect of decreasing the calcination temperature and thus shortening the length of Li diffusion channels with the smaller grains, which plays a significant role in optimization of the fast-charging ability. The pure Wadsley-Roth phase is obtained at 1000 ℃ with the certain degree of iron substitution (Fe: Ti: Nb = 0.4: 1.6: 10, denoted as FTNO1.6-1000) while a higher temperature is required for pristine TNO (e.g., 1100 ℃, denoted as TNO-1100). Benefiting from the reduced grain size along the diffusion channel, FTNO1.6-1000 presents enhanced rate ability with reversible capacity of 73.7 mAh g-1 at 50 C compared to the 1100 ℃ counterpart. Various electrochemical models confirm the improved diffusion coefficient and the reduced possibility of generating overpotential in FTNO1.6-1000. Furthermore, another novel effect of iron substitution is revealed by detailed operando XRD analysis, which indicates that the lattice variation during lithiation can be suppressed along a-direction. DFT calculations confirm and provide a theoretical explanation. Thus, FTNO1.6 electrodes exhibit enhanced durability after extended cycling at both 2 C and 10 C. Our work provides a simple strategy to improve not only the fast-charging ability but also the structural stability by iron substitution.

E.2.3
12:00
Authors : Wilgner L. da Silva, Emma Kendrick, Richard Walton
Affiliations : Department of Chemistry and Warwick Manufacturing Group, University of Warwick, Gibbet Hill Road, Coventry CV4 7AL, United Kingdom; School of Metallurgy and Materials, University of Birmingham, Edgbaston, Birmingham B15 2TT, United Kingdom; Department of Chemistry, University of Warwick, Gibbet Hill Road, Coventry CV4 7AL, United Kingdom

Resume : With electrification of society, the discovery of materials with higher energy densities, Li-ion storage capacities, and substantial stability at low voltages compared to graphite (theoretical capacity of 372 mA·h/g) is essential, but greener synthetic routes must also be the way forward. Herein, we report the hydrothermal synthesis of a novel rutile Fe2+/3+0.8Nb1.5O4.6 (FNO1) at 240 C for 48 hours in basic solution using stoichiometric ratios of Nb/Fe precursors. Rutile FNO1 crystalises in a disordered structure with corner- and edge-shared octahedral metals in the space group P42/mnm [1]. Nb/Fe atoms are randomly distributed over the octahedral sites in the tetragonal unit cell. When annealed in air, FNO1 collapses to a monoclinic FeNbO4 and Nb2O5 at temperatures above 750 C, due to Fe oxidation. This metastable FNO1 structure, when annealed under N2, transitions to an orthorhombic polymorph (FNO2) or an Fe columbite structure at 700 C. The orthorhombic polymorph has a layered structure of slightly distorted hcp oxygen sublattice with octahedral metal sites in the space group Pbcn [2]. 57Fe Mössbauer spectroscopy confirms that FNO1 has 90 % of Fe2+ and the remainder is Fe3+. More than 3 Fe sites are distinguished, revealing a complex disorder. FNO2 has similar proportions of the two oxidation states, with Fe2+ sites in a range of 92 to 97 %, and Fe3+ sites in between 8 to 3 %. X-ray absorption near edge structure (XANES) of a series of samples were analysed to determine phase stability under different annealing temperatures below (400 C) or above phase transition (900 C), and atmospheres (air or N2). For all samples, Nb K-edge XANES corresponds to Nb5+. The Fe K-edge showed that all samples annealed under N2 have oxidation state closer to 2+, but when annealed in air, Fe oxidises to 3+ above 400 C. EXAFS fitting agrees with Rietveld refinement, and only a disordered Fe/Nb crystal structure accounts for the local and bulk FNO1 crystal structures. On the other hand, an ordered columbite crystal structure provides a good agreement with the sintered FNO2 under N2. There is indication of Nb/Fe ordering within the stacking layers. Scalability to a few grams of sample was feasible using 200 mL stainless steel autoclaves, and the large batch samples were used to prepare an ink. A slurry composition was made of 80 % of active material, 10 % of C65 and 10 % of binder (PVDF in NMP), which was coated onto Cu foil. 15 mm discs were cut and assembled into coin cells. Cyclability (200 cycles) and capacity retention at various current densities were performed. The samples show different electrochemical performances because of their structures. FNO1 has the first discharge capacity (lithiation) above 600 mA·h/g and FNO2 above 300 mA·h/g. The theoretical capacity for both samples are 468 mA·h/g, corresponding to the insertion of 4.5 Li+ to reduce Nb5+ to Nb2+. However, these samples have different Li-ion mechanism upon insertion, which were characterised by ex-situ X-ray diffraction. FNO2 has better structural stability than FNO1, showing characteristics of an insertion type electrode. FNO1, in contrast, becomes less crystalline when discharge to 0.005 V. This amorphisation process could be related to a conversion type mechanism upon Li insertion. References: [1] Tealdi, C. et al. Columbite-type FexMn1-xNb2O6 Solid Solution: Structural and Magnetic Characterization. Physical Chemistry Chemical Physics 6, 4056-4061 (2004). [2] Hansen, S., et al. Cation Ordering Waves in Trirutiles - When X-ray Crystallography Fails. Acta Crystallographica Section A 51, 514-519 (1995).

E.2.4
12:15
Authors : Alex Sargent, Phoebe Allan, Peter Slater, Alex Watson, Ben Spencer, Zoe Henderson, Rob Sommerville and Emma Kendrick
Affiliations : University of Birmingham; University of Birmingham; University of Birmingham; University of Manchester; University of Manchester; University of Manchester; University of Birmingham; University of Birmingham

Resume : The purchase of electric vehicles has increased from 13,000 in the year 2012 to 6.6 million in 2021. [1] This drastic increase is driven by changes in government policies, in an attempt to delay the worsening effects of climate change. Each of these electric vehicles uses a pack of lithium-ion batteries (LiB) weighing about 250 kg. [2] If the electric vehicle revolution is the next step toward carbon neutrality and sustainability, recycling of these batteries must be built in from the start. Current industrial and laboratory advances in recycling LiBs have significant biases towards the cathode. This bias results in the anode either being discarded or even pyrolysed, despite the fact that natural graphite appears on the EU's 2020 list of critical materials.[3] Here we demonstrate the use of water to delaminate disassembled anode sheets from a Nissan Leaf cell at its end of life, with the ability to recover high performing anode graphite. The technique utilises the hydrolysis of trace amounts of lithiated graphite to provide changes in pressure via the effervescence of H2 that dislodges the active material away from the current collector. This process provides a rapid, low-cost technique for graphite reclamation even in the case of PVDF bound material as utilised in these early cells. Analysis via XPS, Raman and SEM determined that graphite from highly deteriorated anode material had little degradation, however, the surface was coated with an organic residue. This indicates that battery ageing occurs via solid electrolyte interface growth or electrolyte degradation rather than cracking and exfoliation. The graphite extracted from batteries also had a similar crystallinity to that of pristine electrochemical grade graphite. Electrochemical testing of the extracted active material not only showed stable cycling close to the theoretical capacity limit for graphite but that they could outperform MAGE 3, an electrochemical grade graphite. [1] IEA (2022), Electric cars fend off supply challenges to more than double global sales, IEA, Paris https://www.iea.org/commentaries/electric-cars-fend-off-supply-challenges-to-more-than-double-global-sales. [2] Harper, G., Sommerville, R., Kendrick, E. et al. Recycling lithium-ion batteries from electric vehicles. Nature, 575, 75–86 (2019). https://doi.org/10.1038/s41586-019-1682-5. [3] Critical Raw Materials Resilience: Charting a Path towards greater Security and Sustainability, 2020. https://eur-lex. europa.eu/legal-content/EN/TXT/?uri=CELEX:52020DC0474.

E.2.5
12:30 Lunch break    
14:00
Authors : Magda Titirici, Heather Au, Maria Crespo, Hui Luo
Affiliations : Imperial College London

Resume : It is imperative we mitigate and then reverse carbon emissions. COPS 26 just happened with the goal of global commitment to keep 1.5 C within reach by 2050. A green industrial revolution powered by many of sustainable innovations evolving in parallel is essential. Yet we need to make sure that this new revolution happens sustainably and does not create more damage. We must learn from past mistakes and learn how to see the bigger picture rather than immediate goals. Batteries and catalytic processes are key for delivering the green industrial revolution by storing the intermittent renewable energy and releasing it when is needed most to decarbonize our economy across various sectors. Yet, battery materials and catalysts for various sustainable technologies are facing real challenges as they are based on critical and expensive metals. In this talk, I will present recent research advances from my research team in the area of sustainable batteries with focus on Na and Al as well as the production of green H2 and sustainable plastics via electrocatalysis.

E.3.1
14:30
Authors : Rebecka Löfgren, Dr. Kouki Oka, Dr. Rikard Emanuelsson, Prof. Hiroyuki Nishide, Prof. Kenichi Oyaizu, Prof. Maria Strømme, Prof. Martin Sjödin
Affiliations : Department of Applied Chemistry and Research Institute for Science and Engineering Waseda University: Dr. K. Oka, Prof.H. Nishide, Prof.K. Oyaizu Nanotechnology and Functional Materials, Materials Science and Engineering The Ångström Laboratory, Uppsala University: Dr. K. Oka, R. Löfgren, Dr. R. Emanuelsson, Prof.M. Strømme, Prof.M. Sjödin

Resume : As Greta Thunberg claims – it is time to take severe action in order to stop the climate crisis. To do so we need to, as we all know, increase the use of renewable energy sources and use sustainable and green energy storage solutions. Unfortunately, the fantastic lithium-ion battery we use today is facing problems associated with element deficiency and large carbon emissions. Therefore, the challenge is to invent batteries composed of environmentally friendly compartments that have high capacity and high power as lithium-ion batteries. Our research group develops organic conducting redox polymers (CRP) as electrode materials for batteries. CRP material is associated with large resource abundance, low cost, and flexible properties. CRP constitutes of a polymer backbone, that contributes with very good electrical conductance, and a redox-active group, that is attached to the polymer and contributes with high capacity. The redox-active group we focus on is quinones that have the ability to cycle both metal ions and protons (H+). This versatile cycle ability is utilized to make both all organic quinone CRP proton batteries and hybrid quinone CRP metal batteries. To develop organic battery material, we have evaluated the versatile cycling chemistry of different quinones with several cycle ions. Moreover, we have also deposited our quinone CRP material on a porous carbon substrate in order to mass load material to enable higher capacity. This quinone CRP carbon construction has been used as an anode in a secondary manganese battery justifying that the concept works. Our current projects are about designing a battery consisting of quinone CRP material and calcium, magnesium, sodium, or potassium, and constructing an all organic battery using quinone CRP carbon electrodes and protons, which hopefully will provide new ideas within the green energy storage research field.

E.3.2
14:45
Authors : Hewei Xu, Alexandru Vlad.
Affiliations : Institute of Condensed Matter and Nanosciences, Molecular Chemistry, Materials and Catalysis, Université catholique de Louvain, Louvain-la-Neuve B-1348, Belgium hewei.xu@uclouvain

Resume : Currently, lithium-ions battery as the most important energy storage device has occupied most markets. High safety and high energy density batteries are still urgently required in our life. Some novel electrolyte matching high-voltage battery endurance has attracted much attention.[1] Concentrated electrolytes thanks to their large electrochemical window, are promising electrolytes.[2] We study here different concentrated solutions as electrolytes composed of LiTFSI salt and methanol solvent. Here a methanol-in-salt (MIS) electrolyte with 17 M LiTFSI in methanol is explored. As alcohol-based electrolyte with an alcohol solvation structure is formed, the 17 M electrolytes show better electrochemistry window which can reach a 3.13 volts potential platform and the maximum voltage can reach to 5.23 volts. The LiFePO4/active carbon and Li4Ti5O12/active carbon cells can cycle stably using the 17 M electrolytes. Furthermore, some high-voltage cell of LiMn2O4, Li1.03(Ni0.5Co0.2Mn0.3)0.97O2 still can work with the MIS electrolytes. A full cell using LiFePO4/Li4Ti5O12 can cycle more than 100 cycles with the 17 M electrolyte at a high-rate current. It shed a light that the nontoxic and low temperature alcohol-based electrolytes can be used in high-rate batteries in the future. Reference: [1] Wang Y, Zhong W-H. Development of Electrolytes towards Achieving Safe and High-Performance Energy-Storage Devices: A Review. ChemElectroChem. 2015;2:22-36. [2] Borodin O, Self J, Persson KA, Wang C, Xu K. Uncharted Waters: Super-Concentrated Electrolytes. Joule. 2020;4:69-100.

E.3.3
15:00
Authors : Rebecca Grieco, Diego A. Alván, Marta Liras, Nagaraj Patil, and Rebeca Marcilla
Affiliations : Electrochemical Processes Unit, IMDEA Energy, Avda. Ramón de la Sagra 3, 28935 Móstoles, Spain

Resume : The expected growth over the next few years in the battery sector is huge, with approximately 7 million tons of new batteries manufactured per year. This growth is mainly triggered by the deployment of the electric vehicle and by the energy storage coupled to wind and photovoltaic generation. However, the massive development of the sector could become an environmental problem since most commercial batteries are based on inorganic materials such as lithium, nickel and cobalt in lithium-ion batteries or vanadium in flow batteries. These materials are scarce, their production in some cases is not sustainable and some are even toxic. In this context, the replacement of these materials by organic compounds based on elements as abundant as C-H-O-N has become a very promising alternative [1]. In this talk we will focus on exposing the enormous structural and synthetic possibilities of redox-type polymers and their application in different types of batteries including Li-ion and Post-lithium ion battery technologies. Among the huge variety of redox-active polymers, here I will present our recent research on Conjugated Microporous Polymers (CMPs) having redox functionalities as excellent candidates for battery electrodes. Conjugated microporous polymers (CMPs) are a unique subclass of amorphous polymers that combine extended π-conjugation with inherent 3D permanent microporosity, large specific surface area and high physicochemical stability. In this talk, I will present the synthesis

E.3.4
15:15
Authors : Xiaolong Guo, Jiande Wang, Petru Apostol, Darsi Rambabu, Mengyuan Du, Xiaodong Lin, Alexandru Vlad
Affiliations : Institute of Condensed Matter and Nanosciences, Molecular Chemistry, Materials and Catalysis, Université catholique de Louvain, Louvain-la-Neuve B-1348, Belgium

Resume : In recent years, lithium-ion batteries have established themselves as the primary power source for portable electronic devices and have seen widespread use in a variety of emerging applications, including electric cars and smart grids. Compared to conventional automobiles, electric vehicles have less direct emissions, which is favorable to maintaining global warming below 1.5 degrees Celsius, which would be critical for the future sustainable development of humanity. However, the current lithium-ion battery technology depends mostly on transition metal oxide cathode materials. These materials have a low theoretical energy density and are near to the theoretical value commercially. This raises a number of concerns in terms of the economics, environmental pollution, sustainability, and other related topics. Compared to inorganic electrodes, organic electrodes are comprised of resource-rich light components (such as C, H, O, N, P, S, etc.) and can be manufactured by mild procedures; some of these chemicals can even be extracted directly from natural plants, maximizing their environmental friendliness and sustainability. Furthermore, organic molecule architectures are varied and straightforward to build and regulate, allowing for better adjustment of theoretical capacity and operational potential, hence optimizing battery energy density. To summarize, organic electrodes may serve as a suitable alternative to inorganic electrodes in certain applications. Electroactive organic materials can be classified into three types: p-type, n-type and bipolar. For p-type organics, the reaction occurs between the electrically neutral state (P) and the positively charged state (P+), which outcome in oxidation followed by reduction in the battery; for n-type organics, the redox reaction occurs between the negatively charged state (N-) and the electrically neutral state (N); bipolar organics can lose electrons from the electrically neutral state to the oxidation state or gain electrons to the reduction state under different potential range. The organic molecule's redox active group determines the sort of electrochemical reaction. And the n-type molecules are the ones that get the most research because they can adapt to the characteristics of today's commercial batteries, as well as their better molecular flexibility for larger theoretical capacity. N-type organics, however, often have an operating voltage that is lower than 3 V versus Li+/Li0. As a consequence of this, the majority of the currently available Li-containing n-type organics are oxidized or hydrolyzed when they are handled in environmental circumstances (i.e., when exposed to oxygen and moisture). Therefore, when n-type organics are now used to organic batteries, lithium metal or its alloy is required as the negative electrode for lithium source since it does not contain lithium (in their oxidation states). This poses a significant threat to the industrial safety since the solution of lithium dendrites in liquid batteries is still indistinct. In addition to this, the battery with low working voltage limits the energy density of batteries. As a result, organic cathodes with n-type, Li-containing, and high working potentials (air stable) are critical for the further development of organic battery. The sulfonamides recently reported by our group fully achieve these goals, thanks to their high operating voltage and complete structural conjugation. In this manuscript, a further organic high-voltage, Li-containing and air-stable trifluorosulfonamide and cyanamide family has been revealed by molecular design based on sulfonamide, as indicated in scheme 1B. As knows, trifluoromethanesulfonyl group and cyano group are stronger electron-withdrawing groups compared to methansulfonyl group. The introduction of trifluoromethanesulfonyl group will increase the working voltage of the chemicals significantly, and different halogen substituents have also been investigated considering the electronic inductive effect further increases the working potential. Trifluorosulfonamide family include Li2-PDFSA (dilithium 1,4-phenylenebis((trifluoromethylsulfonyl)amide), Li2-DC-PDFSA (dilithium (2,5-dichloro-1,4-phenylene)bis((trifluoromethylsulfonyl)amide)), Li2-DF-PDFSA (dilithium (2,5-fluoro-1,4-phenylene)bis((trifluoromethylsulfonyl)amide)) and Li4-PTFSA (tetralithium benzene-1,2,4,5-tetrayltetrakis((trifluoromethylsulfonyl)amide)). Besides, the cyano group can improve the working voltage and at the same time because of its small molecular mass, it can also improve the theoretical capacity. The cyanamide family include Li2-PDCA (1,4-phenylene dicyanamide), Li2-DC-PDCA (1,4-dicyanamido-2,5-dichlorobenzene) and Li2-DF-PDCA (1,4-dicyanamido-2,5-difluorobenzene). The trifluorosulfonamide family has a very high redox potential, which ranges from 3.2V to 3.7V versus Li+/Li0. A redox potential of 3.7V versus Li+/Li0 for the Li2-DF-PDFSA is among the highest achieved so far for organic Li-containing cathodes, and this might serve as inspiration for the development of high working potential Li-containing organic cathodes and the creation of organic cathodes compatible with inorganic cathodes. Alternatively, the cyanamide family has a high redox potential between 3.1V to 3.3V versus Li+/Li0 as well as a high theoretical capacity. Take Li2-PDCA as an example; its specific energy at the level of the active material is up to 960 Wh Kg-1. Again, more importantly, all these cathodic materials are Li-containing (reduced phase), air-stable (oxygen and moisture).

E.3.5
15:30 Coffee break    
16:00
Authors : M. Rosa Palacin
Affiliations : ICMAB-CSIC, Campus UAB 08193 Bellaterra, Catalonia (SPAIN)

Resume : Current societal challenges in terms of energy storage have prompted to an intensification in the research aiming at unravelling new high energy density battery technologies with the potential of having disruptive effects in the world transition towards a less carbon dependent energy economy through transport electrification and renewable energy integration. Aside from controversial debates on lithium supply, the development of new sustainable battery chemistries based on abundant elements is appealing, especially for large scale stationary applications. Interesting alternatives are to use sodium, magnesium or calcium instead of lithium and figures of merit attainable at the cell level computed using simple models indicate that the theoretical energy densities could easily top the state-of-the-art Li-ion, with costs being potentially much lower. While for the Na-ion case fast progresses are expected as a result of chemical similarities with lithium and the cumulated Li-ion battery know how over the years, for Ca and Mg the situation is radically different. On one hand, the possibility to use Ca or Mg metal anodes which would bring a breakthrough in terms of energy density, on the other, development of suitable electrolytes and cathodes with efficient multivalent ion diffusion are bottlenecks to overcome. The presentation will serve to discuss such promises and challenges, paying special attention to the research in materials which can potentially be used as positive electrodes. Overall, there is a long and winding road to follow before reliable proof-of-concept can be achieved and technological prospects evaluated. Development of reliable experimental setups, including reference and counter electrodes, coupled to complementary characterization techniques, as well as computational tools, is mandatory if steady progress is to be achieved.

E.4.1
16:30
Authors : Darya Snihirova , Linqian Wang, Min Deng, Bahram Vaghefinazari, Daniel Höche, Sviatlana V. Lamaka, Mikhail L. Zheludkevich
Affiliations : Institute of Surface Science, Helmholtz-Zentrum Hereon, 21502 Geesthacht, Germany Institute of Materials Science, Faculty of Engineering, Kiel University, 24143 Kiel, Germany

Resume : Mg-air battery is a primary aqueous battery with high theoretical voltage and specific energy density. Aqueous Mg-air batteries consist of magnesium anode coupled with an air electrode. During the discharge, high self-corrosion rate and low utilization efficiency of Mg anode reduce the performance of Mg-air battery. Additionally, the layer of corrosion products precipitated on magnesium reduces the active surface of the anode. Several strategies evolved to overcome these issues, alloy development and electrolyte modification. Use of electrolyte additives is an effective way to control interfacial process. It is inexpensive and straight-forward approach for improving issues related to self-corrosion of Mg. As was previously shown, Mg2+ complexing agents are able to improve the anodic efficiency by decreasing the occurrence of self-corrosion and “chunk-effect” [1-3]. Usually the additives have higher impact on either utilization efficiency or discharge potential. The use of versatile electrolyte additive is needed. In this work we demonstrate the performance of 2,6-dihydroxybenzoate (2,6DHB) as versatile additive positively affecting both mentioned parameters. The presence of 2,6DHB in the electrolyte reveals simultaneous improvement of the discharge activity and inhibition of the self-corrosion of Mg-0.15Ca anode, leading to negative average potential and high anodic utilization efficiency. EIS measurements during the discharge and real-time hydrogen evolution measurements were used for elucidation of the effective mechanism. Additionally, 2,6DHB shows improvement of the discharge behavior for Mg-air battery with different alloys as anode material. [1] B. Vaghefinazari, D. Höche, S.V. Lamaka, D. Snihirova, M.L. Zheludkevich, Tailoring the Mg-air primary battery performance using strong complexing agents as electrolyte additives, J. Power Sources, 453 (2020) 227880. [2] L. Wang, D. Snihirova, M. Deng, B. Vaghefinazari, S.V. Lamaka, D. Höche, M.L. Zheludkevich, Tailoring electrolyte additives for controlled Mg-Ca anode activity in aqueous Mg-air batteries, J. Power Sources, 460 (2020) 228106. [3] 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.

E.4.2
16:45
Authors : Conor Jason Price, Steven Paul Hepplestone
Affiliations : University of Exeter

Resume : Magnesium metal has been long-considered to be a safe and inexpensive alternative to lithium in rechargeable intercalation batteries due to its low cost, high abundance, and environmental safety. Due the diagonal relationship between lithium and magnesium they are also chemically similar, but with the extra valence electron of magnesium opening up the possibility of larger charger transfer during cycling of a cell to dramatically increase the overall energy storage of a device. Due to the breadth of materials available through choice of constituent elements, the transition metal dichalcogenide (TMDC) family has received a lot of attention over recent years for the wide range of properties they have demonstrated. In particular, their layered structure makes them ideal candidates for intercalation electrodes due to the weakly interacting layers separated by van der Waals gaps. Further to this, the layered material opens up the possibility to explore the effects of superlattice and heterostructure systems. Whilst many of these materials have been explored for use as lithium-ion batteries, there are few studies exploring them for use as magnesium-ion batteries. Using first principles density functional theory, we here investigate the whole family of TMDC materials and their heterostructures for use as Mg-ion intercalation electrodes. We are able to predict their open-circuit voltages, the electrical conductivity and volumetric expansion, properties which are all vital for the choice of an effective electrode material. We are also able to use thermodynamic to comment on the stability of these materials during cycling of a cell and predict the Mg capacity, a quantity that is vital for maximising the overall energy density of a battery.

E.4.3
17:00
Authors : Zahra Abedi, Desiree Leistenschneider, Weixing Chen, and Douglas G. Ivey
Affiliations : Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Canada

Resume : The cost-effectiveness, safe operation and high energy density of rechargeable zinc-air batteries (ZABs) make them promising candidates for energy storage devices. A ZAB typically contains two electrodes, the air electrode and the metallic zinc electrode, separated by an alkaline electrolyte. The air electrode is usually carbon based. Oxygen reduction and oxygen evolution reactions (OER and OER) occur at the air electrode, both of which suffer from poor kinetics. This affects the efficiency and cycle life of a ZAB. Using effective electrocatalysts can improve the performance of ZABs. Precious metals, like Pt and Ru, have typically been used as ORR and OER electrocatalysts, respectively. However, these metals are rare and expensive and are not stable during cycling. Alternative electrocatalysts include transition metal oxides (TMOs). Although TMOs are inexpensive, effective and abundant and have high activities towards both ORR and OER, they suffer from poor electrical conductivity. Coupling TMOs with conductive carbonaceous materials can lead to high performance, nano-engineered air electrodes with sufficient electrical conductivity. In this work, spinel type MnCo2O4 was coated on carbon fibers (MnCo2O4/CF), which were utilized to make air electrodes. Asphaltene, the by-product of oil sands operations was used as a novel precursor for carbon fiber. A polyacrylic acid (PAA)-KOH hydrogel was used as the electrolyte to prepare all solid state ZABs. Scanning/transmission electron microscopy (SEM/TEM) and x-ray photoelectron spectroscopy (XPS) techniques were employed to characterize the electrode material. Rheological and visual tests were carried out to investigate the properties of the hydrogel electrolytes. The battery performance was examined in terms of full cell charge/discharge voltage, power density and cycling life in the temperature range of 25oC to -45oC and was compared with ZABs using air electrodes with the benchmark Pt-RuO2 electrocatalyst. MnCo2O4/CF had superior performance to that of Pt-RuO2 at all temperatures. The efficiencies at 10 mA/cm2 for MnCo2O4/CF and Pt-RuO2 were 63.1% and 61.3%, respectively, at 25oC and 53.0% and 42.8%, respectively, at -10oC. MnCo2O4/CF was able to complete 200 charge/discharge cycles even at -45oC without failing, while Pt-RuO2 was unable to complete 200 cycles even at 25oC.

E.4.4
17:15
Authors : Zixuan Li, Alex Robertson
Affiliations : University of Oxford

Resume : Aqueous zinc-ion batteries are compelling next-generation energy storage devices due to the merits of zinc metal including mineral abundance, stable electrochemical activity, low cost, and environmental friendliness. However, one of the issues leading to zinc-ion battery capacity decay is zinc dendrite growth which will puncture the separator. Although there are a lot of efforts have been devoted to preventing dendrite like anode surface modification and electrolyte manipulation, understanding of science foundation of zinc deposition in electrolyte remains limited. In this work, we comprehensively study the dependence of zinc morphology on different deposition conditions (current density and capacity) with combined characterization method of liquid cell transmission electron microscopy and SEM. We found that in the most widely used zinc electrolyte ZnSO4, the nuclei density of deposited zinc will increase with the increasing current density from 1 mA cm-2 to 120 mA cm-2. Contradicted with the general kinetics understanding of metal nucleation model Sand’s time which said high current density will render short zinc dendrite formation time, we found that a high current density like 120 mA cm-2 can generate more nuclei active sites and more uniform surface. We attribute it to the thermodynamics factor, which means high current density can enable high energy nucleation seeds while low current density can only active low energy nucleation sites like grain boundary. The crystallographic orientation of zinc texture behavior was also studied by XRD with the indicator of the peak intensity ratio of (002)Zn and (101)Zn. The deposited zinc at ultrahigh current density 120 mA cm-2 shows the highest I002:I101, which means the surface is (002) plane dominated. Since (002)Zn is parallel to the electrode, more (002) plane indicates the electrode is more uniform and flatter, which is consistent with the previous result. Finally, based on this finding, we developed a simple method to prolong the cycling performance of zinc-ion battery without any modification. This work not only unravels the nucleation behavior of zinc from low current density to high current density, but also provides an effective strategy to achieve long-term zinc-ion battery.

E.4.5
17:30
Authors : Ankur Yadav, Prem Sagar Shukla, Monojit Bag
Affiliations : Indian Institute of Technology(IIT) Roorkee

Resume : Organometallic trihalide perovskites exhibit high power conversion efficiency, making them potential candidates for next-generation photovoltaic solar cells. In addition to their unique physical and optoelectronic properties, perovskites have strong optical absorption in the visible range, ambipolar charge transport, high carrier mobility and long photo generated carrier diffusion lengths. The ionic response of these materials is quite high. As a result, these materials are also equally promising for energy storage applications. Recently, halide perovskites have been used in supercapacitors due to their large surface area and good ionic mobility with different charge storage characteristics. One of the critical aspects of halide perovskites for electrochemical energy storage application is the ion migration in the active electrode. A significant increase in capacitance is achieved by combining halide perovskite and carbon nanoparticles. Although a complete knowledge of the charge-storage mechanism in halide perovskite-based supercapacitors is still lacking, the ionic conductivity of the active electrode in perovskite enhances the overall charge storage capacity. The ionic conductivity of MAPbI3 samples is substantially higher than that of MAPbBr3 samples because the Pb-Br link is shorter than the Pb-I bond. As a result, bromide-perovskite-based supercapacitors have an overall energy density of 10 – 12 Wh kg-1. Iodide-based perovskites, on the other hand, are extremely unstable in the environment. As a result, the best feasible solution for reliable and efficient energy storage applications may be to manufacture mixed halide perovskite-based supercapacitors. There has been a general approach for preparing mixed halide perovskites by mixing methylammonium iodide (MAI) and methylammonium bromide (MABr) in the precursor solution. However, due to the phase segregation, inhomogeneous iodine-rich and bromine-rich perovskite thin films are formed. Due to local inhomogeneity and enhanced ionic conductivity, these materials are unstable. Another method is to make single crystals of MAPbBr3 and MAPbI3 and mix them in powder form to retain the nanoparticles in their purest phases. We have prepared a series of porous electrodes for supercapacitor applications by combining powders of various halide-based perovskite single crystals. We've shown that a specific bromide composition to iodide ratio with an energy density of 22 Wh kg-1 and a power density of 600 W kg-1 achieves maximum efficiency. The ionic conductivity of the mixed halide sample is at least two orders higher than that of pure halide perovskites, at 3.2 ×10-13 m2 s-1, while charge transfer resistance is reduced to 40.5 cm-2. With increased iodide content, however, overall device stability and coulombic efficiency diminish. With bromide ions in excess, cyclic stability of roughly 87 percent and columbic efficiency of 89 percent can be achieved.

E.13.0
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09:00
Authors : Juhyoun Park, Hiram Kwak, Yeji Choi, Yoon Seok Jung
Affiliations : Department of Chemical and Biomolecular Engineering, Yonsei University

Resume : Serious safety concerns stemming from the use of organic liquid electrolytes and the fast-rising price of Li for conventional lithium-ion batteries (LIBs) have impeded their wide applications for energy storage systems (ESSs). In this regard, all-solid-state Na or Na-ion batteries (ASNBs) are considered a promising alternative. Owing to their high ionic conductivities reaching max. 10 mS cm-1 and favorable processability, sulfide solid electrolytes (SEs) have been extensively investigated for developing practical all-solid-state batteries. However, they suffer from poor high-voltage and chemical stabilities. Recently, halide SEs emerge because of their excellent (electro)chemical oxidation stability. Since the first halide Li+ superionic conductor Li3YCl6 was identified in 2018, several new halide SEs, such as L2ZrCl6 and Li3InCl6, have been developed. However, only a few Na+ analogs have been reported thus far. In this presentation, we report on our recent developments of new Na+ halide superionic conductors. Importantly, it is demonstrated that stable cycling performances at room temperature for ASNBs are achieved by employing Na+ halide SEs with cost-effective and abundant elements. References [1] Hiram Kwak, Shuo Wang, Juhyoun Park, Yunsheng Liu, Kyu Tae Kim, Yeji Choi, Yifei Mo, Yoon Seok Jung, ACS Energy Lett. 2022, 7, 1776. [2] Hiram Kwak, Daseul Han, Jeyne Lyoo, Juhyoun Park, Sung Hoo Jung, Yoonjae Han, Gihan Kwon, Hansu Kim, Seung-Tae Hong, Kyung-Wan Nam, Yoon Seok Jung, Adv. Energy Mater. 2021, 11, 2003190. [3] Hiram Kwak, Jeyne Lyoo, Juhyoun Park, Yoonjae Han, Ryo Asakura, Arndt Remhof, Corsin Battaglia, Hansu Kim, Seung-Tae Hong, Yoon Seok Jung, Energy Storage Mater. 2021, 37, 47.

E.5.1
09:30
Authors : Benjamin A. D. Williamson, Sverre M. Selbach
Affiliations : Department of Materials Science and Engineering, NTNU Norwegian University of Science and Technology, Trondheim, Norway

Resume : Solid state electrolytes offer the potential to drastically increase the overall stability of rechargeable lithium batteries as well as provide the means to realise the use of Li-metal anodes maximising the charge capacity of a device. At present, batteries use liquid electrolytes such as [LiPF6]- which although they possess high ionic conductivities of 1x10-2 S cm-1 limit the safe temperature ranges a battery can be operated at as well as forbidding the use of Li-metal anodes due to dendrite formation leading to short circuiting and “thermal runaway”. Solid electrolytes such as the Li-rich garnet materials, LLZO, or anti-perovskites, Li3OCl, have demonstrated low migration barriers (<0.3 eV), however issues arise regarding stability or a competing lower conductivity phase. In this work, we have identified a promising Earth-abundant, non-toxic, stable Li-solid electrolyte. Using a combination of density functional theory and experiment, we show that this material possesses thermodynamic, dynamic and electrochemical stability, ideal defect chemistry and low migration barriers leading to undoped conductivities of ~10-5 S cm-1 which are expected to rise to at least 10-3 S cm-1 with minimal doping.

E.5.2
09:45
Authors : Eveline van der Maas, Swapna Ganapathy, Marnix Wagemaker
Affiliations : Delft university of technology

Resume : Halide solid electrolytes with formula Li3M(III)X6 (M(III) = In, Sc, Y, Lanthanides, X = Cl, Br, U) are fast ionic conductors that can be used as solid electrolytes for all-solid state batteries (ASSB). Especially chlorides have demonstrated excellent performance in ASSB cycled with uncoated NCMs, demonstrating their compatibility against high voltage cathodes. Due to these promising results, it is interesting to learn about the structure to property relationship so that guidelines can be created for optimal material design. We have found that for Li3HoCl6, small lithium deficiency during the synthesis leads to a trigonal to orthorhombic phase transition, improving the ionic conductiviy by one order of magnitude. Investigating aliovalent substitution in monoclinic Li3-xIn1-xZrxCl6, the ionic conductivity is maximum at 30% Zr, indicating that the introduction of Li-vacancies aids diffusion. Solid-state NMR measurements show multiple jump processes in the pristine material, which paired with the model of the crystal structure reveals anisotropy of the diffusion. Halogen substitution in Li3YBrxCl1-x reveal a tradeoff between ionic conductivity and electrochemical stability, as the larger Br opens up the Li-ion paths but is more prone to oxidize. Finally, an Li3YI6 was synthesized and the structure characterizede by neutron diffraction and single crystal x-ray diffraction. The Li-ion dynamics is characterized on multiple length scales using AC-impedance and a variety of NMR measurements.

E.5.3
10:00
Authors : Benjamin A. D. Williamson, Sverre M. Selbach
Affiliations : Department of Materials Science and Engineering, NTNU Norwegian University of Science and Technology, Trondheim, Norway

Resume : Solid state electrolytes offer the potential to drastically increase the overall stability of rechargeable lithium batteries as well as provide the means to realise the use of Li-metal anodes maximising the charge capacity of a device. At present, batteries use liquid electrolytes such as [LiPF6]- which although they possess high ionic conductivities of 1x10-2 S cm-1 limit the safe temperature ranges a battery can be operated at as well as forbidding the use of Li-metal anodes due to dendrite formation leading to short circuiting and “thermal runaway”. At present, however, there is a dearth of materials suitable for the role of a highly conductive, stable, solid electrolyte. Current highly conductive materials such as the agyrodites (Li6PS5X; X=Cl,Br ) or LGPS (Li10GeP2S12) typically possess stability issues, whilst more stable materials show low conductivities, e.g. tetragonal LLZO (Li7La3Zr2O12). Understanding the fundamental processes that govern ionic conductivity in such materials has long been a focus of research, however limited information is available on how the intrinsic lattice dynamics of a material influence this, and whether it is a governing factor. In this work we look at understanding the phonon processes between the bulk crystal lattice and a vacanncy migration event in the Li-rich antiperovskites (Li3OX ; X=Cl,Br,I). In studying the phonons in this way, we aim to question how phonon-based descriptors can be applied to materials discovery and whether diffusion processes can be enhanced via external stimuli.

E.5.4
10:15
Authors : Sudarshan Narayanan, Mauro Pasta
Affiliations : Department of Materials, University of Oxford, Parks Road, Oxford OX1 3PH, United Kingdom

Resume : All-solid-state batteries (ASSBs) are becoming increasingly attractive for the development of high-capacity rechargeable batteries for electric vehicles (EVs), with increased safety and high coulombic efficiencies even after several hundreds of charge-discharge cycles. By employing Li metal as the anode, ASSBs also enable energy densities high enough to meet performance criteria of current commercial EV battery modules. Moreover, the development of ASSBs in an “anode-less” configuration presents opportunities to reach even higher energy densities.[1] In particular, the use of sulphide-type solid electrolytes like argyrodites (Li6PS5X, X = Cl, Br, I) provides for a viable and manufacturable approach to ASSBs owing to their relatively high ionic conductivities and easy processability.[2] Few reports have investigated the evolution of the anode electrode-electrolyte interface where the choice of electrolyte material has been shown to determine the nature and composition of the interphase thus formed.[3] In our study, we probe the interphasial chemistry as a function of the applied current density at the current collector-electrolyte (Li6PS5Cl) interface in an “anode-less” configuration using X-ray photoelectron spectroscopy (XPS) under operando conditions. By correlating observed chemical evolution with electrochemical characterisation, we also demonstrate that this electrodeposition process and the corresponding morphology are strongly mediated by the current density at which the process is operated.[4] In my talk, I will also discuss the implications of these results in the context of controlling the morphology of electrodeposited Li at the anode and its effect on the efficiency of subsequent Li stripping and plating processes. References: [1] Lee, YG., Fujiki, S., Jung, C. et al. “High-energy long-cycling all-solid-state lithium metal batteries enabled by silver–carbon composite anodes”. Nature Energy 5, 299–308 (2020). [2] Pasta, M., Armstrong, D., Brown, Z.L., Bu, J., Castell, M.R., Chen, P., Cocks, A., Corr, S.A., Cussen, E.J., Darnbrough, E., et al. “2020 roadmap on solid-state batteries”. Journal of Physics: Energy 2 (2020), p 032008 [3] A. L. Davis, E. Kazyak, D. W. Liao, K. N. Wood, N. P. Dasgupta. “Operando Analysis of Interphase Dynamics in Anode-Free Solid-State Batteries with Sulfide Electrolytes”. Journal of Electrochemical Society (2021), 168, 070557 [4] S. Narayanan, U. Ulissi, J. S. Gibson, Y. A. Chart, R. S. Weatherup, M. Pasta. "Effect of current density on the Li – Li6PS5Cl solid electrolyte interphase". ChemRxiv (2022).

E.5.5
10:30 Coffee break    
11:00
Authors : Petra de Jongh, Valerio Gulino, Peter Ngene
Affiliations : Materials Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, The Netherlands, P.E.deJongh@uu.nl

Resume : Complex metal hydrides are a promising class of solid state electrolytes for future generation all-solid-state batteries. In this presentation I will share information about the research in this field in our group over the past five years, most notably discussing: * improved conductivity in nanocomposites, by combining with high surface area/porous oxides ("interface engineering") * design rules how to maximum the room temperature conductivity * synergy between anion replacement and nanocomposites * progress towards practical room temperature all-solid-state batteries based on these electrolytes references: Suwarno et al, J. Phys Chem C 121 (2017) 4197 Zettl et al. J Phys Chem C 124 (2020), 2806 Gulino et al, ACS Appl. Ener. Mater. 121 (2017), 4941 de Kort et al, J. Alloys Comp. 901 (2022) 163474

E.6.1
11:30
Authors : Yuanye Huang, Arndt Remhof, Radovan Černý, Corsin Battaglia
Affiliations : Empa, Swiss Federal Laboratories for Materials Science and Technology, Ueberlandstrasse 129, 8600, Dübendorf, Switzerland; DQMP, University of Geneva, Quai Ernest-Ansermet 24, 1211, Geneva, Switzerland

Resume : Hydroborates are a yet underexplored class of solid electrolytes that combine very attractive material properties, including compatibility with lithium and sodium metal anodes, low gravimetric density (<1.2 g/cm3), high thermal and chemical stability, low toxicity, solution processability, and mechanical properties that enable cold pressing. Mixing cage-like hydro-closo-borate [BnHn] and/or hydro-closomonocarbaborate[CB(n-1)Hn] ions, ionic conductivities above 1mS/cm were obtained [1-4]. Stable cycling for a 3V class all-solid-state battery based on Na4(B12H12)(B10H10) as solid electrolyte consisting of a sodium metal anode and NaCrO2 as cathode active material was achieved [2]. Thereby the cathode composite can be assembled by cold pressing at pressures of typically 200 MPa. Here we discuss the role of the applied pressure on the structure of mixed Na2B10H10:Na2B12H12 electrolytes and their conductivity. Two ratios of Na2B10H10:Na2B12H12 were investigated, 1:1 and 1:3. The as-synthesized powders are phase pure and crystallize both in a single, face-centered cubic (FCC) structure. After applying pressure to densify the materials, the pellet shows a phase segregation into an FCC and a body-centered cubic (BCC) phase, the latter being recently observed in NaCB11H12 electrolyte [5]. The higher the pressure the higher the amount of BCC phase, which is the high temperature and high con-ductivity phase of Na2B12H12. The BCC content saturates at about 300 MPa to the amount of Na2B12H12 in the initial synthesized powder. The room temperature conductivity follows the same trend. For the 1:1 ratio it increases from 0.2 mS/cm at 10% BCC contend to about 1 mS/cm at 50% BCC contend. Our results show that expensive Na2B10H10 can in part be replaced by cheaper Na2B12H12 and that pressing is a prerequisite to achieve the high conductivities by the introduction of a highly con-ductive bcc phase. [1] L. Duchêne, R.-S. Kühnel, D. Rentsch, A. Remhof, H. Hagemann, C. Battaglia, Chem. Comm. 53, 4195 (2017) [2] L. Duchêne, R.-S. Kühnel, E. Stilp, E. Cuervo Reyes, A. Remhof, H. Hagemann, C. Battaglia, Energy & Environmental Science 10, 2609 (2017) [3] R. Asakura, D. Reber, L. Duchêne, S. Payandeh, A. Remhof, H. Hagemann, C. Batta-glia, Energy & Environmental Science 13, 5048 (2020) [4] Brighi M., Murgia F., Lodziana Z., Schouwink P., Wolczyk A. and Černý R. J. Power Sources 404, 7 (2018) [5] M. Brighi, F. Murgia, L. Piveteau, C. E. Avalos, V. Gulino, M. C. Nierstenhöfer, P. Ngene, P. de Jongh, R. Černý, ACS Appl. Mater. Interfaces 13, 61346 (2021)

E.6.2
11:45
Authors : Fabrizio Murgia,1 Matteo Brighi,1 Laura Piveteau,2 Claudia E. Avalos,2 Valerio Gulino,3 Marc C. Nierstenhöfer,4 Laura Caggiu,1 Peter Ngene,3 Petra de Jongh3 and Radovan Černý1
Affiliations : 1Laboratory of Crystallography, Department of Quantum Matter Physics, University of Geneva, Quai Ernest-Ansermet 24, CH-1211 Geneva, Switzerland 2Institute of Chemical Sciences and Engineering, NMR Platform, Ecole Polytechnique Fédérale de Lausanne, Station 6, CH-1015 Lausanne, Switzerland 3Materials Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, 3584 CG Utrecht, The Netherlands 4Fakultät für Mathematik und Naturwissenschaften, Anorganische Chemie, Bergische Universität Wuppertal, Gaußstr. 20, 42119 Wuppertal, Germany

Resume : In the search for safer and more efficient electrochemical energy storage systems, Na-based all-solid-state batteries (Na-ASSBs) represent a viable evolution from the current Li-ion technology. Na-ASSBs combine the advantages of availability and low cost of Na precursors, with both intrinsic enhanced safety and extended temperature operating range offered by the non-flammable solid electrolyte (SE) when compared to lithium-ion batteries.1,2 The challenge for Na-ASSBs has been mainly the development of room temperature (rt) SE that withstand elevated current densities, i.e. providing both (electro)chemical robustness and favourable mechanical properties. Sodium salts of large-cage hydridoborates [BxHx]2- (x = 10,12), and their C-derivatives [CBx-1Hx]- have proven to be promising Na-based SE. Indeed, they show an excellent electrochemical stability, arising from the strong electron delocalization on the anion cluster, as well as low area resistance, low density and soft mechanical properties.3 Fast cationic motion generally occurs after a polymorphic transition towards higher-symmetry phases. This order-disorder phase transition provides structures with more free sites for the cations, as well as an increased rotational energy of the anion cages, which enhances the cation motion (e.g. paddle-wheel effect).4 However, such phase change occurs far above rt, thus hampering practical applications. Lowering (or suppressing) the phase transition has been made possible by chemical tuning (anion substitution) or physical treatments implying either the formation of composites, nanoconfined materials or by mixing anionic (or neutral) hydridoborate clusters.5,6 In contrast to these strategies, here we present the effect of mechanical milling in stabilizing at rt the superionic conductive phase of a single-anion material, NaCB11H12. The high-energy ball milling quenches the metastable, body-centred cubic (bcc) polymorph, which exhibits a larger number of available Na+ sites. Macroscopically, this results in a conductivity of 4 mS cm-1 at 20°C (Fig. 1), without altering the electrochemical stability.7 Preliminary electrochemical tests show that bcc-NaCB11H12 withstand a critical current density of 0.12 mA cm-2. Finally, the rich polymorphism of NaCB11H12 has been thoroughly elucidated by temperature-dependent synchrotron X-ray diffraction. 1 S. Ferrari et al., Adv. Energy Mater., 2021, 2100785, 2100785. 2 C. Vaalma et al., Nat. Mater. Rev., 2018, 3, 18013. 3 R. Černý, M. Brighi and F. Murgia, Chemistry (Easton)., 2020, 2, 805–826. 4 T. J. Udovic et al., Chem. Commun., 2014, 50, 3750. 5 M. Brighi et al., J. Power Sources, 2018, 404, 7–12. 6 L. Duchêne et al., Chem. Commun., 2017, 53, 4195–4198. 7 F. Murgia et al., ACS Appl. Mater. Interfaces, 2021, 13, 61346–61356.

E.6.3
12:00
Authors : Ashish Raj, Bruno Grignard, Christophe Detrembleur, Jean-François 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, 4000 Liège, Belgium

Resume : Green and sustainable energy materials research are very much needed for eco-friendly technical innovations as current lithium batteries consist of more or less highly toxic constituents. While polyethene oxide (PEO) based solid-state batteries have been a front runner in the polymer electrolyte research, it does come up with certain trade-offs. Many polymer composites/blends have been demonstrated as better alternatives to a pure polymer exhibiting superior electrochemical and mechanical properties but are less environmentally friendly. In our project, we developed a composite of PEO and soybean derived carbonated soybean oil (CSBO) by a facile approach. The physical blend of PEO and CSBO with lithium bis(trifluoromethanesulfonyl) imide salt resulted in the free-standing membranes comprising of ether and cyclic carbonate functionality in their molecules. It facilitates the polymer composite with amorphous and adhesive nature owing to CSBO resulting in a better interface with electrodes. With the conductivity of 3.3 x 10-5 S-cm-1¬ at room temperature, a broad electrochemical stability window (> 4.2 V) was observed with high stability versus lithium metal electrodes as inferred from stripping and plating (> 300h). The composite membrane-based lithium metal battery prototype with Lithium ferrophosphate (LiFePO4) delivered 108.2 mAhg-1 of specific capacity with high coulombic efficiency at 0.1C, 60 o C. These materials like CSBO-PEO composite are showing the path to complete or partly bio-based alternatives for reducing the toxic-footprint of overall battery materials and development.

E.6.4
12:15
Authors : Sunil Lonkar*, Chiara Busa, Vincenzo Giannini
Affiliations : Advanced Materials Research Center Technology Innovation Institute PO Box: 9639 Masdar City, Abu Dhabi, UAE

Resume : The ever-growing demands and rapid development of sustainable energy storage devices and systems pressed the need for low-cost yet highly performing electrode materials. The transition metal oxide and sulfide-based hybrids holds great promise as the active electrode materials in supercapacitors, due to their large surface area and variable oxidation states. These properties enable significantly high energy storage via electrical double layer and pseudocapacitive charge storage mechanisms. Herein, we discuss a facile, scalable, and environment-friendly preparation process to produce transition metal sulfide and oxides based on resource rich metals such as Mn, Fe, V etc. and their hybrids with carbonaceous materials, such as carbon nanotubes and graphene. This strategy encompasses solvent-less mixing of a metal salt, surfeit yet non-toxic abundant elemental sulfur and carbon precursor under continuous ball milling and thermo-annealing. The resulting nanohybrids were thoroughly investigated by means of several techniques. XRD, HRTEM, SEM, Raman and BET could gather insights on the morphology and the fine material structure, as well as on the spectroscopic properties. Finally, the electrochemical properties as supercapacitor components were investigated in regards with varyingly increasing carbon content. The nanohybrids were tested in both aqueous and organic electrolytes for bettering energy and power performances. Charge storage performances and components stability in both symmetric and asymmetric devices were assessed via CV, GCD, EIS.

E.6.5
12:30 Lunch break    
14:00
Authors : Yuanzheng Yue
Affiliations : Department of Chemistry and Bioscience, Aalborg University, 9220 Aalborg, Denmark

Resume : There are many ways to enhance the performances of Li-ion batteries (LIBs). In recent years, substantial effort has been made in developing both electrodes and electrolyte for high-performance LIBs. However, there is still a huge room for LIBs to be further developed to keep up with the accelerating evolution of energy technology during the current green transition. Five years ago, we proposed the order/disorder engineering concept to improve the electrochemical properties of electrodes for LIBs [1,2]. This concept here refers to four aspects: 1) Designing a glass system that can undergo partial disorder-to-order transition during charge/discharge; 2) Generating micro/nano crystals in glass, i.e., fabricating glass-ceramics; 3) Making crystals electrochemically active by amorphization; 4) Transforming glass into high potential state through charging/discharging. In this context, I present four case studies to demonstrate the enhancing effect of order/disorder engineering on electrochemical performances of electrodes. First, the vanadium-tellurite (VT) glasses were synthesized as LIB anode materials. It was found that nanocrystals formed in VT glass anode during charge/discharge cycling, leading to enhancement of both cycling stability and electronic/ionic conductivities [2]. Second, NaFePO4 with maricite structure, which is electrochemically inactive for sodium-ion storage, was amorphized as cathode for NIBs by ball-milling. The induced disorder caused much improved sodium storage with an initial capacity of 115 mA h g−1 at 1 C and enhanced cycling stability [3]. Third, the Al-metal-organic framework (Al-MOF)/graphene composite was synthesized as LIB anode [4]. It was found that lithiation/delithiation induced an order-disorder transition in Al-MOF. This transition resulted in a capacity increase from 60 to 400 mA h g-1 at the current density of 100 mA g-1. Fourth, we invented the first MOF glass anode for LIBs, which exhibited two-fold enhancement of the specific capacity after 1000 cycles of charging/discharging [5]. Such glass anode exhibited much higher lithium storage capacity (306 mA h g-1 at 2 A g-1) than the crystalline anode. The microscopic mechanism of such capacity enhancement has been revealed by structural analyses [5]. The above findings suggest that glass is a promising material for developing superior LIBs and NIBs. References [1] Y. Z. Yue, A plenary talk at 3rd International Conference on Nanoenergy and Nanosystems, Beijing, China, October 21-23, 2017. [2] Y. F. Zhang, P. X. Wang, T. Zheng, D. M. Li, G. D. Li, Y. Z. Yue, Nano Energy 49 (2018) 596-602. [3] F. Y. Xiong, Q. Y. An, L. X. Xia, Y. Zhao, L. Q. Mai, H. Z. Tao, Y. Z. Yue, Nano Energy 57 (2019) 608-615. [4] C. W. Gao, P. X. Wang, Z. Y. Wang, S. K. Kær, Y. F. Zhang, Y. Z. Yue, Nano Energy 65 (2019) 104032. [5] C. W. Gao, Z. J. Jiang, S. B. Qi, P. X. Wang, L. R. Jensen, M. Johansen, C. K. Christensen, Y. F. Zhang, D. B. Ravnsbæk, Y. Z. Yue, Adv. Mater. 34 (2022) 2110048.

E.7.1
14:30
Authors : Sumair Imtiaz, Ibrahim Saana Amiinu, Tadhg Kennedy, Kevin M. Ryan
Affiliations : University of Limerick

Resume : Silicon nanowires (Si NWs) are a promising anode material for lithium-ion batteries (LIBs) due to their high specific capacity1. Achieving adequate mass loadings for binder-free Si NWs is restricted by low surface area, mechanically unstable and poorly conductive current collectors (CCs), as well as com-plicated/expensive fabrication routes2,3. Herein, a tunable mass loading and dense Si NW growth on a conductive, flexible, fire-resistant, and mechanically robust interwoven stainless-steel fiber cloth (SSFC) using a simple glassware setup is reported. The SSFC CC facilitates dense growth of Si NWs where its open structure allows a buffer space for expansion/contraction during Li-cycling. The Si NWs@SSFC anode displays a stable performance for 500 cycles with an average Coulombic effi-ciency of >99.5%. Galvanostatic cycling of the Si NWs@SSFC anode with a mass loading of 1.32 mg.cm−2 achieves a stable areal capacity of ≈2 mAh.cm−2 at 0.2 C after 200 cycles. Si NWs@SSFC anodes with different mass loadings are characterized before and after cycling by scan-ning and transmission electron microscopy to examine the effects of Li-cycling on the morphology. Notably, this approach allows the large-scale fabrication of robust and flexible binder-free Si NWs@SSFC architectures, making it viable for practical applications in high energy density LIBs. References: 1 Y. Jin, B. Zhu, Z. Lu, N. Liu, J. Zhu, Adv. Energy Mater., 2017, 7, 1700715 2 T. Kennedy, M. Brandon, K. M. Ryan, Adv. Mater., 2016, 28, 5696 3 T. D. Bogart, D. Oka, X. Lu, M. Gu, C. Wang, B. A. Korgel, ACS Nano, 2014, 8, 915

E.7.2
14:45
Authors : K.-H. Heinig1, H.-J. Engelmann1, O. Andersen2, R. Hauser2, D. Tucholski1, C. Gerking3, S. Lindow3, A. Almousli4
Affiliations : 1 Helmholtz-Zentrum Dresden-Rossendorf (HZDR), D-01328 Dresden, Germany; 2 Fraunhofer IFAM, D-01277 Dresden, Germany; 3 NANOVAL GmbH & Co. KG, D-13403 Berlin, Germany; 4 Custom Cells GmbH, D-25524 Itzehoe, Germany

Resume : Six carbon atoms of graphite of lithium ion battery (LIB) anodes can store one lithium atom, whereas one Si atom can store nearly four lithium atoms. Theoretically, the replacement of graphite by silicon could reduce the weight of the anode by a factor of nearly 10. However, due to the strong swelling of silicon upon lithiation, Si anodes suffer from pulverization which reduces drastically the life cycle of LIBs. It has been shown that nanostructured silicon with structure sizes <200nm can withstand pulverization. There are many activities to develop an economic large-scale fabrication of such nanosilicon. We form Si nanostructures by phase separation during quenching of AlSi alloy droplets. At atomization of the AlSi melt the microdroplet solidify extremely fast which results in nanoscale Si pattern. Subsequently the Al is removed by selective etching leading to nanoporous Si microspheres. We show that the structure depends strongly on the AlSi composition, the particle sizes and impurities. Promising nanosilicon for LIB anodes with a good cycling have been found. This work is supported by the German federal ministry for economic affairs and climate protection under grant number 01221755/1.

E.7.3
15:00
Authors : Assoc. Prof. Dr. Neslihan Yuca Doğdu Assoc. Prof Dr. Ömer Suat Taşkın Emre Güney M.Sc. Büşra Çetin İlknur Kalafat
Affiliations : 1) Enwair Energy Technologies Corporation, Kagithane, Istanbul 34415, Turkey; 2) Institution of Energy, Istanbul Technical University, Istanbul 34469, Turkey 3) Department of Chemical Oceanography, Institute of Marine Science and Management, Istanbul University, Istanbul 34134, Turkey Büşra Çetin: Affiliations 1 Neslihan Yuca Doğdu : Affiliations 1;2 Emre Güney: Affiliations 1 İlknur Kalafat: Affiliations 1 Ömer Suat Taşkın: Affiliations 1;3

Resume : Self-healing is a measure of material's ability to repair damage. Physical and chemical processes have been used to obtain self-healing polymers for various applications. Different approaches are involved for these systems, such as shape-memory effects, covalent-bond reform, heterogeneous systems, diffusion and flow, and the dynamics of supramolecular chemistry. Different approaches are used to achieve self-healing polymers, in particular, the role of the healing system in chemistry is highlighted, which enables thermal transients, damage repairing and reconnection. Moreover, self-healing systems and their energy storage applications are currently getting great importance. Inspired by the dynamic network structure of animal dermis, in which collagen fibril (rigid and strong) and elastin fibril (soft and elastic) crosslink through supramolecular interactions to form a sturdy and flexible material we hypothesized that the combination of a rigid conductive polymer with a soft hydrophilic polymer through proper supramolecular interactions would yield a strong and robust polymer binder. According to the literature, the external stimulus such as heat, light, pH and redox initiate the healing process. This process is known as non-autonomous self-healing when some additional external stimulus is needed. Considering the battery chemistry, it is the most functional method to choose self-healing structures and batteries with the help of hydrogen bonds in order to make the self-healing process occurs autonomously. In the literature, polymerized β-cyclodextrin (β-CD) has been used as an advanced binder for Si-nanoparticle anodes, and cracks in the electrode can be avoided with its reversible properties through supramolecular cyclodextrin or hydrogen bonding compounds. In one of the another effective research, Si anode was coated with hydrogen bond oriented polymer binder layers based on polyamide polymer, which was resulted by ten times longer electrochemical performances than conventional silicon anodes. In this work, we report a supramolecular strategy to prepare conductive hydrogels with outstanding mechanical and electrochemical properties, which are utilized as self-healable polymer binder for silicon anodes with high performance. The supramolecular assembly of polyaniline and polyvinyl alcohol through dynamic boronate bond yields the polyaniline-polyvinyl alcohol hydrogel, which shows remarkable tensile strength and electrochemical performance. The borax structure binds the polymer to form a self-healing structure around the active nanoparticles. With the self-healing chemistry created, unbalanced volumetric changes in the materials and cracks on the electrode surface are prevented. Thus, electrochemical performance losses are decreased. The self-healing functionalized components of lithium-ion batteries, which focus on improving and optimizing properties such as high energy density, high voltage, long life and cycle stability, are of great importance for next-generation batteries. This project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement 957225 (BAT4EVER).

E.7.4
15:15
Authors : Marius C. Stoian*, Irina-Nicoleta Bratosin*, Cosmin Romanitan*, Gabriel Craciun*, Nikolay Djourelov**, Mihaela Kusko*, Antonio Radoi*
Affiliations : *National Institute for Research and Development in Microtechnologies (IMT-Bucharest), 126A Erou Iancu Nicolae Street, 077190, Voluntari, Romania; **Extreme Light Infrastructure-Nuclear Physics (ELI-NP), “Horia Hulubei” National R&D Institute for Physics and Nuclear Engineering (IFIN-HH), Magurele, Ilfov, 077125, Romania.

Resume : In an attempt to reach new environmentally friendlier alternative technologies for energy storage, the supercapacitors (SCs) have revealed great potential, showing several advantages, such as long cycling stability, high power density, fast charge/discharge [1], while they have been used in many applications, for hybrid electric vehicles and portable electronic devices in combination with rechargeable batteries [2]. Most of the research to increase the supercapacitors’ performance which is highly dependent on the electrode material, is concentrated on developing new nanosystems capable to exploit the properties of each component but also the synergetic effect between them [3]. A viable alternative for developing supercapacitor electrodes is represented by porous silicon as backbone architecture for its great abundance and high conductivity, paired with deposition of thin carbon layer or other nanoparticles on its surface to further increase the supercapacitor performance [4]. Herein, we report a scalable route to wafer-size processing for fabrication of hybrid electrodes based on cobalt hexacyanoferrate/carbon/porous silicon (CoHCF/C/Si) via electrochemical processes [5]. First, an electrochemical etching process was used to obtain a 3D nanoporous matrix on the top of silicon wafer, then the resulted high surface was covered with active nanomaterials by the successive electrochemical deposition of an ultra-thin carbon layer and CoHCF nanocubes, respectively. The fabricated symmetric supercapacitor device was investigated by cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) and electrochemical impedance spectroscopy (EIS), showing excellent volumetric capacitance of about 5 F cm-3 at the current density of 0.7 mA cm-2, an outstanding volumetric power density of 19.42 W cm-3 with a high energy density of 0.98 mWh cm-3, and good cycling stability with a capacitance retention of 61% after 5000 cycles at 100 A g-1. The CoHCF phase favors migration of Li+ ions into the material, followed by charge transfer reactions via insertion/extraction of alkaline ions into/from the cyano-bridged framework during the redox reactions of FeII/III and CoII/III ions as evidenced by CV and GCD. These results support the successful integration of CoHCF nanocubes in hybrid silicon electrodes using electrochemical methods, bringing synergistic effects over the electrochemical performances. References [1] Y. Zhang, J. Wang, M. Li, Y. Wang, J. Electrochem. Soc. 166 (2019) A98–A106. [2] L. Kouchachvili, W. Yaïci, E. Entchev, J. Power Sources 374 (2018) 237–248. [3] S.G. Sayyed, H.M. Pathan, A. V. Shaikh, S.F. Shaikh, A.M. Al-Enizi, J. Energy Storage 33 (2021) 102076. [4] C. Romanitan, P. Varasteanu, I. Mihalache, D. Culita, S. Somacescu, R. Pascu, E. Tanasa, S.A.V. Eremia, A. Boldeiu, M. Simion, A. Radoi, M. Kusko, Sci. Rep. 8 (2018) 1–14. [5] I.-N. Bratosin, C. Romanitan, G. Craciun, N. Djourelov, M. Kusko, M.C. Stoian, A. Radoi, Electrochim. Acta (2022) 140632.

E.7.5
15:30 Coffee break    
16:00
Authors : Jan-Philipp Hoffknecht1,2 Jaschar Atik3, Alina Wettstein4, Andreas Heuer3,4 Diddo Diddens3, Elie Paillard5
Affiliations : 1 University of Muenster, Institute for Inorganic and Analytical Chemistry, Corrensstr. 28/30, 48149 Münster, Germany 2 MEET Battery Research Center, University of Münster, Corrensstrasse 46, D 48149 Münster, Germany 3 Forschungszentrum Juelich-IEK12 dHelmholtz Institute Münster, Corrensstrasse 46, 48149 Münster, Germany 4 University of Münster, Institute for Physical Chemistry, Corrensstrasse 28/30, 48149 Münster, Germany 5 Politecnico di Milano, Dept. Energy, Via Lambruschini 4, 20148, Milan, Italy

Resume : Lithium metal polymer batteries using ‘dry’ PEO-based electrolytes still suffer from too high temperature operation and slow charge. Almost 20 years ago, ionic liquids were proposed as 'an elegant fix' for polymer electrolytes, since they are non-flammable plasticizers1,2. This allowed a tremendous increase of the conductivity of polymer electrolytes at lower temperatures. The ionic liquids used then were based on cations, such as N-alkyl-N-alkyl pyrrolidinium and anions such as bis(trifluoromethanesufonyl)imide. In fact, it had been known for decades that using low coordinating anions, especially in low dielectric constant polymer or ionic liquid-based electrolytes, allows reaching high solubility, dissociation and ionic mobility3. Thus, it has been, so far, considered that low coordinating ionic liquids (ILs) would be the best choices for ternary polymer electrolytes. However, it was shown that these ILs cannot compete with the strongly coordinating PEO chains for lithium solvation 4. As a result, similarly to PEO-salt complexes, the low coordinating anions (and cations, in the case of ILs) are, by far, the most mobile species. In fact, instead of triggering new conduction modes, the main conduction modes of dry PEO-based electrolytes are preserved (i.e. mainly along single chains) and conduction paths become ‘diluted’ by the introduction of the IL. Although ILs act effectively as plasticizer by increasing PEO segmental mobility, they are, for the most part, not liberating Li movement from this segmental mobility. Thus we propose the use of solvating Ionic liquids having either solvating cations5 or solvating anions6 sufficiently stable vs. Li and LiFePO4 and able to compete with PEO for lithium solvation to enable much faster lithium transport in ternary PEO/IL/Li salt ternary complexes. 1. Shin, J. H., Henderson, W. A. & Passerini, S. Ionic liquids to the rescue? Overcoming the ionic conductivity limitations of polymer electrolytes. Electrochem. commun. 5, 1016–1020 (2003). 2. Shin, J.-H., Henderson, W. & Passerini, S. An Elegant Fix for Polymer Electrolytes. Electrochem. Solid-State Lett. 8, A125 (2005). 3. Benrabah, D., Baril, D., Sanchez, J.-Y., Armand, M. & Gard, G. G. Comparative electrochemical study of new poly(oxyethylene)–Li salt complexes. J. Chem. Soc., Faraday Trans. 89, 355–359 (1993). 4. Diddens, D. & Heuer, A. Simulation study of the lithium ion transport mechanism in ternary polymer electrolytes: The critical role of the segmental mobility. J. Phys. Chem. B 118, 1113–1125 (2014). 5. Atik, J. et al. Cation-Assisted Lithium Ion Transport for High Performance PEO based Ternary Solid Polymer Electrolytes. Angew. Chemie - Int. Ed. in press, (2021). 6. Hoffknecht, J.-P. et al. Are Weakly Coordinating Anions Really the Holy Grail of Ternary Solid Polymer Electrolytes Plasticized by Ionic Liquids? Coordinating Anions to the Rescue of the Lithium Ion Mobility. in prep. (2022).

E.8.1
16:30
Authors : Ahiud Morag1, Minghao Yu1*, Xinliang Feng1,2*
Affiliations : 1 Faculty of Chemistry and Food Chemistry & Center for Advancing Electronics Dresden (cfaed), Technische Universität Dresden, 01062 Dresden, Germany; 2 Max Planck Institute of Microstructure Physics Weinberg 2, 06120 Halle, Germany

Resume : Benefiting from the appealing features of the Mg metal anodes, magnesium batteries (MBs) present attractive potential as sustainable batteries of tomorrow. However, the Mg metal anode-compatible electrolytes generally contain large-size and strongly bonded Mg-clusters (i.e., MgxCly2x-y), resulting in the inefficient cathode chemistries associated with the sluggish Mg-species insertion. Here, using the iconic TiS2 cathode, we demonstrate the pronounced effect of ionic liquid on regulating MgxCly2x-y clusters in the MB electrolyte and promoting the high-kinetics multi-Mg-species insertion into TiS2. Specifically, the addition of ionic liquid into the conventional MgCl2-containing electrolyte induces a nontrivial two-plateau charge/discharge profile of the TiS2 electrode, in which Mg2+ and MgCl+ are disclosed to be dominant insertion species at the high-potential plateau and low-potential plateau, respectively. Molecular dynamic simulations indicate that the ionic liquid additive can dissociate large, thermodynamically stable, MgxCly2x-y clusters to produce MgCl+, which can be effectively stabilized by ionic liquid cation and anion. Meanwhile, the ionic liquid cation catalyzes the Mg-Cl dissociation, thus creating the desirable Mg2+ species. These electrolyte-regulation behaviour consequently enable the TiS2 cathode with a decent specific capacity (81 mAh g–1 at 10 mA g–1), high rate capability (63 mAh g–1 at 200 mA g–1), and long-term durability (86% capacity retention after 500 cycles).

E.8.2
16:45
Authors : Priyanka Rani,1 Anupam Midya,1 Dipak K Goswami 2
Affiliations : 1School of Nanoscience and Technology, Indian Institute of Technology Kharagpur, Kharagpur 721302, India, 2 Department of Physics, Indian Institute of Technology Kharagpur, Kharagpur 721302, India

Resume : Inexpensive synthesis with scalable design of biocompatible flexible supercapacitor are highly desirable for portable and wearable electronics. In this article, we have synthesized high-quality and ultrathin nanosheets of transition metal dichalcogenides (TMDs) by easy, fast, scalable and controlled methods. We have also modulated the dimensions and phases of transition metal dichalcogenides to investigate supercapacitive behaviour of nanosheets as an electrode material. In supercapacitor, choice of electrolyte also plays a vital role to define the performance of capacitive behaviour, flexibility and biocompatibility of the device. Room-temperature ionic liquids extensively researched as an electrolyte due to their admirable thermal stability, wide working temperature range, non-volatility, and broad electrochemical window. Ionic liquids (ILs) cytotoxicity enhances their interest in biomedicine by acting as antimicrobial and anticancer agents. Herein, we have used 1-butyl-3-methylimidazolium chloride ionic liquid as an electrolyte and the effect of electrolyte concentration on WS2 based ionic liquid supercapacitor is studied. The ionic liquid 1-butyl-3-methylimidazolium chloride, act as both solvent and mesoporosity-inducer. In this work, we report a flexible solid-state supercapacitor keeping all key components in mind, including the electrodes, binder, separator and electrolyte.

E.8.3
17:00
Authors : Marieke van Leeuwen, Rahul Maity, Nina Plankensteiner, Matias Jobaggy, Joeri F.M. Denayer, Philippe M. Vereecken
Affiliations : imec and KU-Leuven, Leuven, Belgium; Department of Chemical Engineering, Vrije Universiteit Brussel, Belgium; imec, Leuven, Belgium; imec, Leuven, Belgium, Department of Chemical Engineering, Vrije Universiteit Brussel, Belgium; imec and KU-Leuven, Leuven, Belgium

Resume : One step carbon capture and utilization from dilute sources like flue gases can be achieved by using CO2 sorbent materials as electrolytes [1]. Integration of the subsequent separation and reduction steps can highly reduce the costs, thereby paving the way to economically feasible CO2 reduction. Criteria for adequate CO2 sorbent materials include fast kinetics, high sorption capacity and selectivity, and good chemical and thermal stability[2]. Industrial processes for carbon capture, such as CO2 scrubbing from flue gases in monoethanolamine (MEA), have already been implemented worldwide[3]. However, major improvements are still required to make this process more economically attractive. CO2 is separated from the stream in the form of a carbamate compound and released as gas upon heating. Amine-based solvents are often paired with corrosivity, volatility and high energetical cost of regeneration due to the high enthalpy of reaction for the reaction of CO2 and the amine. Alternative candidates, such as ionic liquids, are under investigation as the physisorption mechanism involved requires less energy for solvent regeneration. Moreover, their regeneration is more straightforward due to their typical non-volatility. The large-scale use of bulk ionic liquids is at this point impeded by their high cost and toxicity. Embedding these materials in matrices, such as metal oxides, can enable to maintain their physical properties while limiting these effects[4]. Different studies have reported the uptake of CO2 by mesoporous silica-supported ionic liquids, with an uptake up to 3 mmol/g for pure silica-ionic liquid compounds and with high selectivity, reaching 20 times higher sorption capacities for CO2 than for N2[5]. Modification of these compounds, for example with amine groups, has enabled to reach uptakes up to 5.53 mmol/g[6]. In this work, different ionic liquid templated silica sol-gel processes for CO2 uptake are explored for the first time, both via hydrolytic and non-hydrolytic routes. Next to limiting the amount of ionic liquid needed, the use of composites allows to fixate the ionic liquid and thereby to prevent deleterious leaches. Alkyl chain length of the ionic liquid cation, as well as fluorination of the anion are known to enhance CO2 sorption. Influence of these components on gas uptake in the IL-silica composites are investigated, together with the effect of ionic liquid-to-matrix ratio. The ionic liquid retention in the material, having received very limited attention so far, is explored to probe the prospects for integrated carbon capture and utilization. Effects of synthesis route, silica pore structure and surface groups on stability in aqueous environments are presented. (1) Sullivan, Coupling Electrochemical CO2 Conversion with CO2 Capture. Nat Catal 2021, 4 (11), 952–958. (2) Polesso, Imidazolium-Based Ionic Liquids Impregnated in Silica and Alumina Supports for CO2 Capture. Mat. Res. 2019, 22 (suppl 1), e20180810. (3) Ramdin, State-of-the-Art of CO2 Capture with Ionic Liquids. Ind. Eng. Chem. Res. 2012, 51 (24), 8149–8177. (4) Vioux, Use of Ionic Liquids in Sol-Gel; Ionogels and Applications. Comptes Rendus Chimie 2010, 13 (1), 242–255. (5) Zhu, Effect of Immobilization Methods and the Pore Structure on CO2 Separation Performance in Silica-Supported Ionic Liquids. Microporous and Mesoporous Materials 2018, 260, 190–200. (6) Garip, IL Containing Amine-Based Silica Aerogels for CO2 Capture by Fixed Bed Adsorption. Journal of Molecular Liquids 2020, 310, 113227.

E.8.4
17:15
Authors : Wouter Dirk Badenhorst, Kuldeep, Laura Sanz, Catia Arbizzani, Lasse Murtomäki
Affiliations : Wouter Dirk Badenhorst; Kuldeep; Lasse Murtomäki; Department of Chemistry and Materials Science, School of Chemical Engineering, Aalto University, PO Box 16100, 00076 AALTO, Finland. Laura Sanz; Nvision System & Technologies S.L, Avenida Barcelona (ed ig nova Tecnoespai), 105 - DESP 8, Igualada, 08700, Barcelona, Spain. Catia Arbizzani; Alma Mater Studiorum - University of Bologna, Dept. of Chemistry “Giacomo Ciamician”, Via F. Selmi 2, 40126 Bologna, Italy.

Resume : In recent years the adoption of various renewable energy sources to move away from fossil fuel sources has accelerated the need for large scale energy storage. With numerous of the renewable energy sources being inherently intermittent in their operation large scale energy storage is required to store energy during high production periods, then to later supply the stored energy to the grid. Currently the most widely employed storage method for renewable and non-renewable energy storage is hydropower. While this technology is cost-effective, it is not suitable for all geographical locations as hydropower storage requires distinct geological features to keep costs down. Therefore, as of late the use of large-scale chemical energy storage has been investigated to diversify the available energy storage solutions. The most common chemical energy storage devices are vanadium redox flow batteries (VRFBs), iron chromium redox flow batteries (ICRFBs), and non flow batteries such as the lithium-ion battery. However, due to the large scale of energy storage required to transition fully to renewable energy, further diversification of large-scale energy technology is required, with an emphasis on the technology to be ecologically and economically sustainable. One such alternative to these technologies is the aqueous all copper redox flow battery (CuRFB) that exploits the single element copper to provide an easy to use and relatively low cost RFB. Additionally with the CuRFB the electrolyte is recyclable using existing copper recovery techniques, and the mild copper electrolyte allows for the use of inexpensive and greener membrane alternatives. With the CuRFB currently still being understudied as a complimentary energy storage technology, as a part of the European Union’s Horizon 2020 program, a variety of improvements to the CuRFB technology was studied. Using carbon ink coatings for the copper deposition and modern hydrocarbon separators, the CuRFB was successfully operated at energy efficiencies up to 77 %. An 9 % improvement in energy efficiency was achieved when compared to the previous work. In addition to this the most significant improvement, the operational lifetime of the CuRFB is extended before electrolyte and device maintenance is required. During testing the CuRFB was operated for over 50 charge and discharge cycles (210 hours) with approximately 32 % of the capacity remaining. With the modern ion-exchange membranes showing excellent stability in the mild copper electrolyte, operation well over 1200 hours with little to no degradation in the membrane material was observed. Finally, it was demonstrated that it is technically feasible to regenerate the CuRFB electrolyte to 96 % of its original capacity through mixing of both the catholyte and anolyte. The single element nature of the CuRFB allows for a greatly simplified electrolyte maintenance procedure compared to VRFBs and ICRFBs which require extensive rebalancing cells.

E.8.5
Start atSubject View AllNum.Add
14:00
Authors : S. Bordignon,‡ C. Pistidda,† T. T. Le,† M. R. Chierotti‡
Affiliations : ‡Università degli Studi di Torino, Department of Chemistry and NIS Centre, via P. Giuria 7, 10125, Torino, Italy †Institute of Hydrogen Technology, Helmholtz-Zentrum hereon GmbH, Max-Planck-Straße 1, D-21502 Geesthacht, Germany

Resume : Metal borohydrides, amides of alkaline and alkaline-earth metals, and metal hydride solid-state materials are currently considered a promising option to effectively and safely store hydrogen. In particular, metal amide-hydride mixtures have been extensively studied as potential hydrogen storage media for mobile and stationary applications, owing to their high hydrogen storage capacity and favorable thermodynamics, which in many cases allow releasing hydrogen at temperatures below 150 °C in a reversible way. Since these materials are usually synthesized through mechanochemical methods, their characterization by means of single-crystal X-ray diffraction proves quite challenging. In the present work, we show the ability of solid-state NMR in providing structural information on a series of energy storage materials. In addition to providing some fundamentals of the technique, the talk will focus on its multinuclear approach (e.g. 1H, 7Li, 11B, 15N ...) which allows to clarify polymorphism, phase purity, outcome of the reactions, symmetry of the sites and dynamics. Calculations are also a key tool combined with experimental data as they help in assisting chemical shift assignment and in the structure assessment. Some of the cases presented will concern: metal amide-hydride solid solutions[1-2], borohydrides mixtures [3]; reactions with H2 [4]. References [1] A. Santoru, C. Pistidda, M. H. Sørby, M. R. Chierotti, S. Garroni, E. Pinatel, F. Karimi, H. Cao, N. Bergemann, T. T. Le, J. n Puszkiel, R. Gobetto, M. Baricco, B. C. Hauback, T. Klassen, M. Dornheim Chem. Commun. 52, 11760-11763 (2016) [2] A. Santoru, C. Pistidda, M. Brighi, M. R. Chierotti, M. Heere, F. Karimi, H. Cao, G. Capurso, A.-L. Chaudhary, G. Gizer, S. Garroni, M. H. Sørby, B. C. Hauback, R. Černy,́ T. Klassen, M. Dornheim Inorg. Chem., 57, 3197−3205 (2018) [3] N. Bergemann, C. Pistidda, C. Milanese, T. Emmler, F. Karimi, A.-L. Chaudhary, M. R. Chierotti, T. Klassenad and M. Dornheim Chem. Commun. 52, 4836-4839 (2016) [4] C. Pistidda, A. Santhosh, P. Jerabek, Y. Shang, A. Girella, C. Milanese, M. Dore, S. Garroni, S. Bordignon, M. R Chierotti, T. Klassen, and M. Dornheim J. Phys. Energy 3, 044001 (2021)

E.9.1
14:30
Authors : Martin A. Karlsen, Jonathan De Roo, Simon J. L. Billinge, and Dorthe B. Ravnsbæk
Affiliations : Department of Physics, Chemistry, and Pharmacy, University of Southern Denmark, Campusvej 55, 5230 Odense M, Denmark. Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056 Basel, Switzerland. Department of Applied Physics and Applied Mathematics, Columbia University, 500 W 120th St, New York, NY 10027, USA. Department of Chemistry, Aarhus University, Langelandsgade 140, 8000 Aarhus C, Denmark.

Resume : Total scattering and pair distribution function (PDF) analysis allows one to study the material structure even for non-crystalline materials, whether they are nanocrystalline, disordered, or even amorphous. This goes for ex situ as well as operando studies, where the latter allows one to study material properties during operation. Recently, the website ‘PDF in the cloud’ [1] (PDFitc, pdfitc.org) has been offered to assist PDF analysis through various apps. In this work, the structureMining [3] app has been used for phase identification of ex situ PDF data to obtain starting models for quantitative PDF analysis using the DiffPy-CMI [2] software, the similarityMapping app has been used to study similarity and reversibility for operando data through Pearson cross-correlation, and the nmfMapping [4-5] app has been used to study the number of components (phases) needed to describe operando data through non-negative matrix factorization (NMF). The science case presented here is about TiO2-bronze nanocrystals that have been synthesized approximately 3, 5, and 7 nm in size [6]. The 3 nm nanocrystals have been incorporated into a Li-ion battery and the material evolution during Galvanostatic cycling is studied in an operando total scattering combined with PDF analysis. The analyses of both the ex situ and operando PDF data are highly assisted by the novel tools of PDFitc to elucidate the structural properties of pristine and chemically lithiated materials as well as the structural evolution during Galvanostatic cycling in a Li-ion battery. References [1] Yang et al., Acta Cryst. (2021). A77, 2-6. [2] Juhás et al., Acta Cryst. (2015). A71, 562-568. [3] Yang et al., Acta Cryst. (2020). A76, 395-409. [4] Liu et al., J. Appl. Cryst. (2021). 54, 768-775. [5] Thatcher et al., Acta Cryst. (2022). A78, 242-248. [6] Billet et al., Chem. Mater. 2018, 30, 13, 4298-4306.

E.9.2
14:45
Authors : Julien Morey, Jean-Bernard Ledeuil, Lénaïc Madec, Hervé Martinez
Affiliations : Universite de Pau et des Pays de l’Adour, E2S UPPA, CNRS, IPREM, Pau, France; Universite de Pau et des Pays de l’Adour, E2S UPPA, CNRS, IPREM, Pau, France; Universite de Pau et des Pays de l’Adour, E2S UPPA, CNRS, IPREM, Pau, France; Universite de Pau et des Pays de l’Adour, E2S UPPA, CNRS, IPREM, Pau, France

Resume : Lithium solid-state batteries (SSBs) are a promising technology for electrochemical energy storage systems. However, their development remains limited by the electro-chemo-mechanical properties of the solid/solid interfaces (such as the Li/solid electrolyte one) and their evolution over time [1-2]. Moreover, as these interfaces are buried in the battery stack, their thorough analysis by surface analysis techniques, i.e. XPS, Auger and ToF-SIMS, remains a challenge so far [3]. Indeed, most of the time, a cross sectioning of the battery stack is required to reveal these buried interfaces but it is not a trivial task. In this presentation, it will be showed that using ion milling at liquid nitrogen temperature is a suitable and reproducible method to prepare cross sections even for polymer-based SSBs. Regarding the analysis of the solid/solid interfaces, ex situ analysis over cycling of prepared cross sections is the most used method so far. However, to limit further any possible sample pollution and interfaces degradation, in situ (i.e. sequential analysis and electrochemical cycling) and operando (i.e. analysis and cycling at the same time) analyses have been proposed in the literature [3-5]. In this presentation, operando Auger analysis will be presented for the first time on a model Li/Li6PS5Cl stack. It will be showed that the use of the fully adjustable electron beam of the Auger allows creating a potential difference, then lithium migration, SEI formation and Li platting, thus suppressing the need for a dedicated electrochemical cell. In addition, Auger results will be compared with operando XPS and ToF-SIMS analyses performed on the same model system using the flood gun (charge neutralizer) as electron source. Overall, the advantages and drawbacks of these innovative operando analyses regarding the understanding of the interfaces chemical properties at different length-scales will be discussed. Thus, it is believed that it will greatly benefit to all researchers working on buried interfaces study in SSBs. [1] D. H. S. Tan, et al., Nat. Nanotechnol. 2020, 15, 170-180 [2] C. Sangeland et al., Solid State Ionics, 2019, 343, 115068 [3] J. Morey, et al., J. Matter. Chem. A. 2021, 9 (45), 25341-25368 [4] M. G. Boebinger et al., ACS Energy Letters, 2020, 5, 335-345 [5] X. Liu et al., Nature Communications, 2013, 4, 2568

E.9.3
15:00
Authors : Kai Sellschopp, Paul Jerabek
Affiliations : Institute of Hydrogen Technology, Helmholtz-Zentrum Hereon, Geesthacht, Germany

Resume : Green hydrogen will play a major role in the energy transition towards a cyclic economy, especially for replacing fossil feedstocks in the chemical industry, but also for energy storage. Metal hydrides allow to store hydrogen at pressures and temperatures close to ambient conditions. This can make hydrogen storage more efficient, and at the same time increase safety for mobile and stationary applications. The development of new sustainable metal hydrides with the desired properties, however, necessitates a deeper understanding of these materials as well as a high-throughput screening of interesting candidates. Both can be achieved with computational materials science studies. Ab-initio methods, which work without any experimental input, have the additional advantage of minimizing the required amount of samples, thereby making the materials research itself more sustainable. They are employed to calculate many of the properties relevant when searching for new metal hydrides, such as formation enthalpies, diffusion barriers, and electronic structure. However, all ab-initio methods rely on a set of approximations and choices made by the researcher to reduce the computational effort, which are rarely reviewed. Therefore, this contribution assesses the accuracy of some of the most common of these approximations and choices, such as density functionals, dispersion corrections or how vibrational modes are described, for a set of binary metal hydrides. As a result, modelling recipes for metal hydrides are developed, which can be employed in high-throughput screening of new candidate materials as well as in in-depth studies of material properties. The modelling recipes do not only include the computational settings, but also the workflow to compute desired properties. In the process of testing the recipes, outliers are detected, which reveals errors and shows the necessity to adapt the recipes for certain materials. Creating a cookbook of modelling recipes based on accuracy assessments is meant to build trust into computational results and to enable a partially automated search for new materials. Furthermore, it will make it easier for any materials scientist to dive into the intricate task of computing the properties of metal hydrides, just as a regular cookbook makes it easier for anyone to prepare a tasty dish.

E.9.4
15:15
Authors : Paul Jerabek, Brandon Wood, Tae Wook Heo, Sally Brooker
Affiliations : Institute of Hydrogen Technology, Helmholtz-Zentrum Hereon, Geesthacht, Germany Materials Science Division, Lawrence Livermore National Laboratory, Livermore, USA Department of Chemistry, University of Otago, Dunedin, New Zealand

Resume : Deep understanding of (de)hydrogenation thermodynamics and kinetics of metal hydride materials is essential in order to allow targeted design of novel hydrogen storage materials and optimization of existing compositions tailor-made for specific application scenarios. Scale-bridging computer simulations are a powerful tool to support the experimental efforts by offering in-depth understanding of the underlying physico-chemical processes that enable in-silco materials design with sophisticated models. In this talk, an overview of the multi-scale methodology for metal hydride materials, ranging from atomistic to mesoscale, will be given as currently performed in the joint efforts by the computational materials design groups at “Helmholtz-Zentrum Hereon” and “Lawrence Livermore National Laboratory”. Within the collaboration, a digital workflow is developed linking Density Functional Theory (DFT) methods, thermodynamic modeling and phase-field simulations to allow an integrated description of (de)hydrogenation processes of metal hydrides. Concrete examples from an international experimental/theoretical research project on metal hydride materials jointly performed together with academic partners in New Zealand will be presented as possible use cases for the introduced computational methodology.

E.9.5
15:30 Coffee break    
16:00
Authors : Francesca M. Toma
Affiliations : Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94577

Resume : Carbon neutral energy sources that are scalable, deployable, and cost effective will be required at an unprecedented scale to halt irreversible climate change. To design novel materials that can efficiently produce energy with minimal impact on the environment, few factors are of primary importance: i) complete understanding of the properties of the most selective and efficient reaction environments, and ii) correlative characterization of their behavior under operating conditions. Here, we will focus on the role played by microenvironments and on the opportunities offered by the utilization of sunlight for hydrogen production and CO2 reduction. We will show the synthesis and the advanced characterization of integrated semiconductors and catalysts for (photo)electrocatalytic systems as they can be used under realistic operating conditions for solar fuel production. We will present recent results from our group supported by theoretical calculations that led to highly selective CO2 (photo)reduction on Cu, Ag, and Cu2O electrodes. In addition, we will discuss how to make more durable materials for light-driven H2 production.

E.10.1
16:30
Authors : Terry D. Humphries, Kasper T. Møller, Lucas Poupin, Lucie Desage, Mark Paskevicius, Craig E. Buckley
Affiliations : Terry D. Humphries - Physics and Astronomy, Curtin University, GPO Box U1987, Perth, WA 6845, Australia; Kasper T. Møller - Physics and Astronomy, Curtin University, GPO Box U1987, Perth, WA 6845, Austalia, Department of Biological and Chemical Engineering, Aarhus University, Aabogade 40, Aarhus DK-8200, Denmark; Lucas Poupin - Australia; Physics and Astronomy, Curtin University, GPO Box U1987, Perth, WA 6845, Australia; Lucie Desage - Physics and Astronomy, Curtin University, GPO Box U1987, Perth, WA 6845, Australia; Mark Paskevicius - Physics and Astronomy, Curtin University, GPO Box U1987, Perth, WA 6845, Australia; Craig E. Buckley - Physics and Astronomy, Curtin University, GPO Box U1987, Perth, WA 6845, Australia

Resume : Current global affairs are highlighting that the world is on a knife edge with regards to energy supply and dependency. Utilising renewable energy sources is still at the forefront of climate control and future energy supply, but large-scale energy storage is still a problem to be solved. Thermal Energy Storage (TES) or “Thermal Batteries” (TB) are scalable to an extent that thousands of homes can be powered from one installation. TES using the sensible heat of molten salts has been shown to be successful on a scale of 100’s MW’s, but the energy density is low (413 kJ/kg) and is limited to temperatures of below 565 °C [1, 2]. Many latent heat materials have been investigated, but thermochemical energy storage (TCES) is the most efficient form of thermal energy storage. TCES utilises heat produced from renewable energy sources, or directly from the sun, to heat the TCES material causing bond dissociation to occur. This is an endothermic reaction (charging the TB) with the products being stored separately. To discharge the TB, the materials would be reintroduced causing an exothermic reaction, with the heat being used to produce electricity. Metal hydrides (e.g. CaH2, MgH2, Mg2FeH6) and metal carbonates (e.g. CaCO3, BaCO3) have been investigated as TCES materials and their physical properties optimised to enable reversible gas storage using additives and catalysts [1-4]. While many materials have been recently shown to be potential TES materials on a gram scale, efforts have been made to build TB prototypes with >1 kg of material. These prototypes are not only to demonstrate that the TES materials can cycle at scale, but they must also include other systems be called a TB. This includes the addition of gas storage (store the gas desorbed during charging), heat transfer materials (to deliver heat to the TES material and the heat engine), development of reactor materials that are corrosion resistant and optimisation of thermoclines [5]. This presentation will provide an overview of the development of prototype TB’s produced at Curtin University from materials development, TB design, to heat transfer. References [1] Humphries TD, Paskevicius M, Alamri A, Buckley CE. J Alloys Compd. 2022;894:162404. [2] Adams M, Buckley CE, Busch M, Bunzel R, Felderhoff M, Heo TW, et al. Progress in Energy. 2022. [3] Poupin L, Humphries TD, Paskevicius M, Buckley CE. Int J Hydrogen Energy. 2021;46:38755-67. [4] Møller KT, Humphries TD, Berger A, Paskevicius M, Buckley CE. Chemical Engineering Journal Advances. 2021;8:100168. [5] Desage L, McCabe E, Vieira AP, Humphries TD, Paskevicius M, Buckley CE. Renew Sustain Energy Rev. 2022:submitted.

E.10.2
16:45
Authors : Maria Taeño, Cristina Luengo, Stefania Doppiu, Elena Palomo
Affiliations : CIC energigune, Parque Tecnológico de Álava, Albert Einstein 48, 01510, Vitoria-Gasteiz, Spain

Resume : The increasing use of renewable energy sources has promoted the development of several energy storage systems. In this context, thermal energy storage (TES) has become a key technology which can help to balance energy demand and supply on a daily, weekly, and even seasonal basis. Many materials and processes (sensible, latent and thermochemical storage) can be used to store thermal energy allowing to cover a wide range of applications (low-medium-high temperatures). Materials undergoing solid-solid phase transition are considered promising candidates for thermal energy storage. The system Li2SO4-Na2SO4 has been widely studied because of the fast-ionic conductivity of the observed phases at high temperature. However, the use of these materials for thermal energy storage, has not been thoroughly investigated. As a few examples, Chen et al.1 and Doppiu et al.2 reported different Li2SO4-Na2SO4 compositions with the most promising theoretical enthalpy of transformation, corresponding to Li2SO4-Na2SO4 (79/21 and 50/50 molar ratio), confirming the great potentiality of these materials for TES applications at high temperature (~500 °C). In this work, the stoichiometric compound LiNaSO4 corresponding to the 50/50 mol composition has been synthesized and widely characterized. A robust cycling of the materials was carried out in order to study the long-term stability and how the thermophysical properties are affected by the long thermal cycling (up to 100 cycles). For this purpose, a comprehensive study of the morphological, structural, and thermal properties of the materials subjected to 100 heating/cooling cycles around the phase transition, was carried out. For this composition, the phase transition between β-Li2SO4 (room temperature) and α- Li2SO4 (high temperature) undergoes at 520 °C. The structural and morphological properties were studied using different characterization techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM) or Raman spectroscopy. In addition, in situ X-ray diffraction was also performed in order to study the structural transformation upon heating. The reactivity and the thermal properties of the LiNaSO4 were tested by different thermal techniques. The reaction enthalpy of the materials after 100 cycles was measured by differential scanning calorimetry (DSC), showing values above 150 J/g and confirming the good cyclability. Other important thermophysical parameters such as specific heat capacity, thermal diffusivity or thermal conductivity of the cycled material were also evaluated.

E.10.3
17:00
Authors : K. Williamson1, K.T. Møller2, A.M. D’Angelo3, T.D. Humphries1, M. Paskevicius1, C.E. Buckley1
Affiliations : 1 Department of Physics and Astronomy, Curtin University, Kent St, Bentley, WA 6102, Australia ; 2 Department of Biological and Chemical Engineering, Aarhus University, Aabogade 40, Aarhus, DK-8200, Denmark; 3 Australian Synchrotron, 800 Blackburn Rd, Clayton, VIC 3168, Australia

Resume : The intermittent nature of renewable energy is a major challenge which can be overcome via cheap effective energy storage [1]. Thermochemical energy storage is an upcoming technology that can improve thermal to electric efficiency and lower cost in applications such as concentrated solar power [1]. Metal carbonates have great potential as thermochemical energy storage materials through the reversible endothermic release and exothermic absorption of carbon dioxide (CO2) [2]. However, major materials challenges include the loss of cyclic energy storage capacity and slow reaction kinetics [3]. Previously, it has been established that the release of carbon dioxide from barium carbonate (BaCO3) can be thermodynamically destabilised by the addition of barium silicate (BaSiO3)[4]. This lowers the operating temperature for gas cycling from ~1400 °C to 850 °C to allow operation with second generation concentrated solar plants. Moreover, the addition of a calcium carbonate (CaCO3) catalyst improves kinetics by a factor of 10 [4]. This research explores the thermochemical gas-solid reactions of barium carbonate combined with iron oxide (III). This materials composite reduces the operating temperature from 1400 °C to 875 °C and improves the reaction kinetics of carbon dioxide release and uptake. The study utilises in-situ synchrotron powder X-ray diffraction to show the co- existence of α-BaCO3 and β-BaCO3 structural polymorphs of BaCO3 and their effect on the thermodynamic parameters of calcination. (1) Paskevicius, M.; Sheppard, D. A.; Williamson, K.; Buckley, C. E. Metal Hydride Thermal Heat Storage Prototype for Concentrating Solar Thermal Power. Energy 2015, 88, 469–477. https://doi.org/10.1016/j.energy.2015.05.068. (2) Carrillo, A. J.; González-Aguilar, J.; Romero, M.; Coronado, J. M. Solar Energy on Demand: A Review on High Temperature Thermochemical Heat Storage Systems and Materials. Chem. Rev. 2019, 119 (7), 4777–4816. https://doi.org/10.1021/acs.chemrev.8b00315. (3) Humphries, T. D.; Møller, K. T.; Rickard, W. D. A.; Sofianos, M. V.; Liu, S.; Buckley, C. E.; Paskevicius, M. Dolomite: A Low Cost Thermochemical Energy Storage Material. J. Mater. Chem. A 2019, 7 (3), 1206–1215. https://doi.org/10.1039/C8TA07254J. (4) Møller, K. T.; Williamson, K.; Buckley, C. E.; Paskevicius, M. Thermochemical Energy Storage Properties of a Barium Based Reactive Carbonate Composite. J. Mater. Chem. A 2020, 8 (21), 10935–10942. https://doi.org/10.1039/D0TA03671D.

E.10.4
17:15
Authors : Sul Ki Park, Buddha Deka Boruah, Arvind Pujari and Michael De Volder
Affiliations : Department of Engineering, University of Cambridge, Cambridge CB3 0FS, UK

Resume : Interactions of light with certain active battery or capacitor materials have been shown to enhance the charging rate or even to charge devices directly with light. These devices that combine features of solar cells with classic energy storage devices have gained substantial interest to enhance the rate performance or to even charge energy devices directly with light. To the best of our knowledge, this paper reports the first light-enhanced magnesium (Mg)-ion capacitor (Photo-MIC) system. Vanadium dioxide (VO2) and reduced graphene oxide based photoelectrodes were used in this system to convert light into energy and then store it directly in the same electrode component. The capacity enhancements by the light of up to 33% were observed and the devices achieved a higher energy density of 20.54 mAh kg-1 and power density of 3462.80 W kg-1 when illuminated.

E.10.5
Start atSubject View AllNum.Add
09:00
Authors : Paul Jerabek, Sally Brooker
Affiliations : Paul Jerabek, Helmholtz Zentrum hereon, Germany; Sally Brooker, University of Otago, New Zealand

Resume : This invited lecture, presented virtually, will introduce: (a) New Zealand's situation as regards the development of a green hydrogen economy, and (b) the newly established German-New Zealand Green Hydrogen research, networking and outreach centre, jointly led by Dr Paul Jerabek (HZH) and me (Otago), and funded by the BMBF (Germany) and MBIE (NZ).

E.11.1
09:30
Authors : Chiara Milanese 1, Ilaria Frosi 2 , Alessandro Girella 1 , Adele Papetti 2, W. A. M, A. N. Illankoon 3, S. Sorlini 3, Giacomo Magnani 4, Daniele Pontiroli 4, Mauro Riccò 4
Affiliations : 1Pavia Hydrogen Lab, C.S.G.I. & Chemistry Department, Viale Taramelli 16, Università di Pavia, Italy; 2 Pavia Food Lab, Drug Science Department, Viale Taramelli 14, Università di Pavia, Italy; 3 Civil, Environmental, International Cooperation and Mathematical Engineering, University of Brescia - Via Branze 43, 25123 Brescia, Italy 4 NanoCarbon Lab, DSMFI, Parco Area delle Scienze 7a, Università di Parma, Italy

Resume : Recently biochar, the carbon side-product in the pyrolysis/gasification of residual waste biomasses, started to receive a widespread attention in the field of energy-storage, thanks to its hierarchical porous structure inherited from biomass precursors, its excellent chemical and electrochemical stability, high conductivity, high surface area and inexpensiveness. In particular, biochar converted to activated carbon (SSA > 1000m2/g) through a chemical treatment with KOH appears to be a new cost-effective and environmentally-friendly carbon material with great application prospect in the field of energy-storage. We report here on the preparation of novel hierarchically-porous super-activated carbon materials originating from biochar derived by the pyrolysis of agrifood wastes such as rice bran and husk, and melon and pumpkin peels (Figure 1). The chemical activation process proved to be efficient to remove the majority of impurities other than carbon, stabilizing highly porous hierarchical structures with local graphene-like morphology. The porous compounds obtained by rice bran and husk mixtures demonstrated to behave as excellent electrode materials for high-performance symmetric supercapacitors (SCs), reaching interestingly high specific capacitance and specific energy. On the contrary, the materials obtained by rice bran or the vegetable peels, having specific surface area up to 3000 m2/g, show a very good hydrogen storage ability, adsorbing up to 4.5 wt % of hydrogen in around 20 seconds at 77K and around 1.5 wt% at room temperature. Work is in progress to optimize the pyrolysis and activation conditions and to improve the performance of the materials by decoration with transition metals.

E.11.2
09:45
Authors : Kaufmann, T. F. J.* (1,2); Puszkiel, J. (1,2); Fleming, L. (1,2); Gizer, G. (2); Bellosta von Colbe, J.M.(2); Klassen, T. (1,2); Jepsen, J. (1,2)
Affiliations : (1) Faculty of Mechanical Engineering, Institute of Materials Engineering, Helmut-Schmidt-University, Holstenhofweg 85, 22043, Hamburg, Germany (2) Institute of Hydrogen Technology, Helmholtz-Zentrum Hereon, Max-Planck-Straße 1, 21502 Geesthacht, Germany * lead presenter

Resume : Countries must reduce their greenhouse gas emissions and perform the transition from fossil fuels to renewable energy sources to limit global warming1. Hydrogen as a green energy vector allows the coupling of various sectors like the electrical and gas grid as well as heating and mobility sector. Therefore, it is important to produce so called green hydrogen for instance via electrolysis from renewable energy sources. The gravimetric density of hydrogen is higher than that of conventional fossil fuels. However, the volumetric density of hydrogen at standard temperature and pressure is only 0.01079 MJ/L, the lowest of commonly used fuels and around 3000 times lower than that of petrol 2. Thus, the compression of hydrogen to pressures of at least 350 bar is necessary for several mobile applications like the fueling of trucks or trains, which commonly use pressure tanks in this pressure range. Metal hydride compressors (MHC) are based on the reversible and thermally driven reaction of metal alloys with gaseous hydrogen to form metal hydrides. Compared to conventional mechanical compressors, these compressors require minor electrical energy and can even convert (industrial) waste heat to compress hydrogen. Moreover, owing to the absence of moving parts, MHCs are quite safe and reliable 3. As part of the project Digi-HyPro (Digitalized hydrogen process chain for the energy transition), funded by dtec.bw – Digitalization and Technology Research Center of the Bundeswehr, this work proposes a design of MHC devices for coupling with an electrolyzer. Computer-aided development of MHCs with finite element (FE) simulations is used as a tool to optimize the design. The interaction of a cylindrical 2-stage MHC model based on room temperature AB2 alloys coupled with an alkaline exchange membrane (AEM) electrolyzer is numerically investigated. Since the metal hydride compression is heat-driven, the heat transport through the metal hydride bed is the most relevant factor in the performance of the MHC during compression. A parametric study is performed to determine the ideal ratio between length and diameter (L/D) for the optimized heat management of the cylindrical 2-stages MHC. The metal hydride beds are heated and cooled between 20 °C and 90 °C using a water-glycol mixture as a heat transfer fluid. Hydrogen is supplied by the AEM electrolyzer at 30-35 bar and 1 Nm³/h and then compressed by the MHC up to 350 bar depending on the heat management. References [1] The Intergovernmental Panel on Climate Change (IPCC) https://www.ipcc.ch/report/ar6/wg1/downloads/report/IPCC_AR6_WGI_Full_Report_smaller.pdf, (accessed June 1, 2022) [2] G. Sdanghi et al., “Review of the current technologies and performances of hydrogen compression for stationary and automotive applications,” Renew. Sustain. Energy Rev., vol. 102, no. 1, pp. 150–170, 2019. [3] M. V. Lototskyy et al., “Metal hydride hydrogen compressors: A review,” Int. J. Hydrog. Energy, vol. 39, no. 11, pp. 5818–5851, 2014.

E.11.3
10:00
Authors : Mark Paskevicius, Ainee Ibrahim, Aneeka Patel, Yurong Liu, Yu Liu, Terry Humphries, Craig Buckley
Affiliations : Curtin University, Perth, WA, Australia

Resume : There is a growing need for renewable energy across Europe and Asia. It is becoming more important to investigate implementing hydrogen as a vector to export renewable energy from energy-laden countries like Australia. So-called ‘green’ hydrogen can be exported by ship in a number of forms as either liquid hydrogen, ammonia, liquid organic hydrogen carriers, or as hydrogen-rich powders. Shipping energy using a powdered metal hydride circumvents the requirements for high gas pressures, toxic chemicals, or low temperatures and could offer a low-cost option for hydrogen transport. We have shown that metal hydrides can be produced using renewable energy in Australia and used to transport this energy through hydrogen, which can easily be released at a destination via hydrolysis. We demonstrate the formation of high pressure hydrogen capable of refilling vehicles, avoiding the need for mechanical compression. We also show the pathways to regenerate these metal hydrides from their hydrolysed by-products. Discussion will be presented on the cost comparison of this method with the more well-discussed alternatives for hydrogen export.

E.11.4
10:15
Authors : Gudaysew T. YENESEW Eric QUAREZ Annie LE GAL LA SALLE Clément NICOLLET Olivier JOUBERT
Affiliations : Not available

Resume : For the first time, a strategy for recycling and recovery of Solid Oxide Cell (SOC) components is presented. From commercial cells, electrodes and electrolyte are separated by mechanical scraping and grinding, followed by thermal and chemical treatments. Materials of the solid oxide fuel cell (SOFC) components including air electrode (LaxSr1-xCoO3), nickel oxide (NiO), which accounts for about 50% of the cell weight, and yttria-stabilized zirconia (YSZ), which is coming from both the fuel electrode and the electrolyte, were successfully recovered. The recovered materials are characterized by several techniques: X-ray diffraction, scanning electron microscopy, thermal analysis, chemical analysis and BET surface area measurement. The conductivity level of the recycled electrolyte materials was measured in air by electrochemical impedance spectroscopy from 300°C to 750°C and compared with different compositions of commercial YSZ materials. A total electrolyte conductivity of 9.8 10-3 S cm-1 was measured at 750°C. The contributions of grain and grain boundary conductivities to the total conductivity are clearly distinguishable at lower temperatures. The contribution of grain boundary resistance increases with the presence of impurities. Keywords: Recycling wastes; Solid Oxide Cells; YSZ; Ionic conductivity; Phase separation.

E.11.5
10:30 Coffee break    
11:00
Authors : Marek Polański, Agata Baran
Affiliations : Military University of Technology, 2 Kaliskiego Str., Warsaw, 00-908, Poland

Resume : A new route of materials synthesis, namely, high-temperature, high-pressure reactive planetary ball milling (HTPRM), is presented. HTPRM allows for the mechanosynthesis of materials at fully controlled temperatures of up to 450°C and pressures of up to 100 bar of hydrogen. As an example of this application, a successful synthesis of magnesium hydride is presented. The synthesis was performed at controlled temperatures (room temperature (RT), 100, 150, 200, 250, 300, and 325°C) while milling in a planetary ball mill under hydrogen pressure (>50 bar). Very mild milling conditions (250 rpm) were applied for a total milling time of 2 h, and a milling vial with a relatively small diameter (ϕ = 53 mm, V = ∼0.06 dm3) was used. The effect of different temperatures on the synthesis kinetics and outcome were examined. The particle morphology, phase composition, reaction yield, and particle size were measured and analysed by scanning electron microscopy, X-ray diffraction, and differential scanning calorimetry (DSC) techniques. The obtained results showed that increasing the temperature of the process significantly improved the reaction rate, which suggested the great potential of this technique for the mechanochemical synthesis of materials.

E.12.1
11:30
Authors : Ebert Alvares, Kai Sellschopp, Tae Wook Heo, Paul Jerabek
Affiliations : Institute of Hydrogen Technology, Helmholtz-Zentrum Hereon, Geesthacht, Germany; Institute of Hydrogen Technology, Helmholtz-Zentrum Hereon, Geesthacht, Germany; Materials Science Division, Lawrence Livermore National Laboratory, Livermore, USA; Institute of Hydrogen Technology, Helmholtz-Zentrum Hereon, Geesthacht, Germany

Resume : The use of intermetallics as a medium for hydrogen storage has regained attraction due to their ability to offer safer operational conditions compared to conventional molecular hydrogen storage tanks. The FeTi alloy offers an economic advantage due to its lower cost compared to other intermetallics and is likely to play an important role as the hydrogen-storage material for stationary applications in residential environments, emergency power supply as well as heavy-weight means of transportation. Within this context, understanding the FeTi alloy phase transformation and the underlying mechanisms helps to control the (de)hydrogenation kinetics, while avoiding undesirable microstructural evolutions that may compromise the storage tank performance. This contribution will present the development of a quantitative phase-field model that includes the chemical energies involved in the (de)hydrogenation processes of the FeTi alloy. At the nanoscale, an atomistic model of the habit plane of the hydride formation from the intermetallic matrix is built and the chemical interface energy is calculated through first-principles methods utilizing density functional theory (DFT). At the mesoscale, the local energy of the system is acquired through the integration of the calculated interfacial energy and the Calphad-type assessment of the Gibbs energies of the phases [1] into phase-field models. The presentation will show and discuss simulations of the FeTi hydrogenation accounting for different types of boundary conditions in detail. The present work serves as an important ground for the development of multi-physics simulations of the FeTi hydrogenation and enables the coupling with micromechanics and diffusivities to eventually integrate itself into macroscale simulations of the hydrogen storage tank system. [1] E. Alvares, P. Jerabek, Y. Shang, A. Santhosh, C. Pistidda, T. W. Heo, B. Sundman, M. Dornheim, Modeling the thermodynamics of the FeTi hydrogenation under para-equilibrium: An ab-initio and experimental study, Calphad, vol. 77, 2022. doi.org/10.1016/j.calphad.2022.102426

E.12.2
11:45
Authors : Puszkiel , J. (1,2)*, Warfsmann, J. (1,2), Passing, M, (2), Krause, P. (1,2), Wienken, E. (1,2), Kaufmann, T. (1,2), Fleming, L. (1,2), Covarrubias Guarneros, M. (1,2), Bellosta von Colbe, J.M. (2), Klassen, T. (1,2), Jepsen, J. (1,2)
Affiliations : (1) Faculty of Mechanical Engineering, Institute of Materials Engineering, Helmut-Schmidt-University, Holstenhofweg 85, 22043, Hamburg, Germany (2) Institute of Hydrogen Technology, Helmholtz-Zentrum Hereon, Max-Planck-Straße 1, 21502 Geesthacht, Germany * lead presenter

Resume : The design of hydrogen storage and compression devices based on metal hydrides (MH) requires appropriate evaluation of thermodynamic properties, kinetic behavior, and engineering parameters. In the frame of the project HyReflexS (Hydrogen-based emergency power supply with integrated control power plant through flexible sector coupling and metal hydride storage), funded by the Federal Ministry of Economics and Climate Protection, and project Digi-HyPro (Digitalized hydrogen process chain for the energy transition), funded by dtec.bw – Digitalization and Technology Research Center of the Bundeswehr, it is here proposed a design of MH-storage and -compressor devices for the energy chain transition. The representative characterization of hydrogen storage properties and engineering properties of industrial batch materials is required for the digital design and subsequent construction of hydride forming alloy-based devices. Room temperature hydrides offer flexible tuneability of the equilibrium pressure, appropiate reaction enthalpies of around 20 kJ/mol H2, fast kinetic behavior at ambient temperature, suitable volumetric hydrogen capacity of around 100 kg H2/m3 and easy handling for practical application and system coupling 1,2. In this work, 1.2 t of AB2-commercial available alloy (Hydralloy C5, GfE company) for storage amount of 10 kg H2 is characterized. A sampling procedure designed to yield representative results of the industrial batch is applied. The thermodynamic parameters and the pressure composition isotherms (PCIs) slope variability are determined and modeled. Experimental measurements of PCIs between 273 K and 323 K provide enthalpies and entropies for absorption and desorption within the expected range (Habs.: 22±1 kJ/mol H2 / Sabs.: 96±1 J/ K mol H2, Hdes.: 23±1 kJ/mol H2 / Sdes.: 96±4 J/ K mol H2). The kinetic parameters are first determined from experimental curves applying numerical quadratic approximation of experimental curves, which allow determining values of the activation energies (Ea) and the pre-exponential factors (A) of Ea,abs.: 19.50 kJ/mol H2 / Aabs.: 109.4 1/s, and Ea,des.: 15.00 kJ/mol H2 / Ades.: 14.96 1/s. A semi-empirical kinetic model is also developed in the relevant range of the above mentioned projects of 10 ºC to 60 ºC and 1 bar to 60 bar and compared with the numerical calculations.Further material properties to characterize hydrogen transport and heat transfer phenomena are also determined and utilized to model and design solid-state hydrogen-containing reservoirs based on metal hydride technology for the sector coupling. References [1] Bellosta von Colbe, J.; Ares, J.-R.; Barale, J.; Baricco, M.; Buckley, C.; Capurso, G. et al. (2019): Application of hydrides in hydrogen storage and compression: Achievements, outlook and perspectives. Int. J. of Hydrogen Energy 44 (15), S. 7780–7808 [2] Lototskyy, M.; Linkov, V.: Thermally driven hydrogen compression using metal hydrides. In: Int. J. of Energy Research, John Wiley & Sons Ltd (2022),1–21.

E.12.3
12:00
Authors : Yuanyuan Shang (a), Claudio Pistidda (*a), Chiara Milanese (b), Alessandro Girella (b), Alexander Schökel (c), Thi Thu Le (a), Annbritt Hagenah (a), Oliver Metz (a), Thomas Klassen (a, d), Martin Dornheim (a)
Affiliations : a Department of Materials Design, Institute of Hydrogen Technology, Helmholtz-Zentrum hereon GmbH, Max-Planck-Straße 1, 21502 Geesthacht, Germany. E-mail: claudio.pistidda@hereon.de b C.S.G.I. & Department of Chemistry, Physical Chemistry Section, University of Pavia, Viale Taramelli 16, 27100 Pavia, Italy c Deutsches Elektronen-Synchrotron DESY, Notkestr. 85, 22607 Hamburg, Germany dHelmut Schmidt University, Holstenhofweg 85, 22043 Hamburg, Germany

Resume : To reduce the carbon footprint associated with the production of hydrogen storage materials and to reduce their cost, we pursue the possibility of obtaining high-quality hydride-based materials from industrial metals waste. In particular, in this manuscript, we propose a method for obtaining high-quality NaAlH4, starting from the Al-based automotive recycled alloy DIN-GDAlSi10Mg(Cu). The hydrogen storage properties of the material obtained by ball milling NaH and DIN-GDAlSi10Mg(Cu) under a hydrogen atmosphere were comprehensively explored via a broad range of experimental techniques, e.g. volumetric analysis, ex situ X-ray diffraction (XRD), in situ synchrotron radiation powder X-ray diffraction (SR-PXD), scanning electron microscopy (SEM), and differential thermal analysis (DTA). These investigations show that NaAlH4 was successfully synthesized and that its properties are comparable with those of high-purity commercial NaAlH4.

E.12.4
12:15
Authors : Ivan Saldan, Serhii Tkachenko, Ladislav Čelko, Jan M. Macák
Affiliations : Central European Institute of Technology, Brno University of Technology, Purkyňova 123, 61200 Brno, Czech Republic Center of Materials and Nanotechnologies, Faculty of Chemical Technology, University of Pardubice, Nam. Cs. Legii 565, 530 02 Pardubice, Czech Republic

Resume : Hydride decomposition or formation is a complex physical and chemical process where diffusion through the metal or hydride and recombination of H atoms or dissociation of molecular hydrogen often constitute the rate-limiting step. Multistage dehydrogenation of solid metal hydrides includes decomposition of the hydride phase; diffusion through the metal; release from the metal surface; 2H→H2 recombination; and release of molecular hydrogen. In case of solid hydrides, the catalyst for their decomposition-formation might be considered as a substance that promotes, coordinates and finally creates intermediate complexes with H-ligands. Therefore, chemical properties of the catalyst would be very important. In addition to that, physical properties such as surface structure, thermal stability, heat and electric conductivity of the catalyst might be newsworthy too. Along with porous carbon materials [1], other lightweight materials like metal oxides or pure metals might be considered as nanoscaffolds with a special pore design [2] and, at the same time, as affective heterogeneous catalysts [3]. Proposed nanomaterials must be strongly addressed to meet the onboard vehicular targets [4] set by the US DOE and to provide for manufacturing technology capable of their reproducible production at a large scale. New practical recommendations to develop catalyst for reversible hydrogen sorption are the main purpose of the presentation. [1] J. Zheng et al., AAAS Research, 2021, (2021), ID 3750689. [2] L. Pasquini. Energies, 13, (2020) 3503. [3] L. Luconi, et al., Int. J. Hydrogen Energy, 44, (2019) 25746. [4] E. Boateng, at al., Mater. Today Adv., 6, (2020) 100022.

E.12.5

Symposium organizers
Arndt REMHOFEMPA

Swiss Federal Laboratories for Materials Science and Technology, Überlandstrasse 129, CH-8600 Dübendorf, Switzerland

Arndt.Remhof@empa.ch
Claudio PISTIDDAHelmholtz Zentrum Hereon

Institute of Hydrogen Technology, Max Planck Strasse 1, Geesthacht 21502, Germany

claudio.pistidda@hereon.de
Dorthe BOMHOLDT RAVNSBÆKAarhus University

Department of Chemistry, Langelandsgade 140, 8000 Aarhus C, Denmark

dorthe@chem.au.dk
Michael HEERETechnische Universität Braunschweig

Institute of Internal Combustion Engines, Hermann-Blenk-Straße 42, 38108 Braunschweig, Germany

m.heere@tu-braunschweig.de