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1. A database of experimentally measured lithium solid electrolyte conductivities evaluated with machine learning

Author

Cameron J. Hargreaves, Michael W. Gaultois, Luke M. Daniels, Emma J. Watts, Vitaliy A. Kurlin, Michael Moran, Yun Dang, Rhun Morris, Alexandra Morscher, Kate Thompson, Matthew A. Wright, Beluvalli-Eshwarappa Prasad, Frédéric Blanc, Chris M. Collins, Catriona A. Crawford, Benjamin B. Duff, Jae Evans, Jacinthe Gamon, Guopeng Han, Bernhard T. Leube, Hongjun Niu, Arnaud J. Perez, Aris Robinson, Oliver Rogan, Paul M. Sharp, Elvis Shoko, Manel Sonni, William J. Thomas, Andrij Vasylenko, Lu Wang, Matthew J. Rosseinsky, and Matthew S. Dyer

Subjects
Materials of engineering and construction. Mechanics of materials, TA401-492, Computer software, QA76.75-76.765
Abstract

Abstract The application of machine learning models to predict material properties is determined by the availability of high-quality data. We present an expert-curated dataset of lithium ion conductors and associated lithium ion conductivities measured by a.c. impedance spectroscopy. This dataset has 820 entries collected from 214 sources; entries contain a chemical composition, an expert-assigned structural label, and ionic conductivity at a specific temperature (from 5 to 873 °C). There are 403 unique chemical compositions with an associated ionic conductivity near room temperature (15–35 °C). The materials contained in this dataset are placed in the context of compounds reported in the Inorganic Crystal Structure Database with unsupervised machine learning and the Element Movers Distance. This dataset is used to train a CrabNet-based classifier to estimate whether a chemical composition has high or low ionic conductivity. This classifier is a practical tool to aid experimentalists in prioritizing candidates for further investigation as lithium ion conductors.

Published
2023
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2. Ordered Oxygen Vacancies in the Lithium-Rich Oxide Li4CuSbO5.5, a Triclinic Structure Type Derived from the Cubic Rocksalt Structure

Author

Arnaud J. Perez, Andrij Vasylenko, T. Wesley Surta, Hongjun Niu, Luke M. Daniels, Laurence J. Hardwick, Matthew S. Dyer, John B. Claridge, and Matthew J. Rosseinsky

Subjects
Inorganic Chemistry, Physical and Theoretical Chemistry, Article
Abstract

Li-rich rocksalt oxides are promising candidates as high-energy density cathode materials for next-generation Li-ion batteries because they present extremely diverse structures and compositions. Most reported materials in this family contain as many cations as anions, a characteristic of the ideal cubic closed-packed rocksalt composition. In this work, a new rocksalt-derived structure type is stabilized by selecting divalent Cu and pentavalent Sb cations to favor the formation of oxygen vacancies during synthesis. The structure and composition of the oxygen-deficient Li4CuSbO5.5□0.5 phase is characterized by combining X-ray and neutron diffraction, ICP-OES, XAS, and magnetometry measurements. The ordering of cations and oxygen vacancies is discussed in comparison with the related Li2CuO2□1 and Li5SbO5□1 phases. The electrochemical properties of this material are presented, with only 0.55 Li+ extracted upon oxidation, corresponding to a limited utilization of cationic and/or anionic redox, whereas more than 2 Li+ ions can be reversibly inserted upon reduction to 1 V vs Li+/Li, a large capacity attributed to a conversion reaction and the reduction of Cu2+ to Cu0. Control of the formation of oxygen vacancies in Li-rich rocksalt oxides by selecting appropriate cations and synthesis conditions affords a new route for tuning the electrochemical properties of cathode materials for Li-ion batteries. Furthermore, the development of material models of the required level of detail to predict phase diagrams and electrochemical properties, including oxygen release in Li-rich rocksalt oxides, still relies on the accurate prediction of crystal structures. Experimental identification of new accessible structure types stabilized by oxygen vacancies represents a valuable step forward in the development of predictive models., Controlling the composition and synthesis conditions of Li-rich rocksalt oxides can lead to to new structure types stabilized by oxygen vacancies. The complex atomic ordering of Li4CuSbO5.5 is described and discussed in the context of other oxygen-deficient rocksalt oxides.

Published
2021

3. Stabilization of O–O Bonds by d0 Cations in Li4+xNi1–xWO6 (0 ≤ x ≤ 0.25) Rock Salt Oxides as the Origin of Large Voltage Hysteresis

Author

John B. Claridge, Sarah J. Day, Arnaud J. Perez, Chiu C. Tang, Michael J. Pitcher, Filipe Braga, Laurence J. Hardwick, Marco Zanella, William J. Thomas, Christopher Collins, Jose A. Coca-Clemente, Johnson Timothy Allan, Matthew S. Dyer, Zoe N. Taylor, Nicholas E. Drewett, Vinod R. Dhanak, and Matthew J. Rosseinsky

Subjects
chemistry.chemical_classification, Inorganic chemistry, Oxide, chemistry.chemical_element, Salt (chemistry), General Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Redox, Catalysis, Cathode, 0104 chemical sciences, Ion, law.invention, chemistry.chemical_compound, Colloid and Surface Chemistry, Transition metal, chemistry, law, Single bond, Lithium
Abstract

Multinary lithium oxides with the rock salt structure are of technological importance as cathode materials in rechargeable lithium ion batteries. Current state-of-the-art cathodes such as LiNi1/3Mn1/3Co1/3O2 rely on redox cycling of earth-abundant transition-metal cations to provide charge capacity. Recently, the possibility of using the oxide anion as a redox center in Li-rich rock salt oxides has been established as a new paradigm in the design of cathode materials with enhanced capacities (>200 mAh/g). To increase the lithium content and access electrons from oxygen-derived states, these materials typically require transition metals in high oxidation states, which can be easily achieved using d0 cations. However, Li-rich rock salt oxides with high valent d0 cations such as Nb5+ and Mo6+ show strikingly high voltage hysteresis between charge and discharge, the origin of which is uninvestigated. In this work, we study a series of Li-rich compounds, Li4+ xNi1- xWO6 (0 ≤ x ≤ 0.25) adopting two new and distinct cation-ordered variants of the rock salt structure. The Li4.15Ni0.85WO6 (x = 0.15) phase has a large reversible capacity of 200 mAh/g, without accessing the Ni3+/Ni4+ redox couple, implying that more than two-thirds of the capacity is due to anionic redox, with good cyclability. The presence of the 5d0 W6+ cation affords extensive (>2 V) voltage hysteresis associated with the anionic redox. We present experimental evidence for the formation of strongly stabilized localized O-O single bonds that explain the energy penalty required to reduce the material upon discharge. The high valent d0 cation associates localized anion-anion bonding with the anion redox capacity.

Published
2019
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4. Na2Fe2OS2, a new earth abundant oxysulphide cathode material for Na-ion batteries

Author

Laurence J. Hardwick, Tim D. Veal, Arnaud J. Perez, Leanne A. H. Jones, Rhun E. Morris, Chiu C. Tang, Matthew J. Rosseinsky, John B. Claridge, Marco Zanella, Luke M. Daniels, Jacinthe Gamon, Matthew S. Dyer, Department of Chemistry, University of Liverpool, Stephenson Institute for Renewable Energy, Oliver Lodge Laboratory, Diamond Light Source Ltd, and We thank EPSRC for funding under EP/N004884. We thank Diamond Light Source for access to beamlines I11 and I18, Dr Sarah Day, Prof. Alan Chadwick and Dr Giannantonio Cibin for assistance on the beamlines. We thank STFC for access to Polaris (Xpress proposal 1990220) and Dr Ron Smith for running the measurements. XPS data collection was performed at the EPSRC National Facility for XPS (‘HarwellXPS’), operated by Cardiff University and UCL, under contract No. PR16195. Dr Mark Isaacs is greatly acknowledged for his support during the measurement. MJR thanks the Royal Society for the award of a Research Professor position. We acknowledge Dr Konstantin Luzyanin, Mr Stephen Moss and Mrs Jean Ellis (University of Liverpool) for ICP-OES and CHNS measurements, and Dr Quinn Gibson and Dr Wesley Surta for helpful discussions.

Subjects
Materials science, Extended X-ray absorption fine structure, Renewable Energy, Sustainability and the Environment, Rietveld refinement, 02 engineering and technology, General Chemistry, Crystal structure, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 7. Clean energy, 01 natural sciences, Energy storage, 0104 chemical sciences, Amorphous solid, Ion, Chemical engineering, Phase (matter), General Materials Science, 0210 nano-technology
Abstract

International audience; Multiple anion materials are of particular interest for the discovery of new crystal structures and offer an original way to modulate physical properties, including energy storage materials with enhanced performances. Through careful synthesis optimization, a new Na2Fe2OS2 phase was prepared by two different routes: high temperature solid-state synthesis and simple mechanochemical synthesis. The long-range and local structure of Na2Fe2OS2 was studied by Rietveld refinement of neutron and X-ray diffraction data combined with EXAFS data refinement. The phase comprises an amorphous and a crystalline part which has an anti-K2NiF4 structure, corresponding to the n = 1 member of the homologous anti-Ruddlesden–Popper [AX][ABX3]n series. Its electrochemical properties as a cathode material were studied in Na half cells and Na-ion full cells, revealing that the material becomes fully amorphous upon initial desodiation to Na0.5Fe2OS2, but maintains a reversible capacity of 135 mA h g−1 in full cells where up to 1.2 Na+ can be reversibly extracted and reinserted when compensating for the Na lost in SEI formation. The stability of the pristine material and its structural evolution upon charging are discussed, paving the way for further optimization of this material. Being composed exclusively of earth-abundant elements and stable under dry air, Na2Fe2OS2 perfectly illustrates the great opportunity of multiple anion chemistry to explore new structure types and develop better energy storage systems.

Published
2020
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5. Evolution of Oxygen Ligands upon Large Redox Swings of Li3IrO4

Author

Jordi Cabana, Jean-Marie Tarascon, Marie-Liesse Doublet, Teak D. Boyko, Arnaud J. Perez, John W. Freeland, Beata Taudul, Haifeng Li, Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Collège de France - Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Department of Chemistry, University of Illinois at Chicago, Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Argonne National Laboratory [Lemont] (ANL), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Chaire Chimie du solide et énergie, University of Illinois [Chicago] (UIC), and University of Illinois System

Subjects
Materials science, Renewable Energy, Sustainability and the Environment, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Photochemistry, 01 natural sciences, Redox, Oxygen, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Materials Chemistry, Electrochemistry, [CHIM]Chemical Sciences, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract

International audience; The limits of intercalation electrochemistry continue to be tested in the quest for ever increasing gains in the storage capability of Li-ion cathodes. The subsequent push for multi-electron reactivity has led to the recognition of the extremely versatile role of oxide ligands in charge compensation when there is a large redox swing. Li 3 IrO 4 is a unique model of such activity because it can reversibly cycle between Li 1 IrO 4 and Li 4.7 IrO 4. Here, X-ray spectroscopy, magnetic measurements and computational simulations uncover the evolution of O states in the different steps, compared to the involvement of Ir. While the process between Li 1 IrO 4 and Li 3 IrO 4 is dominated by the unconventional lattice oxygen redox, the process between Li 3 IrO 4 and Li 4.7 IrO 4 involves a conventional change of the formal oxidation state of Ir, which affects O due to the high covalency. The O states of Li 3 IrO 4 exhibit a very high reversibility after the whole 3.7-electron process, completely restoring the pristine state.

Published
2021
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6. Structural Instability Driven by Li/Na Competition in Na(Li 1/3 Ir 2/3 )O 2 Cathode Material for Li-Ion and Na-Ion Batteries

Author

Gwenaëlle Rousse, Jean-Marie Tarascon, Arnaud J. Perez, Sorbonne Université (SU), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Collège de France - Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), and Université Pierre et Marie Curie - Paris 6 (UPMC)

Subjects
Battery (electricity), 010405 organic chemistry, Chemistry, Inorganic chemistry, Stacking, Electrolyte, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, Electrochemistry, 01 natural sciences, Cathode, 0104 chemical sciences, Ion, law.invention, Inorganic Chemistry, Transition metal, law, Phase (matter), Physical and Theoretical Chemistry
Abstract

With increasing hopes placed on the Na-ion battery technology to complement the current Li-ion battery systems, it is important to improve the energy density of Na-based cathode materials. Na-rich rocksalt oxides, Na1+xM1-xO2 (M = transition metal), combining cationic and anionic redox activity, could provide the necessary increase in capacity to achieve this goal, but their synthesis remains challenging compared to the Li analogues. As an alternative, mixed compounds Na(AxM1-x)O2, with A being an electropositive cation such as Li, Mg, or Zn sitting in the transition-metal layer, have been reported. As a continuation, we herein prepared the mixed Na(Li1/3Ir2/3)O2 phase and compared its structure and electrochemical properties with the well-known Li2IrO3 and Na2IrO3 parent materials. By mixing Na and Li in the material, the stacking sequence of the transition-metal honeycomb layers in Na(Li1/3Ir2/3)O2 is modified compared to the two parent materials, resulting in the presence of extra superstructure peaks in X-ray diffraction data. Using electrochemical characterization and an in-situ X-ray diffraction technique, the mixed Na(Li1/3Ir2/3)O2 was found to be unstable both in Li and Na batteries and to separate into Na-rich NaxIrO3 and Li-rich LixIrO3 phases due to the competition between electrochemical (de)insertion, cation exchange with the electrolyte, and segregation of Na and Li in the material. These findings highlight important challenges and offer useful insight into guide the design of new mixed Na(AxM1-x)O2 cathode materials with high capacity for Na-ion batteries.

Published
2019
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7. Structural Instability Driven by Li/Na Competition in Na(Li

Author

Arnaud J, Perez, Gwenaëlle, Rousse, and Jean-Marie, Tarascon

Abstract

With increasing hopes placed on the Na-ion battery technology to complement the current Li-ion battery systems, it is important to improve the energy density of Na-based cathode materials. Na-rich rocksalt oxides, Na

Published
2019

8. Stabilization of O-O Bonds by d

Author

Zoe N, Taylor, Arnaud J, Perez, José A, Coca-Clemente, Filipe, Braga, Nicholas E, Drewett, Michael J, Pitcher, William J, Thomas, Matthew S, Dyer, Christopher, Collins, Marco, Zanella, Timothy, Johnson, Sarah, Day, Chiu, Tang, Vinod R, Dhanak, John B, Claridge, Laurence J, Hardwick, and Matthew J, Rosseinsky

Subjects
Article
Abstract

Multinary lithium oxides with the rock salt structure are of technological importance as cathode materials in rechargeable lithium ion batteries. Current state-of-the-art cathodes such as LiNi1/3Mn1/3Co1/3O2 rely on redox cycling of earth-abundant transition-metal cations to provide charge capacity. Recently, the possibility of using the oxide anion as a redox center in Li-rich rock salt oxides has been established as a new paradigm in the design of cathode materials with enhanced capacities (>200 mAh/g). To increase the lithium content and access electrons from oxygen-derived states, these materials typically require transition metals in high oxidation states, which can be easily achieved using d0 cations. However, Li-rich rock salt oxides with high valent d0 cations such as Nb5+ and Mo6+ show strikingly high voltage hysteresis between charge and discharge, the origin of which is uninvestigated. In this work, we study a series of Li-rich compounds, Li4+xNi1–xWO6 (0 ≤ x ≤ 0.25) adopting two new and distinct cation-ordered variants of the rock salt structure. The Li4.15Ni0.85WO6 (x = 0.15) phase has a large reversible capacity of 200 mAh/g, without accessing the Ni3+/Ni4+ redox couple, implying that more than two-thirds of the capacity is due to anionic redox, with good cyclability. The presence of the 5d0 W6+ cation affords extensive (>2 V) voltage hysteresis associated with the anionic redox. We present experimental evidence for the formation of strongly stabilized localized O–O single bonds that explain the energy penalty required to reduce the material upon discharge. The high valent d0 cation associates localized anion–anion bonding with the anion redox capacity.

Published
2019

9. Elucidation of Active Oxygen Sites upon Delithiation of Li3IrO4

Author

Haifeng Li, Marie-Liesse Doublet, Jordi Cabana, Jean-Marie Tarascon, Arnaud J. Perez, Teak D. Boyko, John W. Freeland, Beata Taudul, Department of Chemistry, University of Liverpool, Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Argonne National Laboratory [Lemont] (ANL), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), University of Illinois [Chicago] (UIC), and University of Illinois System

Subjects
Battery (electricity), Renewable Energy, Sustainability and the Environment, Chemistry, Inorganic chemistry, Oxide, Energy Engineering and Power Technology, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Cathode, 0104 chemical sciences, Redox Activity, law.invention, Active oxygen, chemistry.chemical_compound, Fuel Technology, Transition metal, Chemistry (miscellaneous), law, Materials Chemistry, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract

Transformational increases in the storage capacity of battery cathodes could be achieved by tapping into the redox activity at oxide ligands in addition to conventional transition metal couples. Yet the key signatures that govern such lattice oxygen redox (LOR) have not been ascertained. Li3IrO4 has the largest reversible LOR, rendering it a unique model system. Here, X-ray spectroscopy and computational simulations reveal that LOR in Li3IrO4 is selectively compensated via O sites with 3 lone pairs, which are activated by Li/Ir disorder. The 2-electron LOR can be reversed to regenerate the initial state without unlocking competing bulk reactions observed in many other compounds. We uncover an intricate interplay between stoichiometry, O coordination and non-bonding states in LOR and pinpoint spectroscopic signatures. This interplay is indispensable to design materials with 3d metals that fulfill the promise of LOR to overcome the bottlenecks of current cathodes for future implementation in practical batteries.

Published
2021
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10. Evidence for anionic redox activity in a tridimensional-ordered Li-rich positive electrode β-Li2IrO3

Author

Artem M. Abakumov, Dominique Foix, Arnaud J. Perez, Gustaaf Van Tendeloo, Marie-Liesse Doublet, Paul E. Pearce, Jean-Marie Tarascon, Dmitry Batuk, Mathieu Saubanère, Gwenaëlle Rousse, Eric McCalla, Chimie du solide et de l'énergie (CSE), Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), University of Antwerp (UA), Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of Minnesota [Twin Cities] (UMN), University of Minnesota System, Skolkovo Institute of Science and Technology [Moscow] (Skoltech), Chaire Chimie du solide et énergie, Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Collège de France - Chaire Chimie du solide et énergie, Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC), and EMAT University of Antwerp - Groenenborgerlaan 171, B-2020 Antwerp, Belgique

Subjects
Solid-state chemistry, Inorganic chemistry, Neutron diffraction, 02 engineering and technology, 010402 general chemistry, Electrochemistry, 01 natural sciences, Redox, Solid state chemistry, Batteries, [CHIM]Chemical Sciences, General Materials Science, Batteries, Solid state chemistry, Chemistry, Physics, Mechanical Engineering, Cationic polymerization, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Crystallography, Mechanics of Materials, Transmission electron microscopy, Electrode, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Density functional theory, [CHIM.OTHE]Chemical Sciences/Other, 0210 nano-technology
Abstract

International audience; Lithium-ion battery cathode materials have relied on cationic redox reactions until the recent discovery of anionic redox activity in Li-rich layered compounds which enables capacities as high as 300 mAh g-1. In the quest for new high-capacity electrodes with anionic redox, a still unanswered question was remaining regarding the importance of the structural dimensionality. The present manuscript provides an answer. We herein report on a β-Li2IrO3 phase which, in spite of having the Ir arranged in a tridimensional (3D) framework instead of the typical two-dimensional (2D) layers seen in other Li-rich oxides, can reversibly exchange 2.5 e- per Ir, the highest value ever reported for any insertion reaction involving d-metals. We show that such a large activity results from joint reversible cationic (Mn+) and anionic (O2)n- redox processes, the latter being visualized via complementary transmission electron microscopy and neutron diffraction experiments, and confirmed by density functional theory calculations. Moreover, β-Li2IrO3 presents a good cycling behaviour while showing neither cationic migration nor shearing of atomic layers as seen in 2D-layered Li-rich materials. Remarkably, the anionic redox process occurs jointly with the oxidation of Ir4+ at potentials as low as 3.4 V versus Li+/Li0, as equivalently observed in the layered α-Li2IrO3 polymorph. Theoretical calculations elucidate the electrochemical similarities and differences of the 3D versus 2D polymorphs in terms of structural, electronic and mechanical descriptors. Our findings free the structural dimensionality constraint and broaden the possibilities in designing high-energy-density electrodes for the next generation of Li-ion batteries.

Published
2017
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11. Evidence for anionic redox activity in a tridimensional-ordered Li-rich positive electrode β-Li

Author

Paul E, Pearce, Arnaud J, Perez, Gwenaelle, Rousse, Mathieu, Saubanère, Dmitry, Batuk, Dominique, Foix, Eric, McCalla, Artem M, Abakumov, Gustaaf, Van Tendeloo, Marie-Liesse, Doublet, and Jean-Marie, Tarascon

Abstract

Lithium-ion battery cathode materials have relied on cationic redox reactions until the recent discovery of anionic redox activity in Li-rich layered compounds which enables capacities as high as 300 mAh g

Published
2016

12. Strong oxygen participation in the redox governing the structural and electrochemical properties of Na-rich layered oxide <tex>Na_{2}IrO_{3}$</tex>

Author

Romain Dugas, Karel H. W. van den Bos, Eric McCalla, Arnaud J. Perez, Dmitry Batuk, Erik J. Berg, Gustaaf Van Tendeloo, Danielle Gonbeau, Artem M. Abakumov, Marie-Liesse Doublet, Jean-Marie Tarascon, Dominique Foix, Gwenaëlle Rousse, Matthieu Saubanère, Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU), University of Antwerp (UA), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of Minnesota [Twin Cities] (UMN), University of Minnesota System, Paul Scherrer Institute (PSI), Skolkovo Institute of Science and Technology [Moscow] (Skoltech), Collège de France - Chaire Chimie du solide et énergie, Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Chemistry, General Chemical Engineering, Physics, Inorganic chemistry, Cationic polymerization, Oxide, 02 engineering and technology, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, Redox, 0104 chemical sciences, Metal, chemistry.chemical_compound, X-ray photoelectron spectroscopy, Formula unit, visual_art, Phase (matter), Materials Chemistry, visual_art.visual_art_medium, 0210 nano-technology
Abstract

International audience; The recent revival of the Na-ion battery concept has prompted intense activities in the search for new Na-based layered oxide positive electrodes. The largest capacity to date was obtained for a Na-deficient layered oxide that relies on cationic redox processes only. To go beyond this limit, we decided to chemically manipulate these Na-based layered compounds in a way to trigger the participation of the anionic network. We herein report the electrochemical properties of a Na-rich phase Na2IrO3, which can reversibly cycle 1.5 Na+ per formula unit while not suffering from oxygen release nor cationic migrations. Such large capacities, as deduced by complementary XPS, X-ray/neutron diffraction and transmission electron microscopy measurements, arise from cumulative cationic and anionic redox processes occurring simultaneously at potentials as low as 2.7 V vs Na+/Na. The inability to remove more than 1.5 Na+ is rooted in the formation of an O1-type phase having highly stabilized Na sites as confirmed by DFT calculations, which could rationalize as well the competing metal/oxygen redox processes in Na2IrO3. This work will help to define the most fertile directions in the search for novel high energy Na-rich materials based on more sustainable elements than Ir.

Published
2016
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13. Proton Ion Exchange Reaction in Li3 IrO4 : A Way to New H3+ x IrO4 Phases Electrochemically Active in Both Aqueous and Nonaqueous Electrolytes

Author

Elodie Salager, Jean-Marie Tarascon, Zifeng Lin, Pierre-Louis Taberna, Robin Beer, Arnaud J. Perez, Patrice Simon, and Artem M. Abakumov

Subjects
Materials science, Aqueous solution, Ion exchange, Renewable Energy, Sustainability and the Environment, Crystal chemistry, Inorganic chemistry, Oxide, Protonation, 02 engineering and technology, Electrolyte, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Redox, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Phase (matter), General Materials Science, 0210 nano-technology
Abstract

Progress over the past decade in Li‐insertion compounds has led to a new class of Li‐rich layered oxide electrodes cumulating both cationic and anionic redox processes. Pertaining to this new class of materials are the Li/Na iridate phases, which present a rich crystal chemistry. This work reports on a new protonic iridate phase H3+xIrO4 having a layered structure obtained by room temperature acid‐leaching of Li3IrO4. This new phase shows reversible charge storage properties of 1.5 e− per Ir atom with high rate capabilities in both nonaqueous (vs Li+/Li) and aqueous (vs capacitive carbon) media. It is demonstrated that Li‐insertion in carbonate LiPF6‐based electrolyte occurs through a classical reduction process (Ir5+ ↔ Ir3+), which is accompanied by a well‐defined structural transition. In concentrated H2SO4 electrolyte, this work provides evidence that the overall capacity of 1.7 H+ per Ir results from two additive redox processes with the low potential one showing ohmic limitations. Altogether, the room temperature protonation approach, which can be generalized to various Li‐rich phases containing either 3d, 4d or 5d metals, offers great opportunities for the judicious design of attractive electrode materials.

Published
2018
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14. The Li 3 Ru y Nb 1– y O 4 (0 ≤ y ≤ 1) System: Structural Diversity and Li Insertion and Extraction Capabilities

Author

Gwenaëlle Rousse, Dmitry Batuk, Arnaud J. Perez, Quentin Jacquet, Gustaaf Van Tendeloo, Jean-Marie Tarascon, Collège de France - Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), University of Antwerp (UA), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)

Subjects
Crystal chemistry, Chemistry, General Chemical Engineering, Physics, Extraction (chemistry), Cationic polymerization, Nanotechnology, 02 engineering and technology, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, Redox, 0104 chemical sciences, Crystallography, Zigzag, Phase (matter), Materials Chemistry, 0210 nano-technology, Lone pair
Abstract

Searching for novel high-capacity electrode materials combining cationic and anionic redox processes is an ever-growing activity within the field of Li-ion batteries. In this respect, we report on the exploration of the Li3RuyNb1yO4 (0 ≤ y ≤ 1) system with an O/M ratio of 4 to maximize the number of oxygen lone pairs, responsible for the anionic redox. We show that this system presents a very rich crystal chemistry with the existence of four structural types, which derive from the rocksalt structure but differ in their cationic arrangement, creating either zigzag, helical, jagged chains or clusters. From an electrochemical standpoint, these compounds are active on reduction via a classical cationic insertion process. The oxidation process is more complex, because of the instability of the delithiated phase. Our results promote the use of the rich Li3MO4 family as a viable platform for a better understanding of the relationships between structure and anionic redox activity.

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