Origin of the High Capacity Manganese-Based Oxyfluoride Electrodes for Rechargeable Batteries

Zhang, Leiting; Dambournet, Damien; Iadecola, Antonella; Batuk, Dmitry; Borkiewicz, Olaf J.; Wiaderek, Kamila M.; Salager, Elodie; Shao, Minhua; Chen, Guohua; Tarascon, Jean -Marie

doi:10.1021/acs.chemmater.8b02182

Title: Origin of the High Capacity Manganese-Based Oxyfluoride Electrodes for Rechargeable Batteries

Journal Article · Tue Jul 17 00:00:00 EDT 2018 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.8b02182· OSTI ID:1480116

^[1];

^[2]; Iadecola, Antonella ^[3];

^[4]; Borkiewicz, Olaf J. ^[5]; Wiaderek, Kamila M. ^[5];

^[6];

^[7];

^[8]; Tarascon, Jean -Marie ^[9]

College de France, Paris Cedex (France); The Hong Kong Univ. of Science and Technology, Hong Kong SAR (China); The Hong Kong Polytechnic Univ., Hong Kong SAR (China)
Sorbonne Univ., Paris (France); Reseau sur le Stockage Electrochimique de l'Energie (RS2E), Amicens (France)
Reseau sur le Stockage Electrochimique de l'Energie (RS2E), Amicens (France)
College de France, Paris Cedex (France); Univ. of Antwerp, Antwerp (Belgium)
Argonne National Lab. (ANL), Argonne, IL (United States)
Reseau sur le Stockage Electrochimique de l'Energie (RS2E), Amicens (France); Univ. d'Orleans, Orleans Cedex (France)
The Hong Kong Univ. of Science and Technology, Hong Kong (China)
The Hong Kong Polytechnic Univ., Hong Kong SAR (China)
College de France, Paris Cedex (France); Reseau sur le Stockage Electrochimique de l'Energie (RS2E), Amicens (France); Sorbonne Univ., Paris (France)

In the quest for high energy density rechargeable batteries, conversion-type cathode materials stand out with their appealing multielectron transfer properties. However, they undergo a series of complex phase transitions upon initial cycling as opposed to conventional intercalation-type materials. Within this category, iron-based mixed-anion solid solutions (FeO_xF_2-x) have captured the most attention of the battery community, owing to their high theoretical capacity and moderate cyclability. In the meantime, it was recently demonstrated, via a series of electrochemical cycling experiments, the in situ preparation of manganese-based mixed-anion cathode materials based on decomposition of electrolyte salt LiPF6 in the presence of MnO. To take a step forward, we herein report a routine protocol to prepare 220 mAh g^-1-class composite cathodes. In addition, we provide a comprehensive understanding of the in situ fluorination and locally reversible phase transitions using complementary analytical techniques. The charged phase, with an average Mn oxidation state of ca. +2.8, consists of a highly disordered O-rich cubic-spinel-like core and an F-rich amorphous shell. Upon discharge, lithiation induces further phase transition, forming LiF, MnO, and a lithiated rocksalt-like phase. Furthermore this work, which we also extended to the iron-based system, offers insights into modification of chemical and electronic properties of electrode materials by in situ fluorination.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: Agence Nationale de la recherche (ANR); USDOE

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1480116

Journal Information:: Chemistry of Materials, Vol. 30, Issue 15; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 14 works

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References (46)

Electrical Energy Storage for the Grid: A Battery of Choices Dunn, B.; Kamath, H.; Tarascon, J. -M. Science, Vol. 334, Issue 6058 https://doi.org/10.1126/science.1212741	journal	November 2011
Towards greener and more sustainable batteries for electrical energy storage Larcher, D.; Tarascon, J-M. Nature Chemistry, Vol. 7, Issue 1 https://doi.org/10.1038/nchem.2085	journal	November 2014
Ultimate Limits to Intercalation Reactions for Lithium Batteries Whittingham, M. Stanley Chemical Reviews, Vol. 114, Issue 23 https://doi.org/10.1021/cr5003003	journal	October 2014
Storylines in intercalation chemistry Lerf, A. Dalton Trans., Vol. 43, Issue 27 https://doi.org/10.1039/C4DT00203B	journal	January 2014
Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries Poizot, P.; Laruelle, S.; Grugeon, S. Nature, Vol. 407, Issue 6803, p. 496-499 https://doi.org/10.1038/35035045	journal	September 2000
Reversible Formation and Decomposition of LiF Clusters Using Transition Metal Fluorides as Precursors and Their Application in Rechargeable Li Batteries Li, H.; Richter, G.; Maier, J. Advanced Materials, Vol. 15, Issue 9 https://doi.org/10.1002/adma.200304574	journal	May 2003
Beyond Intercalation-Based Li-Ion Batteries: The State of the Art and Challenges of Electrode Materials Reacting Through Conversion Reactions Cabana, Jordi; Monconduit, Laure; Larcher, Dominique Advanced Materials, Vol. 22, Issue 35 https://doi.org/10.1002/adma.201000717	journal	August 2010
Conversion Reaction Mechanisms in Lithium Ion Batteries: Study of the Binary Metal Fluoride Electrodes Wang, Feng; Robert, Rosa; Chernova, Natasha A. Journal of the American Chemical Society, Vol. 133, Issue 46 https://doi.org/10.1021/ja206268a	journal	November 2011
Iron Oxyfluorides as High Capacity Cathode Materials for Lithium Batteries Pereira, N.; Badway, F.; Wartelsky, M. Journal of The Electrochemical Society, Vol. 156, Issue 6, p. A407-A416 https://doi.org/10.1149/1.3106132	journal	January 2009
Structural phase transformation and Fe valence evolution in FeOxF2−x/C nanocomposite electrodes during lithiation and de-lithiation processes Sina, M.; Nam, K. -W.; Su, D. Journal of Materials Chemistry A, Vol. 1, Issue 38 https://doi.org/10.1039/c3ta12109g	journal	January 2013
Structure Stabilization by Mixed Anions in Oxyfluoride Cathodes for High-Energy Lithium Batteries Kim, Sung-Wook; Pereira, Nathalie; Chernova, Natasha A. ACS Nano, Vol. 9, Issue 10 https://doi.org/10.1021/acsnano.5b03643	journal	September 2015
Comprehensive Insights into the Structural and Chemical Changes in Mixed-Anion FeOF Electrodes by Using Operando PDF and NMR Spectroscopy Wiaderek, Kamila M.; Borkiewicz, Olaf J.; Castillo-Martínez, Elizabeth Journal of the American Chemical Society, Vol. 135, Issue 10 https://doi.org/10.1021/ja400229v	journal	March 2013
Synthesis of FeOF using roll-quenching method and the cathode properties for lithium-ion battery Kitajou, Ayuko; Komatsu, Hideyuki; Nagano, Rintarou Journal of Power Sources, Vol. 243 https://doi.org/10.1016/j.jpowsour.2013.06.053	journal	December 2013
The preparation and properties of rutile-type transition metal oxyfluorides Chamberland, B. L.; Sleight, A. W.; Cloud, W. H. Journal of Solid State Chemistry, Vol. 2, Issue 1 https://doi.org/10.1016/0022-4596(70)90032-0	journal	June 1970
Electrochemical Splitting of LiF: A New Approach to Lithium-Ion Battery Materials Dimov, N.; Kitajou, A.; Hori, H. ECS Transactions, Vol. 58, Issue 12 https://doi.org/10.1149/05812.0087ecst	journal	February 2014
Lithium-free transition metal monoxides for positive electrodes in lithium-ion batteries Jung, Sung-Kyun; Kim, Hyunchul; Cho, Min Gee Nature Energy, Vol. 2, Issue 2 https://doi.org/10.1038/nenergy.2016.208	journal	January 2017
Triggering the In Situ Electrochemical Formation of High Capacity Cathode Material from MnO Zhang, Leiting; Chen, Guohua; Berg, Erik J. Advanced Energy Materials, Vol. 7, Issue 8 https://doi.org/10.1002/aenm.201602200	journal	December 2016
An Electrochemical Cell for Operando Study of Lithium Batteries Using Synchrotron Radiation Leriche, J. B.; Hamelet, S.; Shu, J. Journal of The Electrochemical Society, Vol. 157, Issue 5 https://doi.org/10.1149/1.3355977	journal	January 2010
PDFfit2 and PDFgui: computer programs for studying nanostructure in crystals Farrow, C. L.; Juhas, P.; Liu, J. W. Journal of Physics: Condensed Matter, Vol. 19, Issue 33 https://doi.org/10.1088/0953-8984/19/33/335219	journal	July 2007
ROCK: the new Quick-EXAFS beamline at SOLEIL Briois, V.; La Fontaine, C.; Belin, S. Journal of Physics: Conference Series, Vol. 712 https://doi.org/10.1088/1742-6596/712/1/012149	journal	May 2016
Performance of Bellcore's plastic rechargeable Li-ion batteries Tarascon, J.-M.; Gozdz, A. S.; Schmutz, C. Solid State Ionics, Vol. 86-88, Issue Part 1, p. 49-54 https://doi.org/10.1016/0167-2738(96)00330-X	journal	July 1996
Modelling one- and two-dimensional solid-state NMR spectra: Modelling 1D and 2D solid-state NMR spectra Massiot, Dominique; Fayon, Franck; Capron, Mickael Magnetic Resonance in Chemistry, Vol. 40, Issue 1 https://doi.org/10.1002/mrc.984	journal	December 2001
Underneath the Bragg Peaks Egami, T.; Billinge, S. J. L. Materials Today, Vol. 6, Issue 6 https://doi.org/10.1016/S1369-7021(03)00635-7	journal	June 2003
The crystal structure of manganese trifluoride, MnF ₃ Hepworth, M. A.; Jack, K. H. Acta Crystallographica, Vol. 10, Issue 5 https://doi.org/10.1107/S0365110X57001024	journal	May 1957
In Situ X-ray Absorption Spectroscopy Investigation of a Bifunctional Manganese Oxide Catalyst with High Activity for Electrochemical Water Oxidation and Oxygen Reduction Gorlin, Yelena; Lassalle-Kaiser, Benedikt; Benck, Jesse D. Journal of the American Chemical Society, Vol. 135, Issue 23 https://doi.org/10.1021/ja3104632	journal	June 2013
In situ X-ray absorption spectroscopy of transition metal based water oxidation catalysts van Oversteeg, Christina H. M.; Doan, Hoang Q.; de Groot, Frank M. F. Chemical Society Reviews, Vol. 46, Issue 1 https://doi.org/10.1039/C6CS00230G	journal	January 2017
Determination of Mn valence states in mixed-valent manganates by XANES spectroscopy Manceau, A.; Marcus, M. A.; Grangeon, S. American Mineralogist, Vol. 97, Issue 5-6 https://doi.org/10.2138/am.2012.3903	journal	May 2012
XPS determination of Mn oxidation states in Mn (hydr)oxides Ilton, Eugene S.; Post, Jeffrey E.; Heaney, Peter J. Applied Surface Science, Vol. 366 https://doi.org/10.1016/j.apsusc.2015.12.159	journal	March 2016
Use of XPS to Identify the Oxidation State of Mn in Solid Surfaces of Filtration Media Oxide Samples from Drinking Water Treatment Plants Cerrato, José M.; Hochella, Michael F.; Knocke, William R. Environmental Science & Technology, Vol. 44, Issue 15 https://doi.org/10.1021/es100547q	journal	August 2010
XPS study of MnO oxidation Di Castro, V.; Polzonetti, G. Journal of Electron Spectroscopy and Related Phenomena, Vol. 48, Issue 1 https://doi.org/10.1016/0368-2048(89)80009-X	journal	January 1989
Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Cr, Mn, Fe, Co and Ni Biesinger, Mark C.; Payne, Brad P.; Grosvenor, Andrew P. Applied Surface Science, Vol. 257, Issue 7, p. 2717-2730 https://doi.org/10.1016/j.apsusc.2010.10.051	journal	January 2011
A comparative XPS surface study of Li ₂ FeSiO ₄ /C cycled with LiTFSI- and LiPF ₆ -based electrolytes Ensling, David; Stjerndahl, Mårten; Nytén, Anton J. Mater. Chem., Vol. 19, Issue 1 https://doi.org/10.1039/B813099J	journal	January 2009
Comprehensive Study of the CuF ₂ Conversion Reaction Mechanism in a Lithium Ion Battery Hua, Xiao; Robert, Rosa; Du, Lin-Shu The Journal of Physical Chemistry C, Vol. 118, Issue 28 https://doi.org/10.1021/jp503902z	journal	July 2014
Investigation of particle isolation in Li-ion battery electrodes using 7Li NMR spectroscopy Kerlau, Marie; Reimer, Jeffrey A.; Cairns, Elton J. Electrochemistry Communications, Vol. 7, Issue 12 https://doi.org/10.1016/j.elecom.2005.09.003	journal	December 2005
Influence of relative humidity on the structure and electrochemical performance of sustainable LiFeSO ₄ F electrodes for Li-ion batteries Zhang, Leiting; Tarascon, Jean-Marie; Sougrati, Moulay Tahar Journal of Materials Chemistry A, Vol. 3, Issue 33 https://doi.org/10.1039/C5TA05107J	journal	January 2015
Decomposition of CoF3 during battery electrode processing Li, Wei; Groult, Henri; Borkiewicz, Olaf J. Journal of Fluorine Chemistry, Vol. 205 https://doi.org/10.1016/j.jfluchem.2017.11.012	journal	January 2018
Identifying the Local Structures Formed during Lithiation of the Conversion Material, Iron Fluoride, in a Li Ion Battery: A Solid-State NMR, X-ray Diffraction, and Pair Distribution Function Analysis Study Yamakawa, Naoko; Jiang, Meng; Key, Baris Journal of the American Chemical Society, Vol. 131, Issue 30 https://doi.org/10.1021/ja902639w	journal	August 2009
Lithium insertion into manganese spinels Thackeray, M. M.; David, W. I. F.; Bruce, P. G. Materials Research Bulletin, Vol. 18, Issue 4, p. 461-472 https://doi.org/10.1016/0025-5408(83)90138-1	journal	April 1983
Lithium insertion into Fe3O4 Islam, M. S.; Catlow, C. R. A. Journal of Solid State Chemistry, Vol. 77, Issue 1 https://doi.org/10.1016/0022-4596(88)90106-5	journal	November 1988
Lithium Insertion Mechanism in Iron-Based Oxyfluorides with Anionic Vacancies Probed by PDF Analysis Dambournet, Damien; Chapman, Karena W.; Duttine, Mathieu ChemistryOpen, Vol. 4, Issue 4 https://doi.org/10.1002/open.201500031	journal	June 2015
Lithium manganese oxyfluoride as a new cathode material exhibiting oxygen redox House, Robert A.; Jin, Liyu; Maitra, Urmimala Energy & Environmental Science, Vol. 11, Issue 4 https://doi.org/10.1039/C7EE03195E	journal	January 2018
Solid Oxides and Hydroxides of Manganese ¹ Moore, T. E.; Ellis, Marylinn; Selwood, P. W. Journal of the American Chemical Society, Vol. 72, Issue 2 https://doi.org/10.1021/ja01158a056	journal	February 1950
Fluorination of Lithium-Excess Transition Metal Oxide Cathode Materials Richards, William D.; Dacek, Stephen T.; Kitchaev, Daniil A. Advanced Energy Materials, Vol. 8, Issue 5 https://doi.org/10.1002/aenm.201701533	journal	October 2017
Electrochemically activated MnO as a cathode material for sodium-ion batteries Zhang, Leiting; Batuk, Dmitry; Chen, Guohua Electrochemistry Communications, Vol. 77 https://doi.org/10.1016/j.elecom.2017.02.020	journal	April 2017
New Iron-Based Intercalation Host for Lithium-Ion Batteries Jung, Sung-Kyun; Hwang, Insang; Cho, Sung-Pyo Chemistry of Materials, Vol. 30, Issue 6 https://doi.org/10.1021/acs.chemmater.7b05017	journal	March 2018
Rationalization of the Low-Potential Reactivity of 3d-Metal-Based Inorganic Compounds toward Li Poizot, P.; Laruelle, S.; Grugeon, S. Journal of The Electrochemical Society, Vol. 149, Issue 9 https://doi.org/10.1149/1.1497981	journal	January 2002

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Electrochemical properties of chromium oxyfluoride CrO _2−x F _x with 0 ≤ x ≤ 0.3 Mukai, Kazuhiko; Uyama, Takeshi; Yamada, Ikuya Inorganic Chemistry Frontiers, Vol. 6, Issue 11 https://doi.org/10.1039/c9qi00765b	journal	January 2019
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