Tuning Bulk Redox and Altering Interfacial Reactivity in Highly Fluorinated Cation-Disordered Rocksalt Cathodes

Crafton, Matthew J.; Huang, Tzu-Yang; Yue, Yuan; Giovine, Raynald; Wu, Vincent C.; Dun, Chaochao; Urban, Jeffrey J.; Clément, Raphaële J.; Tong, Wei; McCloskey, Bryan D.

doi:10.1021/acsami.2c16974

Title: Tuning Bulk Redox and Altering Interfacial Reactivity in Highly Fluorinated Cation-Disordered Rocksalt Cathodes

Journal Article · Tue Apr 04 00:00:00 EDT 2023 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.2c16974· OSTI ID:2326185

^[1];

^[1]; Yue, Yuan ^[2];

^[3];

^[4];

^[5];

^[3];

^[2];

^[1]

University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States), Energy Storage and Distributed Resources Division
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States), Energy Storage and Distributed Resources Division
University of California, Santa Barbara, CA (United States)
The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry

Lithium-excess, cation-disordered rocksalt (DRX) materials have been subject to intense scrutiny and development in recent years as potential cathode materials for Li-ion batteries. Despite their compositional flexibility and high initial capacity, they suffer from poorly understood parasitic degradation reactions at the cathode-electrolyte interface. These interfacial degradation reactions deteriorate both the DRX material and electrolyte, ultimately leading to capacity fade and voltage hysteresis during cycling. In this work, differential electrochemical mass spectrometry (DEMS) and titration mass spectrometry are combined to quantify the extent of bulk redox and surface degradation reactions for a set of Mn^2+/4+-based DRX oxyfluorides during initial cycling with a high-voltage charging cutoff (4.8 V vs Li/Li⁺). Increasing the fluorine content from 7.5 to 33.75% is shown to diminish oxygen redox and suppresses high-voltage O₂ evolution from the DRX surface. Additionally, electrolyte degradation processes resulting in the formation of both gaseous species and electrolyte-soluble protic species are observed. Subsequently, DEMS is paired with a fluoride-scavenging additive to demonstrate that increasing fluorine content leads to increased dissolution of fluorine from the DRX material into the electrolyte. Finally, a suite of ex situ spectroscopy techniques (X-ray photoelectron spectroscopy, inductively coupled plasma optical emission spectroscopy, and solid-state nuclear magnetic resonance spectroscopy) are employed to study the change in DRX composition during charging, revealing the dissolution of manganese and fluorine from the DRX material at high voltages. Here this work provides insight into the degradation processes occurring at the DRX-electrolyte interface and points toward potential routes of interfacial stabilization.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; DMR 1720256; DGE 1650114

OSTI ID:: 2326185

Journal Information:: ACS Applied Materials and Interfaces, Vol. 15, Issue 15; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (59)

Review—Lithium-Excess Layered Cathodes for Lithium Rechargeable Batteries Hong, Jihyun; Gwon, Hyeokjo; Jung, Sung-Kyun Journal of The Electrochemical Society, Vol. 162, Issue 14 https://doi.org/10.1149/2.0071514jes	journal	January 2015
Elucidating the Reactivity of Tris(trimethylsilyl)phosphite and Tris(trimethylsilyl)phosphate Additives in Carbonate Electrolytes—A Comparative Online Electrochemical Mass Spectrometry Study Guéguen, Aurélie; Bolli, Christoph; Mendez, Manuel A. ACS Applied Energy Materials, Vol. 3, Issue 1 https://doi.org/10.1021/acsaem.9b01551	journal	November 2019
Challenges for Rechargeable Li Batteries Goodenough, John B.; Kim, Youngsik Chemistry of Materials, Vol. 22, Issue 3, p. 587-603 https://doi.org/10.1021/cm901452z	journal	February 2010
Dissolution of Spinel Oxides and Capacity Losses in 4V Li / Li_xMn₂O₄ Cells Jang, Dong H.; Shin, Young J.; Oh, Seung M. Journal of The Electrochemical Society, Vol. 143, Issue 7, p. 2204-2211 https://doi.org/10.1149/1.1836981	journal	January 1996
Lithium Batteries and Cathode Materials Whittingham, M. Stanley Chemical Reviews, Vol. 104, Issue 10, p. 4271-4302 https://doi.org/10.1021/cr020731c	journal	October 2004
Isotropic High Field NMR Spectra of Li-Ion Battery Materials with Anisotropy >1 MHz Hung, Ivan; Zhou, Lina; Pourpoint, Frédérique Journal of the American Chemical Society, Vol. 134, Issue 4 https://doi.org/10.1021/ja209600m	journal	January 2012
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
Reversible Mn2+/Mn4+ double redox in lithium-excess cathode materials Lee, Jinhyuk; Kitchaev, Daniil A.; Kwon, Deok-Hwang Nature, Vol. 556, Issue 7700 https://doi.org/10.1038/s41586-018-0015-4	journal	April 2018
Mechanisms of manganese spinels dissolution and capacity fade at high temperature Aoshima, Takayuki; Okahara, Kenji; Kiyohara, Chikara Journal of Power Sources, Vol. 97-98 https://doi.org/10.1016/S0378-7753(01)00551-1	journal	July 2001
The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials Seo, Dong-Hwa; Lee, Jinhyuk; Urban, Alexander Nature Chemistry, Vol. 8, Issue 7 https://doi.org/10.1038/nchem.2524	journal	May 2016
Operando Monitoring of F ^– Formation in Lithium Ion Batteries Bolli, Christoph; Guéguen, Aurélie; Mendez, Manuel A. Chemistry of Materials, Vol. 31, Issue 4 https://doi.org/10.1021/acs.chemmater.8b03810	journal	January 2019
Solubilities of six lithium salts in five non-aqueous solvents and in a few of their binary mixtures Xin, Nan; Sun, Yanjun; He, Maogang Fluid Phase Equilibria, Vol. 461 https://doi.org/10.1016/j.fluid.2017.12.034	journal	April 2018
Origin of H ₂ Evolution in LIBs: H ₂ O Reduction vs. Electrolyte Oxidation Metzger, Michael; Strehle, Benjamin; Solchenbach, Sophie Journal of The Electrochemical Society, Vol. 163, Issue 5 https://doi.org/10.1149/2.1151605jes	journal	January 2016
Li2CO3 decomposition in Li-ion batteries induced by the electrochemical oxidation of the electrolyte and of electrolyte impurities Freiberg, Anna T. S.; Sicklinger, Johannes; Solchenbach, Sophie Electrochimica Acta, Vol. 346 https://doi.org/10.1016/j.electacta.2020.136271	journal	June 2020
Unlocking the Potential of Cation-Disordered Oxides for Rechargeable Lithium Batteries Lee, J.; Urban, A.; Li, X. Science, Vol. 343, Issue 6170 https://doi.org/10.1126/science.1246432	journal	January 2014
Twin Problems of Interfacial Carbonate Formation in Nonaqueous Li–O ₂ Batteries McCloskey, B. D.; Speidel, A.; Scheffler, R. The Journal of Physical Chemistry Letters, Vol. 3, Issue 8 https://doi.org/10.1021/jz300243r	journal	March 2012
Fluorination‐Enhanced Surface Stability of Cation‐Disordered Rocksalt Cathodes for Li‐Ion Batteries Li, Linze; Lun, Zhengyan; Chen, Dongchang Advanced Functional Materials, Vol. 31, Issue 25 https://doi.org/10.1002/adfm.202101888	journal	April 2021
Electrolyte Effects on Spinel Dissolution and Cathodic Capacity Losses in 4 V Li∕Li[sub x]Mn[sub 2]O[sub 4] Rechargeable Cells Jang, Dong H. Journal of The Electrochemical Society, Vol. 144, Issue 10 https://doi.org/10.1149/1.1838016	journal	January 1997
Design principles for high transition metal capacity in disordered rocksalt Li-ion cathodes Kitchaev, Daniil A.; Lun, Zhengyan; Richards, William D. Energy & Environmental Science, Vol. 11, Issue 8 https://doi.org/10.1039/C8EE00816G	journal	January 2018
Size and charge effects on the structural stability of LiMO ₂ (M = transition metal) compounds Wu, Eric J.; Tepesch, Patrick D.; Ceder, Gerbrand Philosophical Magazine B, Vol. 77, Issue 4 https://doi.org/10.1080/13642819808206403	journal	April 1998
Li-ion battery materials: present and future Nitta, Naoki; Wu, Feixiang; Lee, Jung Tae Materials Today, Vol. 18, Issue 5 https://doi.org/10.1016/j.mattod.2014.10.040	journal	June 2015
Cation-disordered rocksalt-type high-entropy cathodes for Li-ion batteries Lun, Zhengyan; Ouyang, Bin; Kwon, Deok-Hwang Nature Materials, Vol. 20, Issue 2 https://doi.org/10.1038/s41563-020-00816-0	journal	October 2020
Residual Lithium Carbonate Predominantly Accounts for First Cycle CO ₂ and CO Outgassing of Li-Stoichiometric and Li-Rich Layered Transition-Metal Oxides Renfrew, Sara E.; McCloskey, Bryan D. Journal of the American Chemical Society, Vol. 139, Issue 49 https://doi.org/10.1021/jacs.7b08461	journal	November 2017
Dissolution, migration, and deposition of transition metal ions in Li-ion batteries exemplified by Mn-based cathodes – a critical review Zhan, Chun; Wu, Tianpin; Lu, Jun Energy & Environmental Science, Vol. 11, Issue 2 https://doi.org/10.1039/C7EE03122J	journal	January 2018
The Role of Electron Localization in Covalency and Electrochemical Properties of Lithium‐Ion Battery Cathode Materials Wang, Xuelong; Fan, Xiulin; Yu, Xiqian Advanced Functional Materials https://doi.org/10.1002/adfm.202001633	journal	May 2020
The Li-Ion Rechargeable Battery: A Perspective Goodenough, John B.; Park, Kyu-Sung Journal of the American Chemical Society, Vol. 135, Issue 4 https://doi.org/10.1021/ja3091438	journal	January 2013
Extended Interfacial Stability through Simple Acid Rinsing in a Li-Rich Oxide Cathode Material Ramakrishnan, Srinivasan; Park, Byungchun; Wu, Jue Journal of the American Chemical Society, Vol. 142, Issue 18 https://doi.org/10.1021/jacs.0c02859	journal	April 2020
Solid-state 19F NMR investigation of poly(vinylidene fluoride) with high-power proton decoupling Holstein, Peter; Harris, Robin K.; Say, Barry J. Solid State Nuclear Magnetic Resonance, Vol. 8, Issue 4 https://doi.org/10.1016/S0926-2040(97)00014-3	journal	August 1997
Combining Accurate O ₂ and Li ₂ O ₂ Assays to Separate Discharge and Charge Stability Limitations in Nonaqueous Li–O ₂ Batteries McCloskey, Bryan D.; Valery, Alexia; Luntz, Alan C. The Journal of Physical Chemistry Letters, Vol. 4, Issue 17 https://doi.org/10.1021/jz401659f	journal	August 2013
Review on Challenges and Recent Advances in the Electrochemical Performance of High Capacity Li- and Mn-Rich Cathode Materials for Li-Ion Batteries Nayak, Prasant Kumar; Erickson, Evan M.; Schipper, Florian Advanced Energy Materials, Vol. 8, Issue 8 https://doi.org/10.1002/aenm.201702397	journal	December 2017
Redox Behaviors in a Li-Excess Cation-Disordered Mn–Nb–O–F Rocksalt Cathode Yue, Yuan; Li, Ning; Li, Linze Chemistry of Materials, Vol. 32, Issue 11 https://doi.org/10.1021/acs.chemmater.9b05221	journal	May 2020
The cathode–electrolyte interface in the Li-ion battery Edström, K.; Gustafsson, T.; Thomas, J. O. Electrochimica Acta, Vol. 50, Issue 2-3 https://doi.org/10.1016/j.electacta.2004.03.049	journal	November 2004
Reduction Reactions of Electrolyte Salts for Lithium Ion Batteries: LiPF ₆ , LiBF ₄ , LiDFOB, LiBOB, and LiTFSI Parimalam, Bharathy S.; Lucht, Brett L. Journal of The Electrochemical Society, Vol. 165, Issue 2 https://doi.org/10.1149/2.0901802jes	journal	January 2018
Surface phenomena of high energy Li(Ni1/3Co1/3Mn1/3)O2/graphite cells at high temperature and high cutoff voltages Liu, Ting; Garsuch, Arnd; Chesneau, Frederick Journal of Power Sources, Vol. 269 https://doi.org/10.1016/j.jpowsour.2014.07.051	journal	December 2014
Ten years left to redesign lithium-ion batteries Turcheniuk, Kostiantyn; Bondarev, Dmitry; Singhal, Vinod Nature, Vol. 559, Issue 7715 https://doi.org/10.1038/d41586-018-05752-3	journal	July 2018
Electrolyte Oxidation Pathways in Lithium-Ion Batteries Rinkel, Bernardine L. D.; Hall, David S.; Temprano, Israel Journal of the American Chemical Society, Vol. 142, Issue 35 https://doi.org/10.1021/jacs.0c06363	journal	July 2020
Mitigating oxygen loss to improve the cycling performance of high capacity cation-disordered cathode materials Lee, Jinhyuk; Papp, Joseph K.; Clément, Raphaële J. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-01115-0	journal	October 2017
Short-Range Order and Unusual Modes of Nickel Redox in a Fluorine-Substituted Disordered Rocksalt Oxide Lithium-Ion Cathode Clément, Raphaële J.; Kitchaev, Daniil; Lee, Jinhyuk Chemistry of Materials, Vol. 30, Issue 19 https://doi.org/10.1021/acs.chemmater.8b03794	journal	September 2018
Distinct Reaction Characteristics of Electrolyte Additives for High-Voltage Lithium-Ion Batteries: Tris(trimethylsilyl) Phosphite, Borate, and Phosphate Han, Young-Kyu; Yoo, Jaeik; Yim, Taeeun Electrochimica Acta, Vol. 215 https://doi.org/10.1016/j.electacta.2016.08.131	journal	October 2016
A review of blended cathode materials for use in Li-ion batteries Chikkannanavar, Satishkumar B.; Bernardi, Dawn M.; Liu, Lingyun Journal of Power Sources, Vol. 248 https://doi.org/10.1016/j.jpowsour.2013.09.052	journal	February 2014
Effect of Fluorination on Lithium Transport and Short‐Range Order in Disordered‐Rocksalt‐Type Lithium‐Ion Battery Cathodes Ouyang, Bin; Artrith, Nongnuch; Lun, Zhengyan Advanced Energy Materials, Vol. 10, Issue 10 https://doi.org/10.1002/aenm.201903240	journal	March 2020
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
Determining the Criticality of Li‐Excess for Disordered‐Rocksalt Li‐Ion Battery Cathodes Lee, Jinhyuk; Wang, Chao; Malik, Rahul Advanced Energy Materials, Vol. 11, Issue 24 https://doi.org/10.1002/aenm.202100204	journal	May 2021
Improved Cycling Performance of Li-Excess Cation-Disordered Cathode Materials upon Fluorine Substitution Lun, Zhengyan; Ouyang, Bin; Kitchaev, Daniil A. Advanced Energy Materials, Vol. 9, Issue 2 https://doi.org/10.1002/aenm.201802959	journal	November 2018
Design Principles for High-Capacity Mn-Based Cation-Disordered Rocksalt Cathodes Lun, Zhengyan; Ouyang, Bin; Cai, Zijian Chem, Vol. 6, Issue 1 https://doi.org/10.1016/j.chempr.2019.10.001	journal	January 2020
Depth profile studies on nickel rich cathode material surfaces after cycling with an electrolyte containing vinylene carbonate at elevated temperature Lee, Won Jong; Prasanna, K.; Jo, Yong Nam Phys. Chem. Chem. Phys., Vol. 16, Issue 32 https://doi.org/10.1039/C4CP02075H	journal	January 2014
Anion Reactivity in Cation‐Disordered Rocksalt Cathode Materials: The Influence of Fluorine Substitution Crafton, Matthew J.; Yue, Yuan; Huang, Tzu‐Yang Advanced Energy Materials, Vol. 10, Issue 35 https://doi.org/10.1002/aenm.202001500	journal	August 2020
A carbonate-free, sulfone-based electrolyte for high-voltage Li-ion batteries Alvarado, Judith; Schroeder, Marshall A.; Zhang, Minghao Materials Today, Vol. 21, Issue 4 https://doi.org/10.1016/j.mattod.2018.02.005	journal	May 2018
Understanding the Effect of Cation Disorder on the Voltage Profile of Lithium Transition-Metal Oxides Abdellahi, Aziz; Urban, Alexander; Dacek, Stephen Chemistry of Materials, Vol. 28, Issue 15 https://doi.org/10.1021/acs.chemmater.6b01438	journal	July 2016
Coupled LiPF ₆ Decomposition and Carbonate Dehydrogenation Enhanced by Highly Covalent Metal Oxides in High-Energy Li-Ion Batteries Yu, Yang; Karayaylali, Pinar; Katayama, Yu The Journal of Physical Chemistry C, Vol. 122, Issue 48 https://doi.org/10.1021/acs.jpcc.8b07848	journal	October 2018
NMR evidence of LiF coating rather than fluorine substitution in Li(Ni0.425Mn0.425Co0.15)O2 Ménétrier, M.; Bains, J.; Croguennec, L. Journal of Solid State Chemistry, Vol. 181, Issue 12 https://doi.org/10.1016/j.jssc.2008.09.002	journal	December 2008
Role of Electronic Structure in the Susceptibility of Metastable Transition-Metal Oxide Structures to Transformation Reed, John; Ceder, Gerbrand Chemical Reviews, Vol. 104, Issue 10 https://doi.org/10.1021/cr020733x	journal	October 2004
Quantification of Surface Oxygen Depletion and Solid Carbonate Evolution on the First Cycle of LiNi _0.6 Mn _0.2 Co _0.2 O ₂ Electrodes Renfrew, Sara E.; McCloskey, Bryan D. ACS Applied Energy Materials, Vol. 2, Issue 5 https://doi.org/10.1021/acsaem.9b00459	journal	April 2019
Tailoring the Redox Reactions for High‐Capacity Cycling of Cation‐Disordered Rocksalt Cathodes Yue, Yuan; Li, Ning; Ha, Yang Advanced Functional Materials, Vol. 31, Issue 14 https://doi.org/10.1002/adfm.202008696	journal	January 2021
An Improved 2D Magic-Angle-Turning Pulse Sequence for the Measurement of Chemical-Shift Anisotropy Gan, Zhehong; Ernst, R. R. Journal of Magnetic Resonance, Series A, Vol. 123, Issue 1 https://doi.org/10.1006/jmra.1996.0227	journal	November 1996
Lithium-Ion Battery Supply Chain Considerations: Analysis of Potential Bottlenecks in Critical Metals Olivetti, Elsa A.; Ceder, Gerbrand; Gaustad, Gabrielle G. Joule, Vol. 1, Issue 2 https://doi.org/10.1016/j.joule.2017.08.019	journal	October 2017
Quantification of PF ₅ and POF ₃ from Side Reactions of LiPF ₆ in Li-Ion Batteries Solchenbach, Sophie; Metzger, Michael; Egawa, Masamitsu Journal of The Electrochemical Society, Vol. 165, Issue 13 https://doi.org/10.1149/2.0481813jes	journal	January 2018
Solvents’ Critical Role in Nonaqueous Lithium–Oxygen Battery Electrochemistry McCloskey, B. D.; Bethune, D. S.; Shelby, R. M. The Journal of Physical Chemistry Letters, Vol. 2, Issue 10, p. 1161-1166 https://doi.org/10.1021/jz200352v	journal	May 2011
Cation-disordered rocksalt transition metal oxides and oxyfluorides for high energy lithium-ion cathodes Clément, R. J.; Lun, Z.; Ceder, G. Energy & Environmental Science, Vol. 13, Issue 2 https://doi.org/10.1039/C9EE02803J	journal	January 2020

Similar Records

Anion Reactivity in Cation‐Disordered Rocksalt Cathode Materials: The Influence of Fluorine Substitution

Journal Article · Sun Aug 02 00:00:00 EDT 2020 · Advanced Energy Materials · OSTI ID:2326185

Crafton, Matthew J.; Yue, Yuan; Huang, Tzu‐Yang; +2 more

Fluorination effect for stabilizing cationic and anionic redox activities in cation-disordered cathode materials

Journal Article · Sun Jul 19 00:00:00 EDT 2020 · Energy Storage Materials · OSTI ID:2326185

Zhou, Ke; Zheng, Shiyao; Ren, Fucheng; +9 more

Fluorination‐Enhanced Surface Stability of Disordered Rocksalt Cathodes

Journal Article · Tue Feb 08 00:00:00 EST 2022 · Advanced Materials · OSTI ID:2326185

Li, Linze; Ahn, Juhyeon; Yue, Yuan; +3 more

Related Subjects

25 ENERGY STORAGE
cation-disordered rocksalt
differential electrochemical mass spectrometry
titration mass spectrometry
cathode−electrolyte interface
electrolyte degradation
oxygen redox
high voltage
fluoride-scavenging

Title: Tuning Bulk Redox and Altering Interfacial Reactivity in Highly Fluorinated Cation-Disordered Rocksalt Cathodes

Citation Formats

References (59)

Similar Records

Related Subjects