In Situ Ion‐Exchange Metathesis Induced Conformal LiF Surface Films on Cathode (NMC811) as a Cathode Electrolyte Interphase

Thapaliya, Bishnu P.; Wang, Tao; Borisevich, Albina Y.; Meyer, Harry M.; Sun, Xiao‐Guang; Paranthaman, Mariappan Parans; Bridges, Craig A.; Dai, Sheng

doi:10.1002/adfm.202302443

In Situ Ion‐Exchange Metathesis Induced Conformal LiF Surface Films on Cathode (NMC811) as a Cathode Electrolyte Interphase

Journal Article · Sat Jul 08 00:00:00 EDT 2023 · Advanced Functional Materials

DOI:https://doi.org/10.1002/adfm.202302443· OSTI ID:1997741

^[1]; ^[1]; ^[2]; ^[1]; ^[1]; ^[1]; ^[1]; ^[3]

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)

High-capacity cathodes (LiNi_0.8Mn_0.1Co_0.1O₂, NMC811) are promising for vehicle electrification because of their high gravimetric energy density. However, their electrochemical performance still relies upon the stability of the cathode electrolyte interphase (CEI). A highly reactive cathode interface leads to parasitic side reactions with electrolytes, resulting in accelerated capacity fading. Well-developed LiF and LiF-like inorganic compounds are believed to be good CEI components for stabilizing such reactive electrode interfaces. However, it is challenging to form an optimal surface sub-nanolayer of LiF on the cathode surfaces because of the complexity of the electrochemical reaction during battery cycling. Herein, the formation of a conformal LiF layer on the NMC811 electrode surface via an in situ ion-exchange metathesis process is reported, demonstrating a promising electrochemical performance because of a LiF-stabilized CEI. In situ generated LiF-coated NMC811 electrodes exhibit ≈97% capacity retention up to 100 cycles at a 0.3 C rate with average coulombic efficiency of ≈99.9% and ≈80% capacity retention up to 200 cycles at a 1 C rate with average coulombic efficiency of >99.6%. This finding may pave the way for reengineering the CEI to enhance the electrochemical performances and cycling stability of the high-capacity cathodes.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1997741

Alternate ID(s):: OSTI ID: 1988693

Journal Information:: Advanced Functional Materials, Journal Name: Advanced Functional Materials Journal Issue: 44 Vol. 33; ISSN 1616-301X

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (48)

High-Voltage Lithium-Metal Batteries Enabled by Localized High-Concentration Electrolytes Chen, Shuru; Zheng, Jianming; Mei, Donghai Advanced Materials, Vol. 30, Issue 21 https://doi.org/10.1002/adma.201706102	journal	March 2018
Enhancing Cycling Stability and Capacity Retention of NMC811 Cathodes by Reengineering Interfaces via Electrochemical Fluorination Thapaliya, Bishnu P.; Misra, Sudhajit; Yang, Shi‐ze Advanced Materials Interfaces, Vol. 9, Issue 18 https://doi.org/10.1002/admi.202200035	journal	February 2022
Conformal LiF Stabilized Interfaces via Electrochemical Fluorination on High Voltage Spinel Cathodes (≈4.9 V) for Lithium‐Ion Batteries Thapaliya, Bishnu P.; Borisevich, Albina Y.; Meyer, Harry M. Advanced Materials Interfaces, Vol. 9, Issue 32 https://doi.org/10.1002/admi.202201600	journal	October 2022
From Surface ZrO ₂ Coating to Bulk Zr Doping by High Temperature Annealing of Nickel-Rich Lithiated Oxides and Their Enhanced Electrochemical Performance in Lithium Ion Batteries Schipper, Florian; Bouzaglo, Hana; Dixit, Mudit Advanced Energy Materials, Vol. 8, Issue 4 https://doi.org/10.1002/aenm.201701682	journal	September 2017
Prospect and Reality of Ni-Rich Cathode for Commercialization Kim, Junhyeok; Lee, Hyomyung; Cha, Hyungyeon Advanced Energy Materials, Vol. 8, Issue 6 https://doi.org/10.1002/aenm.201702028	journal	November 2017
Amide‐Functional, Li₃N/LiF‐Rich Heterostructured Electrode Electrolyte Interphases for 4.6 V Li\|\|LiCoO₂ Batteries Liu, Jiandong; Wu, Mingguang; Li, Xin Advanced Energy Materials, Vol. 13, Issue 15 https://doi.org/10.1002/aenm.202300084	journal	March 2023
Nickel-Rich Layered Lithium Transition-Metal Oxide for High-Energy Lithium-Ion Batteries Liu, Wen; Oh, Pilgun; Liu, Xien Angewandte Chemie International Edition, Vol. 54, Issue 15 https://doi.org/10.1002/anie.201409262	journal	March 2015
Armor‐like Inorganic‐rich Cathode Electrolyte Interphase Enabled by the Pentafluorophenylboronic Acid Additive for High‐voltage Li\|\|NCM622 Batteries Yang, Yulu; Wang, Huaping; Zhu, Chunlei Angewandte Chemie International Edition, Vol. 62, Issue 22 https://doi.org/10.1002/anie.202300057	journal	April 2023
Synthesizing High‐Capacity Oxyfluoride Conversion Anodes by Direct Fluorination of Molybdenum Dioxide (MoO ₂ ) Thapaliya, Bishnu P.; Self, Ethan C.; Jafta, Charl J. ChemSusChem, Vol. 13, Issue 15 https://doi.org/10.1002/cssc.202001006	journal	July 2020
Microstructural Degradation of Ni-Rich Li[Ni _x Co _y Mn ₁ _−x−y ]O ₂ Cathodes During Accelerated Calendar Aging Ryu, Hoon-Hee; Park, Geon-Tae; Yoon, Chong S. Small, Vol. 14, Issue 45 https://doi.org/10.1002/smll.201803179	journal	September 2018
An Electron Diffraction and Crystal Chemical Investigation of Oxygen/Fluorine Ordering in Niobium Oxyfluoride, NbO2F Brink, Frank J.; Withers, Ray L.; Norén, Lasse Journal of Solid State Chemistry, Vol. 166, Issue 1 https://doi.org/10.1006/jssc.2002.9562	journal	June 2002
Highly Fluorinated Interphases Enable High-Voltage Li-Metal Batteries Fan, Xiulin; Chen, Long; Ji, Xiao Chem, Vol. 4, Issue 1 https://doi.org/10.1016/j.chempr.2017.10.017	journal	January 2018
Improving the cycling performance of LiNi0.8Co0.1Mn0.1O2 by surface coating with Li2TiO3 Meng, Kui; Wang, Zhixing; Guo, Huajun Electrochimica Acta, Vol. 211 https://doi.org/10.1016/j.electacta.2016.06.110	journal	September 2016
A perspective on nickel-rich layered oxide cathodes for lithium-ion batteries Manthiram, Arumugam; Song, Bohang; Li, Wangda Energy Storage Materials, Vol. 6 https://doi.org/10.1016/j.ensm.2016.10.007	journal	January 2017
Comparison of the structural and electrochemical properties of layered Li[NixCoyMnz]O2 (x = 1/3, 0.5, 0.6, 0.7, 0.8 and 0.85) cathode material for lithium-ion batteries Noh, Hyung-Joo; Youn, Sungjune; Yoon, Chong Seung Journal of Power Sources, Vol. 233 https://doi.org/10.1016/j.jpowsour.2013.01.063	journal	July 2013
Singlet oxygen evolution from layered transition metal oxide cathode materials and its implications for lithium-ion batteries Wandt, Johannes; Freiberg, Anna T. S.; Ogrodnik, Alexander Materials Today, Vol. 21, Issue 8 https://doi.org/10.1016/j.mattod.2018.03.037	journal	October 2018
Significantly improving cycling performance of cathodes in lithium ion batteries: The effect of Al2O3 and LiAlO2 coatings on LiNi0.6Co0.2Mn0.2O2 Liu, Wen; Li, Xifei; Xiong, Dongbin Nano Energy, Vol. 44 https://doi.org/10.1016/j.nanoen.2017.11.010	journal	February 2018
Effect of Anode Slippage on Cathode Cutoff Potential and Degradation Mechanisms in Ni-Rich Li-Ion Batteries Dose, Wesley M.; Xu, Chao; Grey, Clare P. Cell Reports Physical Science, Vol. 1, Issue 11 https://doi.org/10.1016/j.xcrp.2020.100253	journal	November 2020
Capacity Fading of Ni-Rich Li[Ni _x Co _y Mn _{1– x – y} ]O ₂ (0.6 ≤ x ≤ 0.95) Cathodes for High-Energy-Density Lithium-Ion Batteries: Bulk or Surface Degradation? Ryu, Hoon-Hee; Park, Kang-Joon; Yoon, Chong S. Chemistry of Materials, Vol. 30, Issue 3 https://doi.org/10.1021/acs.chemmater.7b05269	journal	January 2018
Evolution of Structure and Lithium Dynamics in LiNi _0.8 Mn _0.1 Co _0.1 O ₂ (NMC811) Cathodes during Electrochemical Cycling Märker, Katharina; Reeves, Philip J.; Xu, Chao Chemistry of Materials, Vol. 31, Issue 7 https://doi.org/10.1021/acs.chemmater.9b00140	journal	March 2019
Phases and Interfaces from Real Space Atomically Resolved Data: Physics-Based Deep Data Image Analysis Vasudevan, Rama K.; Ziatdinov, Maxim; Jesse, Stephen Nano Letters, Vol. 16, Issue 9 https://doi.org/10.1021/acs.nanolett.6b02130	journal	August 2016
Formation of LiF Surface Layer During Direct Fluorination of High-Capacity Co-Free Disordered Rocksalt Cathodes Zhang, Yiman; Self, Ethan C.; Thapaliya, Bishnu P. ACS Applied Materials & Interfaces, Vol. 13, Issue 32 https://doi.org/10.1021/acsami.1c07882	journal	August 2021
Long-Life Nickel-Rich Layered Oxide Cathodes with a Uniform Li ₂ ZrO ₃ Surface Coating for Lithium-Ion Batteries Song, Bohang; Li, Wangda; Oh, Seung-Min ACS Applied Materials & Interfaces, Vol. 9, Issue 11 https://doi.org/10.1021/acsami.7b00070	journal	March 2017
Structural and Electrochemical Aspects of LiNi _0.8 Co _0.1 Mn _0.1 O ₂ Cathode Materials Doped by Various Cations Weigel, Tina; Schipper, Florian; Erickson, Evan M. ACS Energy Letters, Vol. 4, Issue 2 https://doi.org/10.1021/acsenergylett.8b02302	journal	January 2019
Degradation Mechanism of Ni-Enriched NCA Cathode for Lithium Batteries: Are Microcracks Really Critical? Park, Kang-Joon; Hwang, Jang-Yeon; Ryu, Hoon-Hee ACS Energy Letters, Vol. 4, Issue 6 https://doi.org/10.1021/acsenergylett.9b00733	journal	May 2019
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
Dendrite-Free Lithium Deposition via Self-Healing Electrostatic Shield Mechanism Ding, Fei; Xu, Wu; Graff, Gordon L. Journal of the American Chemical Society, Vol. 135, Issue 11, p. 4450-4456 https://doi.org/10.1021/ja312241y	journal	March 2013
Dendrite-Free Lithium Deposition with Self-Aligned Nanorod Structure Zhang, Yaohui; Qian, Jiangfeng; Xu, Wu Nano Letters, Vol. 14, Issue 12 https://doi.org/10.1021/nl5039117	journal	November 2014
Issues and challenges facing rechargeable lithium batteries Tarascon, J.-M.; Armand, M. Nature, Vol. 414, Issue 6861, p. 359-367 https://doi.org/10.1038/35104644	journal	November 2001
Building better batteries Armand, M.; Tarascon, J.-M. Nature, Vol. 451, Issue 7179, p. 652-657 https://doi.org/10.1038/451652a	journal	February 2008
Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries Lin, Feng; Markus, Isaac M.; Nordlund, Dennis Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms4529	journal	March 2014
High-energy cathode material for long-life and safe lithium batteries Sun, Yang-Kook; Myung, Seung-Taek; Park, Byung-Chun Nature Materials, Vol. 8, Issue 4 https://doi.org/10.1038/nmat2418	journal	March 2009
Reviving the lithium metal anode for high-energy batteries Lin, Dingchang; Liu, Yayuan; Cui, Yi Nature Nanotechnology, Vol. 12, Issue 3 https://doi.org/10.1038/nnano.2017.16	journal	March 2017
High energy-density and reversibility of iron fluoride cathode enabled via an intercalation-extrusion reaction Fan, Xiulin; Hu, Enyuan; Ji, Xiao Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-04476-2	journal	June 2018
Identifying the components of the solid–electrolyte interphase in Li-ion batteries Wang, Luning; Menakath, Anjali; Han, Fudong Nature Chemistry, Vol. 11, Issue 9 https://doi.org/10.1038/s41557-019-0304-z	journal	August 2019
Performance and cost of materials for lithium-based rechargeable automotive batteries Schmuch, Richard; Wagner, Ralf; Hörpel, Gerhard Nature Energy, Vol. 3, Issue 4 https://doi.org/10.1038/s41560-018-0107-2	journal	April 2018
Intercalation-conversion hybrid cathodes enabling Li–S full-cell architectures with jointly superior gravimetric and volumetric energy densities Xue, Weijiang; Shi, Zhe; Suo, Liumin Nature Energy, Vol. 4, Issue 5 https://doi.org/10.1038/s41560-019-0351-0	journal	March 2019
All-temperature batteries enabled by fluorinated electrolytes with non-polar solvents Fan, Xiulin; Ji, Xiao; Chen, Long Nature Energy, Vol. 4, Issue 10 https://doi.org/10.1038/s41560-019-0474-3	journal	October 2019
High-nickel layered oxide cathodes for lithium-based automotive batteries Li, Wangda; Erickson, Evan M.; Manthiram, Arumugam Nature Energy, Vol. 5, Issue 1 https://doi.org/10.1038/s41560-019-0513-0	journal	January 2020
Ultra-high-voltage Ni-rich layered cathodes in practical Li metal batteries enabled by a sulfonamide-based electrolyte Xue, Weijiang; Huang, Mingjun; Li, Yutao Nature Energy, Vol. 6, Issue 5 https://doi.org/10.1038/s41560-021-00792-y	journal	March 2021
Non-flammable electrolyte enables Li-metal batteries with aggressive cathode chemistries Fan, Xiulin; Chen, Long; Borodin, Oleg Nature Nanotechnology, Vol. 13, Issue 8 https://doi.org/10.1038/s41565-018-0183-2	journal	July 2018
Self-smoothing anode for achieving high-energy lithium metal batteries under realistic conditions Niu, Chaojiang; Pan, Huilin; Xu, Wu Nature Nanotechnology, Vol. 14, Issue 6 https://doi.org/10.1038/s41565-019-0427-9	journal	April 2019
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
FSI-inspired solvent and “full fluorosulfonyl” electrolyte for 4 V class lithium-metal batteries Xue, Weijiang; Shi, Zhe; Huang, Mingjun Energy & Environmental Science, Vol. 13, Issue 1 https://doi.org/10.1039/C9EE02538C	journal	January 2020
Revealing electrolyte oxidation via carbonate dehydrogenation on Ni-based oxides in Li-ion batteries by in situ Fourier transform infrared spectroscopy Zhang, Yirui; Katayama, Yu; Tatara, Ryoichi Energy & Environmental Science, Vol. 13, Issue 1 https://doi.org/10.1039/C9EE02543J	journal	January 2020
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
Oxygen Release and Its Effect on the Cycling Stability of LiNi _x Mn _y Co _z O ₂ (NMC) Cathode Materials for Li-Ion Batteries Jung, Roland; Metzger, Michael; Maglia, Filippo Journal of The Electrochemical Society, Vol. 164, Issue 7 https://doi.org/10.1149/2.0021707jes	journal	January 2017
Deep data analysis via physically constrained linear unmixing: universal framework, domain examples, and a community-wide platform Kannan, R.; Ievlev, A. V.; Laanait, N. Advanced Structural and Chemical Imaging, Vol. 4, Issue 1 https://doi.org/10.1186/s40679-018-0055-8	journal	April 2018