Influence of Electrolyte Additives on Interfacial Stability of Manganese-Rich Lithium-Ion Battery Cathodes

Dutta, Nikita S.; King, Madison; Wang, Bingning; Liao, Chen; Mangum, John S.; Finegan, Donal P.; Tremolet de Villers, Bertrand J.; Jungjohann, Katherine

doi:10.1021/acsaem.5c00862

Influence of Electrolyte Additives on Interfacial Stability of Manganese-Rich Lithium-Ion Battery Cathodes

Journal Article · Wed Aug 06 04:00:00 EDT 2025 · ACS Applied Energy Materials

DOI:https://doi.org/10.1021/acsaem.5c00862· OSTI ID:2588196

^[1]; ^[2]; Wang, Bingning ^[3]; ^[3]; ^[1]; ^[1]; ^[1]; Jungjohann, Katherine ^[1]

National Renewable Energy Laboratory (NREL), Golden, CO (United States)
National Renewable Energy Laboratory (NREL), Golden, CO (United States); Northern Arizona Univ., Flagstaff, AZ (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)

Affordable, long-lasting energy storage has become critical to support increased electricity demand in recent years. Cobalt-free, lithium- and manganese-rich lithium nickel manganese oxide (LMR-NM) cathodes stand to reduce cost and supply-chain concerns associated with traditional cobalt-containing cathodes for lithium-ion batteries by leveraging more earth-abundant materials; however, they have shown issues with long-term cycling stability. Here, we investigate lithium difluoro(oxalate)borate (LiDFOB), tris(trimethylsilyl) phosphite (TMSPi), and vinylene carbonate (VC) electrolyte additives for their ability to improve cycling performance of LMR-NM (0.3 Li₂MnO₃ + 0.7 LiMn_0.5Ni_0.50₂) cells. Cryogenic scanning transmission electron microscopy (cryo-STEM) with electron energy loss spectroscopy enables the construction of a structure–function relationship between cathode electrolyte interphase (CEI) characteristics and the electrochemical performance of cells aged with these additives. We find the combination of 2 wt % TMSPi + 1 wt % LiDFOB performs better than any single additive, achieving a 28% improvement in specific capacity over the baseline electrolyte after long-term cycling. We attribute this to LiDFOB mitigating Mn ion dissolution, with cryo-STEM showing Mn stabilized up to the CEI surface, coupled with improved CEI structure and chemistry enabled by TMSPi, evidenced by a moderately thick (∼7–15 nm) CEI that appears to protect against further electrolyte reactions with the particle. These results, achieved through site-specific nanoscale characterization, directly reveal mechanisms through which electrolyte engineering can improve the performance of earth-abundant cathodes, enabling informed development of more affordable and reliable batteries to meet future energy storage needs.

View Accepted Manuscript (DOE)

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC36-08GO28308; AC02-06CH11357; NA0003525

OSTI ID:: 2588196

Report Number(s):: NREL/JA--5K00-92105

Journal Information:: ACS Applied Energy Materials, Journal Name: ACS Applied Energy Materials Journal Issue: 16 Vol. 8; ISSN 2574-0962

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (50)

Understanding the Roles of Tris(trimethylsilyl) Phosphite (TMSPi) in LiNi _0.8 Mn _0.1 Co _0.1 O ₂ (NMC811)/Silicon–Graphite (Si–Gr) Lithium‐Ion Batteries Liu, Haidong; Naylor, Andrew J.; Menon, Ashok Sreekumar Advanced Materials Interfaces, Vol. 7, Issue 15 https://doi.org/10.1002/admi.202000277	journal	June 2020
Cobalt‐Free Cathode Materials: Families and their Prospects Zhao, Hong; Lam, Wai‐Yu Ashley; Sheng, Li Advanced Energy Materials, Vol. 12, Issue 16 https://doi.org/10.1002/aenm.202103894	journal	February 2022
Tris(trimethylsilyl) Phosphite and Lithium Difluoro(oxalato)borate as Electrolyte Additives for LiNi_0.5Mn_1.5O₄‐Graphite Lithium‐Ion Batteries Jamal, Ali; Salian, Girish D.; Mathew, Alma ChemElectroChem, Vol. 10, Issue 16 https://doi.org/10.1002/celc.202300139	journal	June 2023
Core level electron energy-loss spectra of minerals: pre-edge fine structures at the oxygen K -edge van Aken, P. A.; Liebscher, B.; Styrsa, V. J. Physics and Chemistry of Minerals, Vol. 25, Issue 7 https://doi.org/10.1007/s002690050140	journal	August 1998
On the use of vinylene carbonate (VC) as an additive to electrolyte solutions for Li-ion batteries Aurbach, D.; Gamolsky, K.; Markovsky, B. Electrochimica Acta, Vol. 47, Issue 9 https://doi.org/10.1016/S0013-4686(01)00858-1	journal	February 2002
An accelerated calendar and cycle life study of Li-ion cells Bloom, I.; Cole, B. W.; Sohn, J. J. Journal of Power Sources, Vol. 101, Issue 2 https://doi.org/10.1016/S0378-7753(01)00783-2	journal	October 2001
Electrolyte additive combinations that enhance performance of high-capacity Li1.2Ni0.15Mn0.55Co0.1O2–graphite cells Zhu, Ye; Li, Yan; Bettge, Martin Electrochimica Acta, Vol. 110 https://doi.org/10.1016/j.electacta.2013.03.102	journal	November 2013
Renovating the electrode-electrolyte interphase for layered lithium- & manganese-rich oxides Wu, Feng; Li, Weikang; Chen, Lai Energy Storage Materials, Vol. 28 https://doi.org/10.1016/j.ensm.2019.12.017	journal	June 2020
Tailoring solvation chemistry in carbonate electrolytes for all-climate, high-voltage lithium-rich batteries Lu, Zheng; Liu, Dong; Dai, Kuan Energy Storage Materials, Vol. 57 https://doi.org/10.1016/j.ensm.2023.02.029	journal	March 2023
Mechanisms for electrochemical performance enhancement by the salt-type electrolyte additive, lithium difluoro(oxalato)borate, in high-voltage lithium-ion batteries Cha, Jiho; Han, Jung-Gu; Hwang, Jaeseong Journal of Power Sources, Vol. 357 https://doi.org/10.1016/j.jpowsour.2017.04.094	journal	July 2017
Evaluating electrolyte additives for lithium-ion cells: A new Figure of Merit approach Tornheim, Adam; Peebles, Cameron; Gilbert, James A. Journal of Power Sources, Vol. 365 https://doi.org/10.1016/j.jpowsour.2017.08.093	journal	October 2017
Cathode-Electrolyte Interphase in Lithium Batteries Revealed by Cryogenic Electron Microscopy Zhang, Zewen; Yang, Jinlong; Huang, William Matter, Vol. 4, Issue 1 https://doi.org/10.1016/j.matt.2020.10.021	journal	January 2021
Data Processing for Atomic Resolution Electron Energy Loss Spectroscopy Cueva, Paul; Hovden, Robert; Mundy, Julia A. Microscopy and Microanalysis, Vol. 18, Issue 4 https://doi.org/10.1017/S1431927612000244	journal	June 2012
Electrolyte Comparison for Li-Metal Anodes with Cryo-Laser PFIB Jungjohann, Katherine; Merrill, Laura; Gannon, Renae Microscopy and Microanalysis, Vol. 27, Issue S1 https://doi.org/10.1017/S1431927621005547	journal	July 2021
Resolving Chemical and Spatial Heterogeneities at Complex Electrochemical Interfaces in Li-Ion Batteries Hestenes, Julia C.; May, Richard; Sadowski, Jerzy T. Chemistry of Materials, Vol. 34, Issue 1 https://doi.org/10.1021/acs.chemmater.1c03185	journal	December 2021
Chemical “Pickling” of Phosphite Additives Mitigates Impedance Rise in Li Ion Batteries Peebles, Cameron; Garcia, Juan; Tornheim, Adam P. The Journal of Physical Chemistry C, Vol. 122, Issue 18 https://doi.org/10.1021/acs.jpcc.8b02056	journal	April 2018
Stabilizing Capacity Retention in NMC811/Graphite Full Cells via TMSPi Electrolyte Additives Vidal Laveda, Josefa; Low, Jia En; Pagani, Francesco ACS Applied Energy Materials, Vol. 2, Issue 10 https://doi.org/10.1021/acsaem.9b00727	journal	September 2019
Insights into the Dual Role of Lithium Difluoro(oxalato)borate Additive in Improving the Electrochemical Performance of NMC811\|\|Graphite Cells Dong, Qingyu; Guo, Feng; Cheng, Zhenjie ACS Applied Energy Materials, Vol. 3, Issue 1 https://doi.org/10.1021/acsaem.9b01894	journal	December 2019
Unexpected Exchange Reactions between LiPF₆ and Additives: Enhancing Thermal Stability and Mitigating Transition-Metal Dissolution Wang, Bingning; Garcia, Juan C.; Chen, Jiajun ACS Applied Engineering Materials, Vol. 2, Issue 12 https://doi.org/10.1021/acsaenm.4c00588	journal	December 2024
Investigating the Compatibility of TTMSP and FEC Electrolyte Additives for LiNi_0.5Mn_0.3Co_0.2O₂ (NMC)–Silicon Lithium-Ion Batteries Haridas, Anulekha K.; Nguyen, Quan Anh; Terlier, Tanguy ACS Applied Materials & Interfaces, Vol. 13, Issue 2 https://doi.org/10.1021/acsami.0c19347	journal	January 2021
Synergistic Effect of TMSPi and FEC in Regulating the Electrode/Electrolyte Interfaces in Nickel-Rich Lithium Metal Batteries Zhang, Xiaoyan; Ren, Yufei; Zhang, Juyan ACS Applied Materials & Interfaces, Vol. 14, Issue 9 https://doi.org/10.1021/acsami.1c24971	journal	February 2022
Spinel/Layered Heterostructured Lithium-Rich Oxide Nanowires as Cathode Material for High-Energy Lithium-Ion Batteries Yu, Ruizhi; Zhang, Xiaohui; Liu, Tao ACS Applied Materials & Interfaces, Vol. 9, Issue 47 https://doi.org/10.1021/acsami.7b11942	journal	November 2017
Nanoscale Elemental Mapping of Intact Solid–Liquid Interfaces and Reactive Materials in Energy Devices Enabled by Cryo-FIB/SEM Zachman, Michael J.; Tu, Zhengyuan; Archer, Lynden A. ACS Energy Letters, Vol. 5, Issue 4 https://doi.org/10.1021/acsenergylett.0c00202	journal	March 2020
Can Cobalt Be Eliminated from Lithium-Ion Batteries? Lee, Steven; Manthiram, Arumugam ACS Energy Letters, Vol. 7, Issue 9 https://doi.org/10.1021/acsenergylett.2c01553	journal	August 2022
Theoretical Studies To Understand Surface Chemistry on Carbon Anodes for Lithium-Ion Batteries: How Does Vinylene Carbonate Play Its Role as an Electrolyte Additive? Wang, Yixuan; Nakamura, Shinichiro; Tasaki, Ken Journal of the American Chemical Society, Vol. 124, Issue 16 https://doi.org/10.1021/ja017073i	journal	April 2002
Data-driven design of electrolyte additives supporting high-performance 5 V LiNi0.5Mn1.5O4 positive electrodes Wang, Bingning; Doan, Hieu A.; Son, Seoung-Bum Nature Communications, Vol. 16, Issue 1 https://doi.org/10.1038/s41467-025-57961-w	journal	April 2025
Cryo-STEM mapping of solid–liquid interfaces and dendrites in lithium-metal batteries Zachman, Michael J.; Tu, Zhengyuan; Choudhury, Snehashis Nature, Vol. 560, Issue 7718 https://doi.org/10.1038/s41586-018-0397-3	journal	August 2018
Li₂MnO₃-stabilized LiMO₂ (M = Mn, Ni, Co) electrodes for lithium-ion batteries Thackeray, Michael M.; Kang, Sun-Ho; Johnson, Christopher S. Journal of Materials Chemistry, Vol. 17, Issue 30, p. 3112-3125 https://doi.org/10.1039/B702425H	journal	January 2007
Performance and design considerations for lithium excess layered oxide positive electrode materials for lithium ion batteries Hy, Sunny; Liu, Haodong; Zhang, Minghao Energy & Environmental Science, Vol. 9, Issue 6 https://doi.org/10.1039/C5EE03573B	journal	January 2016
Lifetime limit of tris(trimethylsilyl) phosphite as electrolyte additive for high voltage lithium ion batteries Qi, Xin; Tao, Liang; Hahn, Hendrik RSC Advances, Vol. 6, Issue 44 https://doi.org/10.1039/C6RA06555D	journal	January 2016
Guidelines and trends for next-generation rechargeable lithium and lithium-ion batteries Wu, Feixiang; Maier, Joachim; Yu, Yan Chemical Society Reviews, Vol. 49, Issue 5 https://doi.org/10.1039/C7CS00863E	journal	January 2020
Developing high-voltage spinel LiNi _0.5 Mn _1.5 O ₄ cathodes for high-energy-density lithium-ion batteries: current achievements and future prospects Liang, Gemeng; Peterson, Vanessa K.; See, Khay Wai Journal of Materials Chemistry A, Vol. 8, Issue 31 https://doi.org/10.1039/D0TA02812F	journal	January 2020
Two electrolyte decomposition pathways at nickel-rich cathode surfaces in lithium-ion batteries Rinkel, Bernardine L. D.; Vivek, J. Padmanabhan; Garcia-Araez, Nuria Energy & Environmental Science, Vol. 15, Issue 8 https://doi.org/10.1039/D1EE04053G	journal	January 2022
Batteries: Materials principles and characterization methods Liao, Chen https://doi.org/10.1088/978-0-7503-2682-7	book	December 2021
Atomic-resolution imaging of oxidation states in manganites Varela, M.; Oxley, M. P.; Luo, W. Physical Review B, Vol. 79, Issue 8 https://doi.org/10.1103/PhysRevB.79.085117	journal	February 2009
A Threshold Selection Method from Gray-Level Histograms Otsu, Nobuyuki IEEE Transactions on Systems, Man, and Cybernetics, Vol. 9, Issue 1 https://doi.org/10.1109/TSMC.1979.4310076	journal	January 1979
Atomic structure of sensitive battery materials and interfaces revealed by cryo–electron microscopy Li, Yuzhang; Li, Yanbin; Pei, Allen Science, Vol. 358, Issue 6362 https://doi.org/10.1126/science.aam6014	journal	October 2017
Capturing the swelling of solid-electrolyte interphase in lithium metal batteries Zhang, Zewen; Li, Yuzhang; Xu, Rong Science, Vol. 375, Issue 6576 https://doi.org/10.1126/science.abi8703	journal	January 2022
The Effects of Acid Treatment on the Electrochemical Properties of 0.5 Li₂MnO₃ ∙ 0.5 LiNi_0.44Co_0.25Mn_0.31O₂ Electrodes in Lithium Cells Kang, S.-H.; Johnson, C. S.; Vaughey, J. T. Journal of The Electrochemical Society, Vol. 153, Issue 6, p. A1186-A1192 https://doi.org/10.1149/1.2194764	journal	January 2006
Electrochemical Protocols to Assess the Effects of Dissolved Transition Metal in Graphite/LiNiO₂ Cells Performance Meunier, Valentin; De Souza, Matheus Leal; Morcrette, Mathieu Journal of The Electrochemical Society, Vol. 169, Issue 7 https://doi.org/10.1149/1945-7111/ac7e7a	journal	July 2022
Electrolyte Study for High-Nickel LiNi_0.9Mn_0.05Co_0.05O₂ Cathodes Wang, Bingning; Gim, Jihyeon; Son, Seoung-Bum Journal of The Electrochemical Society, Vol. 170, Issue 2 https://doi.org/10.1149/1945-7111/acb66d	journal	February 2023
Evaluation of Lithium Metal Anode Volumetric Expansion through Laser Plasma Focused Ion Beam Cross-Sectional Imaging Merrill, Laura C.; Gannon, Renae N.; Jungjohann, Katherine L. Journal of The Electrochemical Society, Vol. 170, Issue 8 https://doi.org/10.1149/1945-7111/acf162	journal	August 2023
Review—Manganese Dissolution from Spinel Cathode: Few Unanswered Questions Bhandari, Arihant; Bhattacharya, Jishnu Journal of The Electrochemical Society, Vol. 164, Issue 2 https://doi.org/10.1149/2.0101614jes	journal	December 2016
Understanding the Effect of Lithium Bis(oxalato) Borate (LiBOB) on the Structural and Electrochemical Aging of Li and Mn Rich High Capacity Li _1.2 Ni _0.16 Mn _0.56 Co _0.08 O ₂ Cathodes Nayak, Prasant Kumar; Grinblat, Judith; Levi, Mikhael Journal of The Electrochemical Society, Vol. 162, Issue 4 https://doi.org/10.1149/2.0251504jes	journal	January 2015
Enabling High-Energy, High-Voltage Lithium-Ion Cells: Standardization of Coin-Cell Assembly, Electrochemical Testing, and Evaluation of Full Cells Long, Brandon R.; Rinaldo, Steven G.; Gallagher, Kevin G. Journal of The Electrochemical Society, Vol. 163, Issue 14 https://doi.org/10.1149/2.0691614jes	journal	January 2016
Advancing Lithium- and Manganese-Rich Cathodes through a Combined Electrolyte Additive/Surface Treatment Strategy Gutierrez, Arturo; He, Meinan; Yonemoto, Bryan T. Journal of The Electrochemical Society, Vol. 166, Issue 16 https://doi.org/10.1149/2.1281915jes	journal	January 2019
Manganese valence imaging in Mn minerals at the nanoscale using STEM-EELS Loomer, D. B.; Al, T. A.; Weaver, L. American Mineralogist, Vol. 92, Issue 1 https://doi.org/10.2138/am.2007.2252	journal	January 2007
Determination of manganese valence states in (Mn3+, Mn4+) minerals by electron energy-loss spectroscopy Zhang, S.; Livi, K. J. T.; Gaillot, A. -C. American Mineralogist, Vol. 95, Issue 11-12 https://doi.org/10.2138/am.2010.3468	journal	November 2010
Understanding and Mitigating the Dissolution and Delamination Issues Encountered with High-Voltage LiNi0.5Mn1.5O4 Wang, Bingning; Son, Seoung-Bum; Badami, Pavan Batteries, Vol. 9, Issue 9 https://doi.org/10.3390/batteries9090435	journal	August 2023
Molecular Dynamics Simulation and Cryo-Electron Microscopy Investigation of AOT Surfactant Structure at the Hydrated Mica Surface Long, Daniel M.; Greathouse, Jeffery A.; Xu, Guangping Minerals, Vol. 12, Issue 4 https://doi.org/10.3390/min12040479	journal	April 2022

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Influence of Electrolyte Additives on Interfacial Stability of Manganese-Rich Lithium-Ion Battery Cathodes

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