LiH formation and its impact on Li batteries revealed by cryogenic electron microscopy

Vilá, Rafael A.; Boyle, David T.; Dai, Alan; Zhang, Wenbo; Sayavong, Philaphon; Ye, Yusheng; Yang, Yufei; Dionne, Jennifer A.; Cui, Yi

doi:10.1126/sciadv.adf3609

Title: LiH formation and its impact on Li batteries revealed by cryogenic electron microscopy

Journal Article · 23 March 2023 · Science Advances

DOI: https://doi.org/10.1126/sciadv.adf3609 · OSTI ID:1984661

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Stanford Univ., CA (United States); Stanford University
Stanford Univ., CA (United States)
Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Institute for Materials and Energy Science (SIMES)

Little is known about how evolved hydrogen affects the cycling of Li batteries. Hypotheses include the formation of LiH in the solid-electrolyte interphase (SEI) and dendritic growth of LiH. Here, we discover that LiH formation in Li batteries likely follows a different pathway: Hydrogen evolved during cycling reacts to nucleate and grow LiH within already deposited Li metal, consuming active Li. We provide the evidence that LiH formed in Li batteries electrically isolates active Li from the current collector that degrades battery capacity. We detect the coexistence of Li metal and LiH also on graphite and silicon anodes, showing that LiH forms in most Li battery anode chemistries. Last, we find that LiH has its own SEI layer that is chemically and structurally distinct from the SEI on Li metal. Our results highlight the formation mechanism and chemical origins of LiH, providing critical insight into how to prevent its formation.

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Research Organization:: Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); National Science Foundation (NSF)

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1984661

Journal Information:: Science Advances, Journal Name: Science Advances Journal Issue: 12 Vol. 9; ISSN 2375-2548

Publisher:: AAASCopyright Statement

Country of Publication:: United States

Language:: English

References (41)

A short review of failure mechanisms of lithium metal and lithiated graphite anodes in liquid electrolyte solutions Aurbach, D. Solid State Ionics, Vol. 148, Issue 3-4 https://doi.org/10.1016/S0167-2738(02)00080-2	journal	June 2002
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
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
High-throughput computational X-ray absorption spectroscopy Mathew, Kiran; Zheng, Chen; Winston, Donald Scientific Data, Vol. 5, Issue 1 https://doi.org/10.1038/sdata.2018.151	journal	July 2018
The Surface Chemistry of Lithium Electrodes in Alkyl Carbonate Solutions Aurbach, Doron Journal of The Electrochemical Society, Vol. 141, Issue 1 https://doi.org/10.1149/1.2054718	journal	January 1994
Electronic structure calculations with the Tran-Blaha modified Becke-Johnson density functional Singh, David J. Physical Review B, Vol. 82, Issue 20 https://doi.org/10.1103/PhysRevB.82.205102	journal	November 2010
Ageing mechanisms in lithium-ion batteries Vetter, J.; Novák, P.; Wagner, M. R. Journal of Power Sources, Vol. 147, Issue 1-2 https://doi.org/10.1016/j.jpowsour.2005.01.006	journal	September 2005
Thermal runaway caused fire and explosion of lithium ion battery Wang, Qingsong; Ping, Ping; Zhao, Xuejuan Journal of Power Sources, Vol. 208 https://doi.org/10.1016/j.jpowsour.2012.02.038	journal	June 2012
X-ray Photoelectron Spectroscopy Study of Surface Films Formed on Li Electrodes Freshly Prepared in Alkyl Carbonate Solutions Schechter, Alex; Aurbach, Doron; Cohen, Hagay Langmuir, Vol. 15, Issue 9 https://doi.org/10.1021/la981048h	journal	April 1999
Optimizing Areal Capacities through Understanding the Limitations of Lithium-Ion Electrodes Gallagher, Kevin G.; Trask, Stephen E.; Bauer, Christoph Journal of The Electrochemical Society, Vol. 163, Issue 2 https://doi.org/10.1149/2.0321602jes	journal	November 2015
Electrocatalytic transformation of HF impurity to H2 and LiF in lithium-ion batteries Strmcnik, Dusan; Castelli, Ivano E.; Connell, Justin G. Nature Catalysis, Vol. 1, Issue 4 https://doi.org/10.1038/s41929-018-0047-z	journal	April 2018
Commentary: The Materials Project: A materials genome approach to accelerating materials innovation Jain, Anubhav; Ong, Shyue Ping; Hautier, Geoffroy APL Materials, Vol. 1, Issue 1 https://doi.org/10.1063/1.4812323	journal	July 2013
Minimizing damage during FIB sample preparation of soft materials: FIB SAMPLE PREPARATION OF SOFT MATERIALS Bassim, N. D.; De Gregorio, B. T.; Kilcoyne, A. L. D. Journal of Microscopy, Vol. 245, Issue 3 https://doi.org/10.1111/j.1365-2818.2011.03570.x	journal	November 2011
Untersuchungen über den Salzcharakter des Lithiumhydrids Moers, Kurt Zeitschrift für anorganische und allgemeine Chemie, Vol. 113, Issue 1 https://doi.org/10.1002/zaac.19201130116	journal	October 1920
Quantitative and time-resolved detection of lithium plating on graphite anodes in lithium ion batteries Wandt, Johannes; Jakes, Peter; Granwehr, Josef Materials Today, Vol. 21, Issue 3 https://doi.org/10.1016/j.mattod.2017.11.001	journal	April 2018
Thermodynamics of open two-phase systems with coherent interfaces: Application to metal–hydrogen systems Schwarz, R. B.; Khachaturyan, A. G. Acta Materialia, Vol. 54, Issue 2 https://doi.org/10.1016/j.actamat.2005.08.044	journal	January 2006
Bandgap measurement of thin dielectric films using monochromated STEM-EELS Park, Jucheol; Heo, Sung; Chung, Jae-Gwan Ultramicroscopy, Vol. 109, Issue 9 https://doi.org/10.1016/j.ultramic.2009.04.005	journal	August 2009
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
Not so smart? “Smart” drugs increase the level but decrease the quality of cognitive effort Bowman, Elizabeth; Coghill, David; Murawski, Carsten Science Advances, Vol. 9, Issue 24 https://doi.org/10.1126/sciadv.add4165	journal	June 2023
The primary gas phase hydration shell of hydroxide Cao, Wenjin; Wen, Hui; Xantheas, Sotiris S. Science Advances, Vol. 9, Issue 12 https://doi.org/10.1126/sciadv.adf4309	journal	March 2023
Neuronal responses to omitted tones in the auditory brain: A neuronal correlate for predictive coding Lao-Rodríguez, Ana B.; Przewrocki, Karol; Pérez-González, David Science Advances, Vol. 9, Issue 24 https://doi.org/10.1126/sciadv.abq8657	journal	June 2023
Identifying the Cause of Rupture of Li-Ion Batteries during Thermal Runaway Finegan, Donal P.; Darcy, Eric; Keyser, Matthew Advanced Science, Vol. 5, Issue 1 https://doi.org/10.1002/advs.201700369	journal	October 2017
Correlating Structure and Function of Battery Interphases at Atomic Resolution Using Cryoelectron Microscopy Li, Yuzhang; Huang, William; Li, Yanbin Joule, Vol. 2, Issue 10 https://doi.org/10.1016/j.joule.2018.08.004	journal	October 2018
Cryo-EM Structures of Atomic Surfaces and Host-Guest Chemistry in Metal-Organic Frameworks Li, Yuzhang; Wang, Kecheng; Zhou, Weijiang Matter, Vol. 1, Issue 2 https://doi.org/10.1016/j.matt.2019.06.001	journal	August 2019
On the possibility of LiH formation on Li surfaces in wet electrolyte solutions Aurbach, Doron; Weissman, Idit Electrochemistry Communications, Vol. 1, Issue 8 https://doi.org/10.1016/S1388-2481(99)00064-8	journal	August 1999
Identification of LiH and nanocrystalline LiF in the solid–electrolyte interphase of lithium metal anodes Shadike, Zulipiya; Lee, Hongkyung; Borodin, Oleg Nature Nanotechnology, Vol. 16, Issue 5 https://doi.org/10.1038/s41565-020-00845-5	journal	January 2021
Resolving Nanoscopic and Mesoscopic Heterogeneity of Fluorinated Species in Battery Solid-Electrolyte Interphases by Cryogenic Electron Microscopy Huang, William; Wang, Hansen; Boyle, David T. ACS Energy Letters, Vol. 5, Issue 4 https://doi.org/10.1021/acsenergylett.0c00194	journal	March 2020
Ocean currents magnify upwelling and deliver nutritional subsidies to reef-building corals during El Niño heatwaves Fox, Michael D.; Guillaume-Castel, Robin; Edwards, Clinton B. Science Advances, Vol. 9, Issue 24 https://doi.org/10.1126/sciadv.add5032	journal	June 2023
Li plating as unwanted side reaction in commercial Li-ion cells – A review Waldmann, Thomas; Hogg, Björn-Ingo; Wohlfahrt-Mehrens, Margret Journal of Power Sources, Vol. 384 https://doi.org/10.1016/j.jpowsour.2018.02.063	journal	April 2018
Corrosion of lithium metal anodes during calendar ageing and its microscopic origins Boyle, David T.; Huang, William; Wang, Hansen Nature Energy, Vol. 6, Issue 5 https://doi.org/10.1038/s41560-021-00787-9	journal	March 2021
Operando NMR of NMC811/Graphite Lithium-Ion Batteries: Structure, Dynamics, and Lithium Metal Deposition Märker, Katharina; Xu, Chao; Grey, Clare P. Journal of the American Chemical Society, Vol. 142, Issue 41 https://doi.org/10.1021/jacs.0c06727	journal	September 2020
Mathematical Modeling of the Lithium Deposition Overcharge Reaction in Lithium-Ion Batteries Using Carbon-Based Negative Electrodes Arora, Pankaj Journal of The Electrochemical Society, Vol. 146, Issue 10 https://doi.org/10.1149/1.1392512	journal	January 1999
Cryogenic Electron Microscopy for Energy Materials Zhang, Zewen; Cui, Yi; Vila, Rafael Accounts of Chemical Research, Vol. 54, Issue 18 https://doi.org/10.1021/acs.accounts.1c00183	journal	July 2021
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
The Formation/Decomposition Equilibrium of LiH and its Contribution on Anode Failure in Practical Lithium Metal Batteries Xu, Gaojie; Li, Jiedong; Wang, Chao Angewandte Chemie, Vol. 133, Issue 14 https://doi.org/10.1002/ange.202013812	journal	February 2021
Quantifying inactive lithium in lithium metal batteries Fang, Chengcheng; Li, Jinxing; Zhang, Minghao Nature, Vol. 572, Issue 7770 https://doi.org/10.1038/s41586-019-1481-z	journal	August 2019
Quantitatively analyzing the failure processes of rechargeable Li metal batteries Xiang, Yuxuan; Tao, Mingming; Zhong, Guiming Science Advances, Vol. 7, Issue 46 https://doi.org/10.1126/sciadv.abj3423	journal	November 2021
Nickel Impurities in the Solid-Electrolyte Interphase of Lithium-Metal Anodes Revealed by Cryogenic Electron Microscopy Vilá, Rafael A.; Huang, William; Cui, Yi Cell Reports Physical Science, Vol. 1, Issue 9 https://doi.org/10.1016/j.xcrp.2020.100188	journal	September 2020
TEM Sample Preparation and FIB-Induced Damage Mayer, Joachim; Giannuzzi, Lucille A.; Kamino, Takeo MRS Bulletin, Vol. 32, Issue 5 https://doi.org/10.1557/mrs2007.63	journal	May 2007
The orientation relationship between lath martensite and austenite in low carbon, low alloy steels Kelly, P. M.; Jostsons, A.; Blake, R. G. Acta Metallurgica et Materialia, Vol. 38, Issue 6 https://doi.org/10.1016/0956-7151(90)90180-O	journal	June 1990
Label-free structural and functional volumetric imaging by dual-modality optical-Raman projection tomography Wang, Nan; Wang, Xinyu; Yan, Tianyu Science Advances, Vol. 9, Issue 12 https://doi.org/10.1126/sciadv.adf3504	journal	March 2023

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Title: LiH formation and its impact on Li batteries revealed by cryogenic electron microscopy

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