Identification of LiH and nanocrystalline LiF in the solid–electrolyte interphase of lithium metal anodes

Shadike, Zulipiya; Lee, Hongkyung; Borodin, Oleg; Cao, Xia; Fan, Xiulin; Wang, Xuelong; Lin, Ruoqian; Bak, Seong-Min; Ghose, Sanjit; Xu, Kang; Wang, Chunsheng; Liu, Jun; Xiao, Jie; Yang, Xiao-Qing; Hu, Enyuan

doi:10.1038/s41565-020-00845-5

Identification of LiH and nanocrystalline LiF in the solid–electrolyte interphase of lithium metal anodes

Journal Article · Thu Jan 28 04:00:00 EST 2021 · Nature Nanotechnology

DOI:https://doi.org/10.1038/s41565-020-00845-5· OSTI ID:1764002

^[1]; Lee, Hongkyung ^[2]; ^[3]; Cao, Xia ^[4]; Fan, Xiulin ^[5]; Wang, Xuelong ^[1]; Lin, Ruoqian ^[1]; ^[1]; Ghose, Sanjit ^[6]; ^[3]; ^[5]; ^[7]; ^[7]; ^[1]; ^[1]

Brookhaven National Lab. (BNL), Upton, NY (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Daegu Gyeongbuk Inst. of Science and Technology (DGIST), Daegu (Korea, Republic of)
Army Research Lab., Adelphi, MD (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Univ. of Maryland, College Park, MD (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Univ. of Washington, Seattle, WA (United States)

A comprehensive understanding of the solid–electrolyte interphase (SEI) composition is crucial to developing high-energy batteries based on lithium metal anodes. A particularly contentious issue concerns the presence of LiH in the SEI. In this work, we report on the use of synchrotron-based X-ray diffraction and pair distribution function analysis to identify and differentiate two elusive components, LiH and LiF, in the SEI of lithium metal anodes. LiH is identified as a component of the SEI in high abundance, and the possibility of its misidentification as LiF in the literature is discussed. LiF in the SEI is found to have different structural features from LiF in the bulk phase, including a larger lattice parameter and a smaller grain size (<3 nm). These characteristics favour Li⁺ transport and explain why an ionic insulator, like LiF, has been found to be a favoured component for the SEI. Finally, pair distribution function analysis reveals key amorphous components in the SEI.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

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

Grant/Contract Number:: SC0012704; AC02-05CH11231; AC05-76RL01830

OSTI ID:: 1764002

Alternate ID(s):: OSTI ID: 1764597
OSTI ID: 1785714

Report Number(s):: BNL--220958-2021-JAAM

Journal Information:: Nature Nanotechnology, Journal Name: Nature Nanotechnology Journal Issue: 5 Vol. 16; ISSN 1748-3387

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (40)

A Review of Solid Electrolyte Interphases on Lithium Metal Anode Cheng, Xin-Bing; Zhang, Rui; Zhao, Chen-Zi Advanced Science, Vol. 3, Issue 3 https://doi.org/10.1002/advs.201500213	journal	November 2015
In Situ Synchrotron X-Ray Techniques for Real-Time Probing of Colloidal Nanoparticle Synthesis Sun, Yugang; Ren, Yang Particle & Particle Systems Characterization, Vol. 30, Issue 5 https://doi.org/10.1002/ppsc.201300033	journal	March 2013
Direct Observation of the Growth of Lithium Dendrites on Graphite Anodes by Operando EC-AFM Shen, Cai; Hu, Guohong; Cheong, Ling-Zhi Small Methods, Vol. 2, Issue 2 https://doi.org/10.1002/smtd.201700298	journal	December 2017
Zur Mischkristallbildung zwischen Lithiumfluorid und Lithiumhydrid Hahn, H.; Strick, G. Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 372, Issue 2 https://doi.org/10.1002/zaac.19703720216	journal	February 1970
Lithium hydride single crystal growth by bridgman-stockbarger method using ultrasound Tyutyunnik, O. I.; Tyutyunnik, V. I.; Shulgin, B. V. Journal of Crystal Growth, Vol. 68, Issue 3 https://doi.org/10.1016/0022-0248(84)90113-1	journal	October 1984
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Thermal expansion of alkali halides above 300°K Srivastava, K. K.; Merchant, H. D. Journal of Physics and Chemistry of Solids, Vol. 34, Issue 12 https://doi.org/10.1016/S0022-3697(73)80055-1	journal	December 1973
Lattice expansion of nanoscale compound particles Fukuhara, Mikio Physics Letters A, Vol. 313, Issue 5-6 https://doi.org/10.1016/S0375-9601(03)00793-X	journal	July 2003
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
Advancing Lithium Metal Batteries Liu, Bin; Zhang, Ji-Guang; Xu, Wu Joule, Vol. 2, Issue 5 https://doi.org/10.1016/j.joule.2018.03.008	journal	May 2018
Cryogenic Electron Microscopy for Characterizing and Diagnosing Batteries Wang, Xuefeng; Li, Yejing; Meng, Ying Shirley Joule, Vol. 2, Issue 11 https://doi.org/10.1016/j.joule.2018.10.005	journal	November 2018
Uncharted Waters: Super-Concentrated Electrolytes Borodin, Oleg; Self, Julian; Persson, Kristin A. Joule, Vol. 4, Issue 1 https://doi.org/10.1016/j.joule.2019.12.007	journal	January 2020
Physico-chemical properties of solutions of lithium bis(fluorosulfonyl)imide (LiFSI) in dimethyl carbonate, ethylene carbonate, and propylene carbonate Neuhaus, Johannes; von Harbou, Erik; Hasse, Hans Journal of Power Sources, Vol. 394 https://doi.org/10.1016/j.jpowsour.2018.05.038	journal	August 2018
In Situ Chemical Imaging of Solid-Electrolyte Interphase Layer Evolution in Li–S Batteries Nandasiri, Manjula I.; Camacho-Forero, Luis E.; Schwarz, Ashleigh M. Chemistry of Materials, Vol. 29, Issue 11 https://doi.org/10.1021/acs.chemmater.7b00374	journal	May 2017
New Insights on the Structure of Electrochemically Deposited Lithium Metal and Its Solid Electrolyte Interphases via Cryogenic TEM Wang, Xuefeng; Zhang, Minghao; Alvarado, Judith Nano Letters, Vol. 17, Issue 12 https://doi.org/10.1021/acs.nanolett.7b03606	journal	November 2017
Multinuclear NMR Study of the Solid Electrolyte Interface Formed in Lithium Metal Batteries Wan, Chuan; Xu, Suochang; Hu, Mary Y. ACS Applied Materials & Interfaces, Vol. 9, Issue 17 https://doi.org/10.1021/acsami.6b15383	journal	April 2017
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
A Mechanism for Non-stoichiometry in the Lithium Amide/Lithium Imide Hydrogen Storage Reaction David, William I. F.; Jones, Martin O.; Gregory, Duncan H. Journal of the American Chemical Society, Vol. 129, Issue 6 https://doi.org/10.1021/ja066016s	journal	February 2007
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
Operando X-ray photoelectron spectroscopy of solid electrolyte interphase formation and evolution in Li2S-P2S5 solid-state electrolytes Wood, Kevin N.; Steirer, K. Xerxes; Hafner, Simon E. Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-04762-z	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
Pathways for practical high-energy long-cycling lithium metal batteries Liu, Jun; Bao, Zhenan; Cui, Yi Nature Energy, Vol. 4, Issue 3 https://doi.org/10.1038/s41560-019-0338-x	journal	February 2019
High-energy lithium metal pouch cells with limited anode swelling and long stable cycles Niu, Chaojiang; Lee, Hongkyung; Chen, Shuru Nature Energy, Vol. 4, Issue 7 https://doi.org/10.1038/s41560-019-0390-6	journal	May 2019
In situ quantification of interphasial chemistry in Li-ion battery Liu, Tongchao; Lin, Lingpiao; Bi, Xuanxuan Nature Nanotechnology, Vol. 14, Issue 1 https://doi.org/10.1038/s41565-018-0284-y	journal	November 2018
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
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
Synthesis and characterization of the crystal structure, the magnetic and the electrochemical properties of the new fluorophosphate LiNaFe[PO4]F Ben Yahia, Hamdi; Shikano, Masahiro; Sakaebe, Hikari Dalton Transactions, Vol. 41, Issue 38 https://doi.org/10.1039/c2dt30739a	journal	January 2012
Size effect on the lattice parameters of nanocrystalline anatase Ahmad, Md. Imteyaz; Bhattacharya, S. S. Applied Physics Letters, Vol. 95, Issue 19 https://doi.org/10.1063/1.3261754	journal	November 2009
A b i n i t i o calculations on the lithium fluoride–ethylene complex Szczȩśniak, Mal/gorzata M.; Ratajczak, Henryk The Journal of Chemical Physics, Vol. 67, Issue 11 https://doi.org/10.1063/1.434654	journal	December 1977
Compression of lithium fluoride to 92 GPa Dong, Haini; Dorfman, Susannah M.; Holl, Christopher M. High Pressure Research, Vol. 34, Issue 1 https://doi.org/10.1080/08957959.2013.878932	journal	January 2014
Two-dimensional detector software: From real detector to idealised image or two-theta scan Hammersley, A. P.; Svensson, S. O.; Hanfland, M. High Pressure Research, Vol. 14, Issue 4-6, p. 235-248 https://doi.org/10.1080/08957959608201408	journal	January 1996
Difference in conductivity between LiD and LiH crystals Varotsos, P. A.; Mourikis, S. Physical Review B, Vol. 10, Issue 12 https://doi.org/10.1103/PhysRevB.10.5220	journal	December 1974
Lattice-Constant Dependence on Isotopic Composition in the Li 7 (H, D) System Zimmerman, W. Bruce Physical Review B, Vol. 5, Issue 12 https://doi.org/10.1103/PhysRevB.5.4704	journal	June 1972
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Origin of Anomalous Lattice Expansion in Oxide Nanoparticles Tsunekawa, S.; Ishikawa, K.; Li, Z. -Q. Physical Review Letters, Vol. 85, Issue 16 https://doi.org/10.1103/PhysRevLett.85.3440	journal	October 2000
PDFgetX2: a GUI-driven program to obtain the pair distribution function from X-ray powder diffraction data Qiu, Xiangyun; Thompson, Jeroen W.; Billinge, Simon J. L. Journal of Applied Crystallography, Vol. 37, Issue 4, p. 678-678 https://doi.org/10.1107/S0021889804011744	journal	July 2004
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
How lithium dendrites form in liquid batteries Xiao, Jie Science, Vol. 366, Issue 6464 https://doi.org/10.1126/science.aay8672	journal	October 2019
Characterization of Lithium Electrode in Lithium Imides/Ethylene Carbonate and Cyclic Ether Electrolytes Ota, Hitoshi; Sakata, Yuuichi; Wang, Xianming Journal of The Electrochemical Society, Vol. 151, Issue 3 https://doi.org/10.1149/1.1644137	journal	January 2004

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