Mitigating Interfacial Mismatch between Lithium Metal and Garnet-Type Solid Electrolyte by Depositing Metal Nitride Lithiophilic Interlayer

Baniya, Abiral; Gurung, Ashim; Pokharel, Jyotshna; Chen, Ke; Pathak, Rajesh; Lamsal, Buddhi Sagar; Ghimire, Nabin; Bobba, Raja Sekhar; Rahman, Sheikh Ifatur; Mabrouk, Sally; Smirnova, Alevtina L.; Xu, Kang; Qiao, Quinn

doi:10.1021/acsaem.1c03157

Title: Mitigating Interfacial Mismatch between Lithium Metal and Garnet-Type Solid Electrolyte by Depositing Metal Nitride Lithiophilic Interlayer

Journal Article · 07 January 2022 · ACS Applied Energy Materials

DOI: https://doi.org/10.1021/acsaem.1c03157 · OSTI ID:2469980

^[1]; Gurung, Ashim ^[2]; Pokharel, Jyotshna ^[2];

^[2]; Pathak, Rajesh ^[3]; Lamsal, Buddhi Sagar ^[2];

^[2]; Bobba, Raja Sekhar ^[1];

^[2]; Mabrouk, Sally ^[1];

^[4]; Xu, Kang ^[5];

^[1]

Syracuse Univ., NY (United States)
South Dakota State Univ., Brookings, SD (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)
South Dakota School of Mines and Technology, Rapid City, SD (United States)
Army Research Lab., Adelphi, MD (United States)

Solid-state lithium batteries are generally considered as the next-generation battery technology that benefits from inherent nonflammable solid electrolytes and safe harnessing of high-capacity lithium metal. Among various solid-electrolyte candidates, cubic garnet-type Li₇La₃Zr₂O₁₂ ceramics hold superiority due to their high ionic conductivity (10^–3 to 10^–4 S cm^-1) and good chemical stability against lithium metal. However, practical deployment of solid-state batteries based on such garnet-type materials has been constrained by poor interfacing between lithium and garnet that displays high impedance and uneven current distribution. Herein, we propose a facile and effective strategy to significantly reduce this interfacial mismatch by modifying the surface of such garnet-type solid electrolyte with a thin layer of silicon nitride (Si₃N₄). This interfacial layer ensures an intimate contact with lithium due to its lithiophilic nature and formation of an intermediate lithium–metal alloy. The interfacial resistance experiences an exponential drop from 1197 to 84.5 Ω cm². Lithium symmetrical cells with Si₃N₄-modified garnet exhibited low overpotential and long-term stable plating/stripping cycles at room temperature compared to bare garnet. Furthermore, a hybrid solid-state battery with Si₃N₄-modified garnet sandwiched between lithium metal anode and LiFePO₄ cathode was demonstrated to operate with high cycling efficiency, excellent rate capability, and good electrochemical stability. This work represents a significant advancement toward use of garnet solid electrolytes in lithium metal batteries for the next-generation energy storage devices.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2469980

Journal Information:: ACS Applied Energy Materials, Journal Name: ACS Applied Energy Materials Journal Issue: 1 Vol. 5; ISSN 2574-0962

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (61)

Dendrite-Free Lithium Deposition Induced by Uniformly Distributed Lithium Ions for Efficient Lithium Metal Batteries Cheng, Xin-Bing; Hou, Ting-Zheng; Zhang, Rui Advanced Materials, Vol. 28, Issue 15 https://doi.org/10.1002/adma.201506124	journal	February 2016
An Artificial Solid Electrolyte Interphase with High Li-Ion Conductivity, Mechanical Strength, and Flexibility for Stable Lithium Metal Anodes Liu, Yayuan; Lin, Dingchang; Yuen, Pak Yan Advanced Materials, Vol. 29, Issue 10 https://doi.org/10.1002/adma.201605531	journal	December 2016
Reducing Interfacial Resistance between Garnet-Structured Solid-State Electrolyte and Li-Metal Anode by a Germanium Layer Luo, Wei; Gong, Yunhui; Zhu, Yizhou Advanced Materials, Vol. 29, Issue 22 https://doi.org/10.1002/adma.201606042	journal	April 2017
Strategies Based on Nitride Materials Chemistry to Stabilize Li Metal Anode Zhu, Yizhou; He, Xingfeng; Mo, Yifei Advanced Science, Vol. 4, Issue 8 https://doi.org/10.1002/advs.201600517	journal	March 2017
Two-Dimensional Materials for Beyond-Lithium-Ion Batteries Peng, Lele; Zhu, Yue; Chen, Dahong Advanced Energy Materials, Vol. 6, Issue 11 https://doi.org/10.1002/aenm.201600025	journal	March 2016
Improved Rechargeability of Lithium Metal Anode via Controlling Lithium-Ion Flux Xiang, Jingwei; Yuan, Lixia; Shen, Yue Advanced Energy Materials, Vol. 8, Issue 36 https://doi.org/10.1002/aenm.201802352	journal	October 2018
Fast Lithium Ion Conduction in Garnet-Type Li₇La₃Zr₂O₁₂ Murugan, Ramaswamy; Thangadurai, Venkataraman; Weppner, Werner Angewandte Chemie International Edition, Vol. 46, Issue 41, p. 7778-7781 https://doi.org/10.1002/anie.200701144	journal	October 2007
Li6PS5X: A Class of Crystalline Li-Rich Solids With an Unusually High Li+ Mobility Deiseroth, Hans-Jörg; Kong, Shiao-Tong; Eckert, Hellmut Angewandte Chemie International Edition, Vol. 47, Issue 4 https://doi.org/10.1002/anie.200703900	journal	January 2008
Nitridosilicates and Oxonitridosilicates: From Ceramic Materials to Structural and Functional Diversity Zeuner, Martin; Pagano, Sandro; Schnick, Wolfgang Angewandte Chemie International Edition, Vol. 50, Issue 34 https://doi.org/10.1002/anie.201005755	journal	July 2011
Hybrid Polymer/Garnet Electrolyte with a Small Interfacial Resistance for Lithium-Ion Batteries Li, Yutao; Xu, Biyi; Xu, Henghui Angewandte Chemie International Edition, Vol. 56, Issue 3 https://doi.org/10.1002/anie.201608924	journal	December 2016
Transient Behavior of the Metal Interface in Lithium Metal-Garnet Batteries Fu, Kun Kelvin; Gong, Yunhui; Fu, Zhezhen Angewandte Chemie International Edition, Vol. 56, Issue 47 https://doi.org/10.1002/anie.201708637	journal	October 2017
Optical band gap of Li₈SiN₄ with disordered structure as a cathode material of lithium secondary batteries Yamashita, T.; Kuwano, S.; Kuriyama, K. physica status solidi c, Vol. 12, Issue 6 https://doi.org/10.1002/pssc.201400214	journal	March 2015
Controlling Nucleation in Lithium Metal Anodes Guan, Xuze; Wang, Aoxuan; Liu, Shan Small, Vol. 14, Issue 37 https://doi.org/10.1002/smll.201801423	journal	July 2018
Microwave Synthesis of Ternary Nitride Materials Houmes, Joel D.; zur Loye, Hans-Conrad Journal of Solid State Chemistry, Vol. 130, Issue 2 https://doi.org/10.1006/jssc.1997.7303	journal	May 1997
Crystal structure and ionic conductivity of Li14Zn(GeO4)4 and other new Li+ superionic conductors Hong, H. Y-P. Materials Research Bulletin, Vol. 13, Issue 2 https://doi.org/10.1016/0025-5408(78)90075-2	journal	February 1978
Preparation of lithium silicon nitrides and their lithium ion conductivity Yamane, H. Solid State Ionics, Vol. 25, Issue 2-3 https://doi.org/10.1016/0167-2738(87)90119-6	journal	November 1987
Electrical properties of amorphous lithium electrolyte thin films Bates, J. B.; Dudney, N. J.; Gruzalski, G. R. Solid State Ionics, Vol. 53-56, Issue Part 1, p. 647-654 https://doi.org/10.1016/0167-2738(92)90442-R	journal	July 1992
Thin-film rechargeable lithium batteries Bates, J. B.; Dudney, N. J.; Lubben, D. C. Journal of Power Sources, Vol. 54, Issue 1, p. 58-62 https://doi.org/10.1016/0378-7753(94)02040-A	journal	March 1995
Synthesis of a new lithium ionic conductor, thio-LISICON–lithium germanium sulfide system Kanno, R. Solid State Ionics, Vol. 130, Issue 1-2 https://doi.org/10.1016/S0167-2738(00)00277-0	journal	May 2000
A new ternary composite lithium silicon nitride as anode material for lithium ion batteries Wen, Zhongsheng; Wang, Ke; Chen, Libao Electrochemistry Communications, Vol. 8, Issue 8 https://doi.org/10.1016/j.elecom.2006.06.022	journal	August 2006
Electrochemical stability of lithium halide electrolyte with antiperovskite crystal structure Dondelinger, Matthew; Swanson, Joel; Nasymov, Golibsho Electrochimica Acta, Vol. 306 https://doi.org/10.1016/j.electacta.2019.03.074	journal	May 2019
PMMA-assisted Li deposition towards 3D continuous dendrite-free lithium anode Guo, Yanpeng; Ouyang, Yan; Li, Dian Energy Storage Materials, Vol. 16 https://doi.org/10.1016/j.ensm.2018.05.012	journal	January 2019
Flower-shaped lithium nitride as a protective layer via facile plasma activation for stable lithium metal anodes Chen, Ke; Pathak, Rajesh; Gurung, Ashim Energy Storage Materials, Vol. 18 https://doi.org/10.1016/j.ensm.2019.02.006	journal	March 2019
Effect of substitution (Ta, Al, Ga) on the conductivity of Li₇La₃Zr₂O₁₂ Allen, J. L.; Wolfenstine, J.; Rangasamy, E. Journal of Power Sources, Vol. 206, p. 315-319 https://doi.org/10.1016/j.jpowsour.2012.01.131	journal	May 2012
Challenges and perspectives of garnet solid electrolytes for all solid-state lithium batteries Liu, Qi; Geng, Zhen; Han, Cuiping Journal of Power Sources, Vol. 389 https://doi.org/10.1016/j.jpowsour.2018.04.019	journal	June 2018
Silicon nitride as anode material for Li-ion batteries: Understanding the SiNx conversion reaction Ulvestad, Asbjørn; Mæhlen, Jan Petter; Kirkengen, Martin Journal of Power Sources, Vol. 399 https://doi.org/10.1016/j.jpowsour.2018.07.109	journal	September 2018
Crystal, electronic structures and photoluminescence properties of rare-earth doped LiSi2N3 Li, Y. Q.; Hirosaki, N.; Xie, R. J. Journal of Solid State Chemistry, Vol. 182, Issue 2 https://doi.org/10.1016/j.jssc.2008.10.031	journal	February 2009
Synthesis of garnet-type Li7−xLa3Zr2O12−1/2x and its stability in aqueous solutions Shimonishi, Yuta; Toda, Akiharu; Zhang, Tao Solid State Ionics, Vol. 183, Issue 1 https://doi.org/10.1016/j.ssi.2010.12.010	journal	February 2011
The role of Al and Li concentration on the formation of cubic garnet solid electrolyte of nominal composition Li₇La₃Zr₂O₁₂ Rangasamy, Ezhiyl; Wolfenstine, Jeff; Sakamoto, Jeffrey Solid State Ionics, Vol. 206, p. 28-32 https://doi.org/10.1016/j.ssi.2011.10.022	journal	January 2012
Interphase formation on lithium solid electrolytes—An in situ approach to study interfacial reactions by photoelectron spectroscopy Wenzel, Sebastian; Leichtweiss, Thomas; Krüger, Dominik Solid State Ionics, Vol. 278 https://doi.org/10.1016/j.ssi.2015.06.001	journal	October 2015
Surface Chemistry Mechanism of Ultra-Low Interfacial Resistance in the Solid-State Electrolyte Li ₇ La ₃ Zr ₂ O ₁₂ Sharafi, Asma; Kazyak, Eric; Davis, Andrew L. Chemistry of Materials, Vol. 29, Issue 18 https://doi.org/10.1021/acs.chemmater.7b03002	journal	September 2017
Lithium Diffusion Pathway in Li _1.3 Al _0.3 Ti _1.7 (PO ₄ ) ₃ (LATP) Superionic Conductor Monchak, Mykhailo; Hupfer, Thomas; Senyshyn, Anatoliy Inorganic Chemistry, Vol. 55, Issue 6 https://doi.org/10.1021/acs.inorgchem.5b02821	journal	March 2016
Conformal, Nanoscale ZnO Surface Modification of Garnet-Based Solid-State Electrolyte for Lithium Metal Anodes Wang, Chengwei; Gong, Yunhui; Liu, Boyang Nano Letters, Vol. 17, Issue 1 https://doi.org/10.1021/acs.nanolett.6b04695	journal	December 2016
Li ₃ N-Modified Garnet Electrolyte for All-Solid-State Lithium Metal Batteries Operated at 40 °C Xu, Henghui; Li, Yutao; Zhou, Aijun Nano Letters, Vol. 18, Issue 11 https://doi.org/10.1021/acs.nanolett.8b03902	journal	October 2018
Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations Zhu, Yizhou; He, Xingfeng; Mo, Yifei ACS Applied Materials & Interfaces, Vol. 7, Issue 42 https://doi.org/10.1021/acsami.5b07517	journal	October 2015
Li ₇ La ₃ Zr ₂ O ₁₂ Interface Modification for Li Dendrite Prevention Tsai, Chih-Long; Roddatis, Vladimir; Chandran, C. Vinod ACS Applied Materials & Interfaces, Vol. 8, Issue 16 https://doi.org/10.1021/acsami.6b00831	journal	April 2016
Study of Lithium Silicide Nanoparticles as Anode Materials for Advanced Lithium Ion Batteries Li, Xuemin; Kersey-Bronec, Faith E.; Ke, John ACS Applied Materials & Interfaces, Vol. 9, Issue 19 https://doi.org/10.1021/acsami.6b16773	journal	May 2017
Drawing a Soft Interface: An Effective Interfacial Modification Strategy for Garnet-Type Solid-State Li Batteries Shao, Yuanjun; Wang, Hongchun; Gong, Zhengliang ACS Energy Letters, Vol. 3, Issue 6 https://doi.org/10.1021/acsenergylett.8b00453	journal	May 2018
Li ₁₀ SnP ₂ S ₁₂ : An Affordable Lithium Superionic Conductor Bron, Philipp; Johansson, Sebastian; Zick, Klaus Journal of the American Chemical Society, Vol. 135, Issue 42 https://doi.org/10.1021/ja407393y	journal	October 2013
Transition from Superlithiophobicity to Superlithiophilicity of Garnet Solid-State Electrolyte Luo, Wei; Gong, Yunhui; Zhu, Yizhou Journal of the American Chemical Society, Vol. 138, Issue 37 https://doi.org/10.1021/jacs.6b06777	journal	September 2016
Synergistic Coupling between Li _6.75 La ₃ Zr _1.75 Ta _0.25 O ₁₂ and Poly(vinylidene fluoride) Induces High Ionic Conductivity, Mechanical Strength, and Thermal Stability of Solid Composite Electrolytes Zhang, Xue; Liu, Ting; Zhang, Shuofeng Journal of the American Chemical Society, Vol. 139, Issue 39 https://doi.org/10.1021/jacs.7b06364	journal	September 2017
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
A solid future for battery development Janek, Jürgen; Zeier, Wolfgang G. Nature Energy, Vol. 1, Issue 9 https://doi.org/10.1038/nenergy.2016.141	journal	September 2016
Batteries: Getting solid Hu, Yong-Sheng Nature Energy, Vol. 1, Issue 4 https://doi.org/10.1038/nenergy.2016.42	journal	April 2016
A lithium superionic conductor Kamaya, Noriaki; Homma, Kenji; Yamakawa, Yuichiro Nature Materials, Vol. 10, Issue 9, p. 682-686 https://doi.org/10.1038/nmat3066	journal	July 2011
Negating interfacial impedance in garnet-based solid-state Li metal batteries Han, Xiaogang; Gong, Yunhui; Fu, Kun (Kelvin) Nature Materials, Vol. 16, Issue 5 https://doi.org/10.1038/nmat4821	journal	December 2016
Lithium metal anodes for rechargeable batteries Xu, Wu; Wang, Jiulin; Ding, Fei Energy Environ. Sci., Vol. 7, Issue 2 https://doi.org/10.1039/C3EE40795K	journal	January 2014
The origin of high electrolyte–electrode interfacial resistances in lithium cells containing garnet type solid electrolytes Cheng, Lei; Crumlin, Ethan J.; Chen, Wei Phys. Chem. Chem. Phys., Vol. 16, Issue 34 https://doi.org/10.1039/C4CP02921F	journal	January 2014
First principles study on electrochemical and chemical stability of solid electrolyte–electrode interfaces in all-solid-state Li-ion batteries Zhu, Yizhou; He, Xingfeng; Mo, Yifei Journal of Materials Chemistry A, Vol. 4, Issue 9 https://doi.org/10.1039/C5TA08574H	journal	January 2016
Surface and interface engineering for organic–inorganic composite membranes Yang, Hao-Cheng; Hou, Jingwei; Chen, Vicki Journal of Materials Chemistry A, Vol. 4, Issue 25 https://doi.org/10.1039/C6TA02844F	journal	January 2016
The effect of sintering process on lithium ionic conductivity of Li _6.4 Al _0.2 La ₃ Zr ₂ O ₁₂ garnet produced by solid-state synthesis Xue, Wenjuan; Yang, Yaping; Yang, Qiaoling RSC Advances, Vol. 8, Issue 24 https://doi.org/10.1039/C8RA01329B	journal	January 2018
A review on strategies addressing interface incompatibilities in inorganic all-solid-state lithium batteries Gurung, Ashim; Pokharel, Jyotshna; Baniya, Abiral Sustainable Energy & Fuels, Vol. 3, Issue 12 https://doi.org/10.1039/C9SE00549H	journal	January 2019
Atomic-scale origin of the large grain-boundary resistance in perovskite Li-ion-conducting solid electrolytes Ma, Cheng; Chen, Kai; Liang, Chengdu Energy & Environmental Science, Vol. 7, Issue 5 https://doi.org/10.1039/c4ee00382a	journal	January 2014
Mastering the interface for advanced all-solid-state lithium rechargeable batteries Li, Yutao; Zhou, Weidong; Chen, Xi Proceedings of the National Academy of Sciences, Vol. 113, Issue 47 https://doi.org/10.1073/pnas.1615912113	journal	November 2016
Toward garnet electrolyte–based Li metal batteries: An ultrathin, highly effective, artificial solid-state electrolyte/metallic Li interface Fu, Kun (Kelvin); Gong, Yunhui; Liu, Boyang Science Advances, Vol. 3, Issue 4 https://doi.org/10.1126/sciadv.1601659	journal	April 2017
Electrical Energy Storage for the Grid: A Battery of Choices Dunn, B.; Kamath, H.; Tarascon, J. -M. Science, Vol. 334, Issue 6058 https://doi.org/10.1126/science.1212741	journal	November 2011
Ionic Conductivity of Solid Electrolytes Based on Lithium Titanium Phosphate Aono, Hiromichi Journal of The Electrochemical Society, Vol. 137, Issue 4 https://doi.org/10.1149/1.2086597	journal	January 1990
Review—Interfaces: Key Issue to Be Solved for All Solid-State Lithium Battery Technologies Ding, Zhanlai; Li, Jianlong; Li, Jiao Journal of The Electrochemical Society, Vol. 167, Issue 7 https://doi.org/10.1149/1945-7111/ab7f84	journal	March 2020
Effect of Gold Layer on Interface Resistance between Lithium Metal Anode and Li _6.25 Al _0.25 La ₃ Zr ₂ O ₁₂ Solid Electrolyte Wakasugi, Jungo; Munakata, Hirokazu; Kanamura, Kiyoshi Journal of The Electrochemical Society, Vol. 164, Issue 6 https://doi.org/10.1149/2.0471706jes	journal	January 2017
Fabrication of Silicon Nitride Ion Sensitive Field‐Effect Transistor for pH Measurement and DNA Immobilization/Hybridization Hashim, U.; Chong, Soon Weng; Liu, Wei-Wen Journal of Nanomaterials, Vol. 2013, Issue 1 https://doi.org/10.1155/2013/542737	journal	January 2013
Lithium Dendrite Formation on a Lithium Metal Anode from Liquid, Polymer and Solid Electrolytes Takeda, Yasuo; Yamamoto, Osamu; Imanishi, Nobuyuki Electrochemistry, Vol. 84, Issue 4 https://doi.org/10.5796/electrochemistry.84.210	journal	January 2016