Mesoscale Interrogation Reveals Mechanistic Origins of Lithium Filaments along Grain Boundaries in Inorganic Solid Electrolytes

Vishnugopi, Bairav S.; Dixit, Marm B.; Hao, Feng; Shyam, Badri; Cook, John B.; Hatzell, Kelsey B.; Mukherjee, Partha P.

doi:10.1002/aenm.202102825

Mesoscale Interrogation Reveals Mechanistic Origins of Lithium Filaments along Grain Boundaries in Inorganic Solid Electrolytes

Journal Article · Wed Dec 15 00:00:00 EST 2021 · Advanced Energy Materials

DOI:https://doi.org/10.1002/aenm.202102825· OSTI ID:1838403

Vishnugopi, Bairav S. ^[1]; Dixit, Marm B. ^[2]; Hao, Feng ^[3]; Shyam, Badri ^[4]; Cook, John B. ^[4]; Hatzell, Kelsey B. ^[5]; ^[1]

School of Mechanical Engineering Purdue University West Lafayette IN 47907 USA
Department of Mechanical Engineering Vanderbilt University Nashville TN 37235 USA
Department of Engineering Mechanics Shandong University Jinan Shandong 250061 China
Xerion Advanced Battery Corporation Kettering OH 45420 USA
Department of Mechanical Engineering Vanderbilt University Nashville TN 37235 USA, Department of Mechanical and Aerospace Engineering Princeton University Princeton NJ 08544 USA

Abstract

Solid‐state batteries (SSBs), utilizing a lithium metal anode, promise to deliver enhanced energy and power densities compared to conventional lithium‐ion batteries. Penetration of lithium filaments through the solid‐state electrolytes (SSEs) during electrodeposition poses major constraints on the safety and rate performance of SSBs. While microstructural attributes, especially grain boundaries (GBs) within the SSEs are considered preferential metal propagation pathways, the underlying mechanisms are not fully understood yet. Here, a comprehensive insight is presented into the mechanistic interactions at the mesoscale including the electrochemical‐mechanical response of the GB‐electrode junction and competing ion transport dynamics in the SSE. Depending on the GB transport characteristics, a highly non‐uniform electrodeposition morphology consisting of either cavities or protrusions at the GB‐electrode interface is identified. Mechanical stability analysis reveals localized strain ramps in the GB regions that can lead to brittle fracture of the SSE. For ionically less conductive GBs compared to the grains, a crack formation and void filling mechanism, triggered by the heterogeneous nature of electrochemical‐mechanical interactions is delineated at the GB‐electrode junction. Concurrently, in situ X‐ray tomography of pristine and failed Li ₇ La ₃ Zr ₂ O ₁₂ (LLZO) SSE samples confirm the presence of filamentous lithium penetration and validity of the proposed mesoscale failure mechanisms.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1838403

Alternate ID(s):: OSTI ID: 1845501
OSTI ID: 1847705
OSTI ID: 23113927

Journal Information:: Advanced Energy Materials, Journal Name: Advanced Energy Materials Journal Issue: 3 Vol. 12; ISSN 1614-6832

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (71)

3D Imaging of Lithium Protrusions in Solid‐State Lithium Batteries using X‐Ray Computed Tomography Hao, Shuai; Bailey, Josh J.; Iacoviello, Francesco Advanced Functional Materials, Vol. 31, Issue 10 https://doi.org/10.1002/adfm.202007564	journal	December 2020
Reviving Lithium-Metal Anodes for Next-Generation High-Energy Batteries Guo, Yanpeng; Li, Huiqiao; Zhai, Tianyou Advanced Materials, Vol. 29, Issue 29 https://doi.org/10.1002/adma.201700007	journal	June 2017
Mechanism of Lithium Metal Penetration through Inorganic Solid Electrolytes Porz, Lukas; Swamy, Tushar; Sheldon, Brian W. Advanced Energy Materials, Vol. 7, Issue 20 https://doi.org/10.1002/aenm.201701003	journal	July 2017
Revealing the Short‐Circuiting Mechanism of Garnet‐Based Solid‐State Electrolyte Song, Yongli; Yang, Luyi; Zhao, Wenguang Advanced Energy Materials, Vol. 9, Issue 21 https://doi.org/10.1002/aenm.201900671	journal	April 2019
Diffusion Limitation of Lithium Metal and Li–Mg Alloy Anodes on LLZO Type Solid Electrolytes as a Function of Temperature and Pressure Krauskopf, Thorben; Mogwitz, Boris; Rosenbach, Carolin Advanced Energy Materials, Vol. 9, Issue 44 https://doi.org/10.1002/aenm.201902568	journal	October 2019
Nonuniform Ionic and Electronic Transport of Ceramic and Polymer/Ceramic Hybrid Electrolyte by Nanometer‐Scale Operando Imaging for Solid‐State Battery Jiang, Chun‐Sheng; Dunlap, Nathan; Li, Yejing Advanced Energy Materials, Vol. 10, Issue 21 https://doi.org/10.1002/aenm.202000219	journal	April 2020
Modulating Nanoinhomogeneity at Electrode–Solid Electrolyte Interfaces for Dendrite‐Proof Solid‐State Batteries and Long‐Life Memristors Lu, Ziheng; Yang, Ziwei; Li, Cheng Advanced Energy Materials, Vol. 11, Issue 16 https://doi.org/10.1002/aenm.202003811	journal	March 2021
Resolving the Grain Boundary and Lattice Impedance of Hot-Pressed Li ₇ La ₃ Zr ₂ O ₁₂ Garnet Electrolytes Tenhaeff, Wyatt E.; Rangasamy, Ezhiyl; Wang, Yangyang ChemElectroChem, Vol. 1, Issue 2 https://doi.org/10.1002/celc.201300022	journal	July 2013
Introduction to the Kinetic Monte Carlo Method Voter, Arthur F. Radiation Effects in Solids https://doi.org/10.1007/978-1-4020-5295-8_1	book	January 2007
Elastic, plastic, and creep mechanical properties of lithium metal Masias, Alvaro; Felten, Nando; Garcia-Mendez, Regina Journal of Materials Science, Vol. 54, Issue 3 https://doi.org/10.1007/s10853-018-2971-3	journal	October 2018
Frequency factors and isotope effects in solid state rate processes Vineyard, George H. Journal of Physics and Chemistry of Solids, Vol. 3, Issue 1-2 https://doi.org/10.1016/0022-3697(57)90059-8	journal	January 1957
Direct observation of lithium dendrites inside garnet-type lithium-ion solid electrolyte Ren, Yaoyu; Shen, Yang; Lin, Yuanhua Electrochemistry Communications, Vol. 57 https://doi.org/10.1016/j.elecom.2015.05.001	journal	August 2015
Microscopic observations of the formation, growth and shrinkage of lithium moss during electrodeposition and dissolution Steiger, Jens; Kramer, Dominik; Mönig, Reiner Electrochimica Acta, Vol. 136 https://doi.org/10.1016/j.electacta.2014.05.120	journal	August 2014
Intergranular Li metal propagation through polycrystalline Li6.25Al0.25La3Zr2O12 ceramic electrolyte Cheng, Eric Jianfeng; Sharafi, Asma; Sakamoto, Jeff Electrochimica Acta, Vol. 223 https://doi.org/10.1016/j.electacta.2016.12.018	journal	January 2017
Temperature dependent flux balance of the Li/Li7La3Zr2O12 interface Wang, Michael; Wolfenstine, Jeffrey B.; Sakamoto, Jeff Electrochimica Acta, Vol. 296 https://doi.org/10.1016/j.electacta.2018.11.034	journal	February 2019
A chemo-mechanical damage model at large deformation: numerical and experimental studies on polycrystalline energy materials Bai, Yang; Santos, David A.; Rezaei, Shahed International Journal of Solids and Structures, Vol. 228 https://doi.org/10.1016/j.ijsolstr.2021.111099	journal	October 2021
Lithium-Metal Growth Kinetics on LLZO Garnet-Type Solid Electrolytes Krauskopf, Thorben; Dippel, Rabea; Hartmann, Hannah Joule, Vol. 3, Issue 8 https://doi.org/10.1016/j.joule.2019.06.013	journal	August 2019
Characterizing the Li-Solid-Electrolyte Interface Dynamics as a Function of Stack Pressure and Current Density Wang, Michael J.; Choudhury, Rishav; Sakamoto, Jeff Joule, Vol. 3, Issue 9 https://doi.org/10.1016/j.joule.2019.06.017	journal	September 2019
High sodium ion conductivity of glass–ceramic electrolytes with cubic Na3PS4 Hayashi, Akitoshi; Noi, Kousuke; Tanibata, Naoto Journal of Power Sources, Vol. 258 https://doi.org/10.1016/j.jpowsour.2014.02.054	journal	July 2014
Characterizing the Li–Li7La3Zr2O12 interface stability and kinetics as a function of temperature and current density Sharafi, Asma; Meyer, Harry M.; Nanda, Jagjit Journal of Power Sources, Vol. 302 https://doi.org/10.1016/j.jpowsour.2015.10.053	journal	January 2016
Li Penetration in Ceramic Solid Electrolytes: Operando Microscopy Analysis of Morphology, Propagation, and Reversibility Kazyak, Eric; Garcia-Mendez, Regina; LePage, William S. Matter, Vol. 2, Issue 4 https://doi.org/10.1016/j.matt.2020.02.008	journal	April 2020
Coupled crack propagation and dendrite growth in solid electrolyte of all-solid-state battery Yuan, Chunhao; Gao, Xiang; Jia, Yikai Nano Energy, Vol. 86 https://doi.org/10.1016/j.nanoen.2021.106057	journal	August 2021
Chemo-Mechanical Challenges in Solid-State Batteries Lewis, John A.; Tippens, Jared; Cortes, Francisco Javier Quintero Trends in Chemistry, Vol. 1, Issue 9 https://doi.org/10.1016/j.trechm.2019.06.013	journal	December 2019
Microstructure and Pressure-Driven Electrodeposition Stability in Solid-State Batteries Verma, Ankit; Kawakami, Hiroki; Wada, Hiroyuki Cell Reports Physical Science, Vol. 2, Issue 1 https://doi.org/10.1016/j.xcrp.2020.100301	journal	January 2021
Elastic Properties of the Solid Electrolyte Li ₇ La ₃ Zr ₂ O ₁₂ (LLZO) Yu, Seungho; Schmidt, Robert D.; Garcia-Mendez, Regina Chemistry of Materials, Vol. 28, Issue 1 https://doi.org/10.1021/acs.chemmater.5b03854	journal	December 2015
Grain Boundary Contributions to Li-Ion Transport in the Solid Electrolyte Li ₇ La ₃ Zr ₂ O ₁₂ (LLZO) Yu, Seungho; Siegel, Donald J. Chemistry of Materials, Vol. 29, Issue 22 https://doi.org/10.1021/acs.chemmater.7b02805	journal	November 2017
Physicochemical Concepts of the Lithium Metal Anode in Solid-State Batteries Krauskopf, Thorben; Richter, Felix H.; Zeier, Wolfgang G. Chemical Reviews, Vol. 120, Issue 15 https://doi.org/10.1021/acs.chemrev.0c00431	journal	July 2020
Toward Safe Lithium Metal Anode in Rechargeable Batteries: A Review Cheng, Xin-Bing; Zhang, Rui; Zhao, Chen-Zi Chemical Reviews, Vol. 117, Issue 15 https://doi.org/10.1021/acs.chemrev.7b00115	journal	July 2017
Energetics Dictates Deposition at Metal/Solid Electrolyte Interfaces Tewari, Deepti; Mukherjee, Partha P. The Journal of Physical Chemistry C, Vol. 125, Issue 4 https://doi.org/10.1021/acs.jpcc.0c05873	journal	August 2020
Synchrotron Imaging of Pore Formation in Li Metal Solid-State Batteries Aided by Machine Learning Dixit, Marm B.; Verma, Ankit; Zaman, Wahid ACS Applied Energy Materials, Vol. 3, Issue 10 https://doi.org/10.1021/acsaem.0c02053	journal	September 2020
Double-Edged Effect of Temperature on Lithium Dendrites Vishnugopi, Bairav Sabarish; Hao, Feng; Verma, Ankit ACS Applied Materials & Interfaces, Vol. 12, Issue 21 https://doi.org/10.1021/acsami.0c04355	journal	May 2020
Tortuosity Effects in Garnet-Type Li ₇ La ₃ Zr ₂ O ₁₂ Solid Electrolytes Dixit, Marm B.; Regala, Matthew; Shen, Fengyu ACS Applied Materials & Interfaces, Vol. 11, Issue 2 https://doi.org/10.1021/acsami.8b16536	journal	December 2018
Grain Boundary Softening: A Potential Mechanism for Lithium Metal Penetration through Stiff Solid Electrolytes Yu, Seungho; Siegel, Donald J. ACS Applied Materials & Interfaces, Vol. 10, Issue 44 https://doi.org/10.1021/acsami.8b17223	journal	October 2018
Enhancement Effects of Co Doping on Interfacial Properties of Sn Electrode−Collector: A First-Principles Study Zhang, Panpan; Wang, Yan; Lei, Weixin ACS Applied Materials & Interfaces, Vol. 11, Issue 27 https://doi.org/10.1021/acsami.9b01418	journal	June 2019
Toward a Fundamental Understanding of the Lithium Metal Anode in Solid-State Batteries—An Electrochemo-Mechanical Study on the Garnet-Type Solid Electrolyte Li _6.25 Al _0.25 La ₃ Zr ₂ O ₁₂ Krauskopf, Thorben; Hartmann, Hannah; Zeier, Wolfgang G. ACS Applied Materials & Interfaces, Vol. 11, Issue 15 https://doi.org/10.1021/acsami.9b02537	journal	March 2019
Dendrites and Pits: Untangling the Complex Behavior of Lithium Metal Anodes through Operando Video Microscopy Wood, Kevin N.; Kazyak, Eric; Chadwick, Alexander F. ACS Central Science, Vol. 2, Issue 11 https://doi.org/10.1021/acscentsci.6b00260	journal	October 2016
Co-Electrodeposition Mechanism in Rechargeable Metal Batteries Vishnugopi, Bairav S.; Hao, Feng; Verma, Ankit ACS Energy Letters, Vol. 6, Issue 6 https://doi.org/10.1021/acsenergylett.1c00677	journal	May 2021
Challenges and Opportunities for Fast Charging of Solid-State Lithium Metal Batteries Vishnugopi, Bairav S.; Kazyak, Eric; Lewis, John A. ACS Energy Letters, Vol. 6, Issue 10 https://doi.org/10.1021/acsenergylett.1c01352	journal	September 2021
Effect of Pore Connectivity on Li Dendrite Propagation within LLZO Electrolytes Observed with Synchrotron X-ray Tomography Shen, Fengyu; Dixit, Marm B.; Xiao, Xianghui ACS Energy Letters, Vol. 3, Issue 4 https://doi.org/10.1021/acsenergylett.8b00249	journal	March 2018
Interphase Morphology between a Solid-State Electrolyte and Lithium Controls Cell Failure Lewis, John A.; Cortes, Francisco Javier Quintero; Boebinger, Matthew G. ACS Energy Letters, Vol. 4, Issue 2 https://doi.org/10.1021/acsenergylett.9b00093	journal	January 2019
Visualizing Chemomechanical Degradation of a Solid-State Battery Electrolyte Tippens, Jared; Miers, John C.; Afshar, Arman ACS Energy Letters, Vol. 4, Issue 6 https://doi.org/10.1021/acsenergylett.9b00816	journal	May 2019
Challenges in Lithium Metal Anodes for Solid-State Batteries Hatzell, Kelsey B.; Chen, Xi Chelsea; Cobb, Corie L. ACS Energy Letters, Vol. 5, Issue 3 https://doi.org/10.1021/acsenergylett.9b02668	journal	February 2020
Effect of Surface Microstructure on Electrochemical Performance of Garnet Solid Electrolytes Cheng, Lei; Chen, Wei; Kunz, Martin ACS Applied Materials & Interfaces, Vol. 7, Issue 3 https://doi.org/10.1021/am508111r	journal	January 2015
Atomic-Scale Influence of Grain Boundaries on Li-Ion Conduction in Solid Electrolytes for All-Solid-State Batteries Dawson, James A.; Canepa, Pieremanuele; Famprikis, Theodosios Journal of the American Chemical Society, Vol. 140, Issue 1 https://doi.org/10.1021/jacs.7b10593	journal	December 2017
Promise and reality of post-lithium-ion batteries with high energy densities Choi, Jang Wook; Aurbach, Doron Nature Reviews Materials, Vol. 1, Issue 4 https://doi.org/10.1038/natrevmats.2016.13	journal	March 2016
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
High-power all-solid-state batteries using sulfide superionic conductors Kato, Yuki; Hori, Satoshi; Saito, Toshiya Nature Energy, Vol. 1, Issue 4 https://doi.org/10.1038/nenergy.2016.30	journal	March 2016
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 electronic conductivity as the origin of lithium dendrite formation within solid electrolytes Han, Fudong; Westover, Andrew S.; Yue, Jie Nature Energy, Vol. 4, Issue 3 https://doi.org/10.1038/s41560-018-0312-z	journal	January 2019
Critical stripping current leads to dendrite formation on plating in lithium anode solid electrolyte cells Kasemchainan, Jitti; Zekoll, Stefanie; Spencer Jolly, Dominic Nature Materials, Vol. 18, Issue 10 https://doi.org/10.1038/s41563-019-0438-9	journal	July 2019
Linking void and interphase evolution to electrochemistry in solid-state batteries using operando X-ray tomography Lewis, John A.; Cortes, Francisco Javier Quintero; Liu, Yuhgene Nature Materials, Vol. 20, Issue 4 https://doi.org/10.1038/s41563-020-00903-2	journal	January 2021
Blocking lithium dendrite growth in solid-state batteries with an ultrathin amorphous Li-La-Zr-O solid electrolyte Sastre, Jordi; Futscher, Moritz H.; Pompizi, Lea Communications Materials, Vol. 2, Issue 1 https://doi.org/10.1038/s43246-021-00177-4	journal	July 2021
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
A sulphide lithium super ion conductor is superior to liquid ion conductors for use in rechargeable batteries Seino, Yoshikatsu; Ota, Tsuyoshi; Takada, Kazunori Energy Environ. Sci., Vol. 7, Issue 2 https://doi.org/10.1039/C3EE41655K	journal	January 2014
Electrochemical in situ investigations of SEI and dendrite formation on the lithium metal anode Bieker, Georg; Winter, Martin; Bieker, Peter Physical Chemistry Chemical Physics, Vol. 17, Issue 14 https://doi.org/10.1039/C4CP05865H	journal	January 2015
Dendrite-free lithium metal anodes: stable solid electrolyte interphases for high-efficiency batteries Cheng, Xin-Bing; Zhang, Qiang Journal of Materials Chemistry A, Vol. 3, Issue 14 https://doi.org/10.1039/C5TA00689A	journal	January 2015
Origin of the low grain boundary conductivity in lithium ion conducting perovskites: Li _3x La _0.67−x TiO ₃ Wu, Jian-Fang; Guo, Xin Physical Chemistry Chemical Physics, Vol. 19, Issue 8 https://doi.org/10.1039/C6CP07757A	journal	January 2017
Transition of lithium growth mechanisms in liquid electrolytes Bai, Peng; Li, Ju; Brushett, Fikile R. Energy & Environmental Science, Vol. 9, Issue 10 https://doi.org/10.1039/C6EE01674J	journal	January 2016
Dead lithium: mass transport effects on voltage, capacity, and failure of lithium metal anodes Chen, Kuan-Hung; Wood, Kevin N.; Kazyak, Eric Journal of Materials Chemistry A, Vol. 5, Issue 23 https://doi.org/10.1039/C7TA00371D	journal	January 2017
Surface diffusion manifestation in electrodeposition of metal anodes Vishnugopi, Bairav S.; Hao, Feng; Verma, Ankit Physical Chemistry Chemical Physics, Vol. 22, Issue 20 https://doi.org/10.1039/D0CP01352H	journal	January 2020
Quantifying the promise of lithium–air batteries for electric vehicles Gallagher, Kevin G.; Goebel, Steven; Greszler, Thomas Energy & Environmental Science, Vol. 7, Issue 5 https://doi.org/10.1039/c3ee43870h	journal	January 2014
Electrochemical aspects of the generation of ramified metallic electrodeposits Chazalviel, J. -N. Physical Review A, Vol. 42, Issue 12 https://doi.org/10.1103/PhysRevA.42.7355	journal	December 1990
The Effect of Interfacial Deformation on Electrodeposition Kinetics Monroe, Charles; Newman, John Journal of The Electrochemical Society, Vol. 151, Issue 6 https://doi.org/10.1149/1.1710893	journal	January 2004
The Impact of Elastic Deformation on Deposition Kinetics at Lithium/Polymer Interfaces Monroe, Charles; Newman, John Journal of The Electrochemical Society, Vol. 152, Issue 2 https://doi.org/10.1149/1.1850854	journal	January 2005
Lithium Electrode Morphology during Cycling in Lithium Cells Yoshimatsu, Isamu Journal of The Electrochemical Society, Vol. 135, Issue 10 https://doi.org/10.1149/1.2095351	journal	January 1988
Molar Volume Mismatch: A Malefactor for Irregular Metallic Electrodeposition with Solid Electrolytes Mistry, Aashutosh; Mukherjee, Partha P. Journal of The Electrochemical Society, Vol. 167, Issue 8 https://doi.org/10.1149/1945-7111/ab8ecd	journal	May 2020
The Role of Local Inhomogeneities on Dendrite Growth in LLZO-Based Solid Electrolytes Barai, Pallab; Ngo, Anh T.; Narayanan, Badri Journal of The Electrochemical Society, Vol. 167, Issue 10 https://doi.org/10.1149/1945-7111/ab9b08	journal	June 2020
Lithium Mechanics: Roles of Strain Rate and Temperature and Implications for Lithium Metal Batteries LePage, William S.; Chen, Yuxin; Kazyak, Eric Journal of The Electrochemical Society, Vol. 166, Issue 2 https://doi.org/10.1149/2.0221902jes	journal	January 2019
Mechanical Stress Induced Current Focusing and Fracture in Grain Boundaries Barai, Pallab; Higa, Kenneth; Ngo, Anh T. Journal of The Electrochemical Society, Vol. 166, Issue 10 https://doi.org/10.1149/2.0321910jes	journal	January 2019
Contact between Garnet-Type Solid Electrolyte and Lithium Metal Anode: Influence on Charge Transfer Resistance and Short Circuit Prevention Basappa, Rajendra Hongahally; Ito, Tomoko; Yamada, Hirotoshi Journal of The Electrochemical Society, Vol. 164, Issue 4 https://doi.org/10.1149/2.0841704jes	journal	January 2017
Lithium Metal Penetration Induced by Electrodeposition through Solid Electrolytes: Example in Single-Crystal Li ₆ La ₃ ZrTaO ₁₂ Garnet Swamy, Tushar; Park, Richard; Sheldon, Brian W. Journal of The Electrochemical Society, Vol. 165, Issue 16 https://doi.org/10.1149/2.1391814jes	journal	January 2018

Similar Records

Mechanical Stress Induced Current Focusing and Fracture in Grain Boundaries

Journal Article · Thu May 30 20:00:00 EDT 2019 · Journal of the Electrochemical Society · OSTI ID:1812866

Mesoscale Interrogation Reveals Mechanistic Origins of Lithium Filaments along Grain Boundaries in Inorganic Solid Electrolytes

Citation Formats

References (71)

Similar Records

Related Subjects