Tuning the Anode–Electrolyte Interface Chemistry for Garnet-Based Solid-State Li Metal Batteries

Deng, Tao; Ji, Xiao; Zhao, Yang; Cao, Longsheng; Li, Shuang; Hwang, Sooyeon; Luo, Chao; Wang, Pengfei; Jia, Haiping; Fan, Xiulin; Lu, Xiaochuan; Su, Dong; Sun, Xueliang; Wang, Chunsheng; Zhang, Ji‐Guang

doi:10.1002/adma.202000030

Tuning the Anode–Electrolyte Interface Chemistry for Garnet-Based Solid-State Li Metal Batteries

Journal Article · Mon May 04 00:00:00 EDT 2020 · Advanced Materials

DOI:https://doi.org/10.1002/adma.202000030· OSTI ID:1631926

Deng, Tao ^[1]; Ji, Xiao ^[2]; Zhao, Yang ^[3]; Cao, Longsheng ^[2]; Li, Shuang ^[4]; ^[4]; Luo, Chao ^[5]; Wang, Pengfei ^[2]; Jia, Haiping ^[6]; Fan, Xiulin ^[2]; Lu, Xiaochuan ^[7]; Su, Dong ^[4]; Sun, Xueliang ^[3]; ^[2]; Zhang, Ji‐Guang ^[6]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Univ. of Maryland, College Park, MD (United States)
Univ. of Maryland, College Park, MD (United States)
Univ. of Western Ontario, London, ON (Canada)
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
George Mason Univ., Fairfax, VA (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
North Carolina A & T State Univ., Greensboro, NC (United States)

Lithium (Li) metal anode is a promising candidate for high energy density solid-state batteries. However, the interface issues, including large interfacial resistance and Li dendrite generation, have always frustrated the attempt to commercialize solid-state Li metal batteries (SSLBs). Here, we report that infusing the garnet-type solid electrolytes (GSEs) with air-stable electrolyte Li₃PO₄ (LPO) dramatically reduces the interfacial resistance to ~1 Ω cm² and achieves a high critical current density of 2.2 mA cm^-2 under ambient condition due to enhanced interfacial stability to Li metal anode. The coated and infused LPO electrolytes not only improve the mechanical strength and Li-ion conductivity of grain boundaries, but also form a stable Li-ion conductive but electron-insulating LPO-derived solid-electrolyte interphase between Li metal and GSEs, and consequently eliminates the Li dendrites growth and prevents the direct reduction of GSEs by Li metal over a long cycle life. This interface engineering approach together with grain-boundary modification on GSEs represents a promising strategy to revolutionize the anode-electrolyte interface chemistry for SSLBs and provides new design strategy for other-types of solid-state batteries.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: SC0012704

OSTI ID:: 1631926

Alternate ID(s):: OSTI ID: 1617070

Report Number(s):: BNL--215968-2020-JAAM

Journal Information:: Advanced Materials, Journal Name: Advanced Materials Journal Issue: 23 Vol. 32; ISSN 0935-9648

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (45)

Electrochemical Stability of Li ₁₀ GeP ₂ S ₁₂ and Li ₇ La ₃ Zr ₂ O ₁₂ Solid Electrolytes Han, Fudong; Zhu, Yizhou; He, Xingfeng Advanced Energy Materials, Vol. 6, Issue 8 https://doi.org/10.1002/aenm.201501590	journal	January 2016
Dopant‐Dependent Stability of Garnet Solid Electrolyte Interfaces with Lithium Metal Zhu, Yisi; Connell, Justin G.; Tepavcevic, Sanja Advanced Energy Materials, Vol. 9, Issue 12 https://doi.org/10.1002/aenm.201803440	journal	January 2019
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
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
Mechanical behavior of Li-ion-conducting crystalline oxide-based solid electrolytes: a brief review Wolfenstine, Jeff; Allen, Jan L.; Sakamoto, Jeff Ionics, Vol. 24, Issue 5 https://doi.org/10.1007/s11581-017-2314-4	journal	November 2017
Perovskite solid electrolytes: Structure, transport properties and fuel cell applications Bonanos, N. Solid State Ionics, Vol. 79 https://doi.org/10.1016/0167-2738(95)00056-C	journal	July 1995
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
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
Phase transition in lithium garnet oxide ionic conductors Li7La3Zr2O12: The role of Ta substitution and H2O/CO2 exposure Wang, Yuxing; Lai, Wei Journal of Power Sources, Vol. 275 https://doi.org/10.1016/j.jpowsour.2014.11.062	journal	February 2015
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 metal coated with amorphous Li3PO4 via magnetron sputtering for stable and long-cycle life lithium metal batteries Wang, Liping; Wang, Qingji; Jia, Weishang Journal of Power Sources, Vol. 342 https://doi.org/10.1016/j.jpowsour.2016.11.097	journal	February 2017
Correlating the interface resistance and surface adhesion of the Li metal-solid electrolyte interface Wang, Michael; Sakamoto, Jeff Journal of Power Sources, Vol. 377 https://doi.org/10.1016/j.jpowsour.2017.11.078	journal	February 2018
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
Demonstration of high current densities and extended cycling in the garnet Li7La3Zr2O12 solid electrolyte Taylor, Nathan J.; Stangeland-Molo, Sandra; Haslam, Catherine G. Journal of Power Sources, Vol. 396 https://doi.org/10.1016/j.jpowsour.2018.06.055	journal	August 2018
A brief review of atomic layer deposition: from fundamentals to applications Johnson, Richard W.; Hultqvist, Adam; Bent, Stacey F. Materials Today, Vol. 17, Issue 5 https://doi.org/10.1016/j.mattod.2014.04.026	journal	June 2014
Inorganic solid Li ion conductors: An overview Knauth, Philippe Solid State Ionics, Vol. 180, Issue 14-16, p. 911-916 https://doi.org/10.1016/j.ssi.2009.03.022	journal	June 2009
Improved lithium-ion transport in NASICON-type lithium titanium phosphate by calcium and iron doping Ortiz, Gregorio F.; López, María C.; Lavela, Pedro Solid State Ionics, Vol. 262 https://doi.org/10.1016/j.ssi.2013.09.012	journal	September 2014
Interface reactions between LiPON and lithium studied by in-situ X-ray photoemission Schwöbel, André; Hausbrand, René; Jaegermann, Wolfram Solid State Ionics, Vol. 273 https://doi.org/10.1016/j.ssi.2014.10.017	journal	May 2015
Effect of Al2O3 on the sintering of garnet-type Li6.5La3Zr1.5Ta0.5O12 Wang, Yuxing; Yan, Pengfei; Xiao, Jie Solid State Ionics, Vol. 294 https://doi.org/10.1016/j.ssi.2016.06.013	journal	October 2016
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
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
Stabilizing the Interface of NASICON Solid Electrolyte against Li Metal with Atomic Layer Deposition Liu, Yulong; Sun, Qian; Zhao, Yang ACS Applied Materials & Interfaces, Vol. 10, Issue 37 https://doi.org/10.1021/acsami.8b06366	journal	August 2018
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
Deposition and Confinement of Li Metal along an Artificial Lipon–Lipon Interface Westover, Andrew S.; Dudney, Nancy J.; Sacci, Robert L. ACS Energy Letters, Vol. 4, Issue 3 https://doi.org/10.1021/acsenergylett.8b02542	journal	February 2019
Alternative Approach to Increasing Li Mobility in Li-La-Nb/Ta Garnet Electrolytes Nyman, May; Alam, Todd M.; McIntyre, Sarah K. Chemistry of Materials, Vol. 22, Issue 19 https://doi.org/10.1021/cm101438x	journal	October 2010
Plating a Dendrite-Free Lithium Anode with a Polymer/Ceramic/Polymer Sandwich Electrolyte Zhou, Weidong; Wang, Shaofei; Li, Yutao Journal of the American Chemical Society, Vol. 138, Issue 30 https://doi.org/10.1021/jacs.6b05341	journal	July 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
Garnet Electrolyte with an Ultralow Interfacial Resistance for Li-Metal Batteries Li, Yutao; Chen, Xi; Dolocan, Andrei Journal of the American Chemical Society, Vol. 140, Issue 20 https://doi.org/10.1021/jacs.8b03106	journal	April 2018
Identification of cathode materials for lithium batteries guided by first-principles calculations Ceder, G.; Chiang, Y. -M.; Sadoway, D. R. Nature, Vol. 392, Issue 6677 https://doi.org/10.1038/33647	journal	April 1998
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
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
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
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
Tailoring grain boundary structures and chemistry of Ni-rich layered cathodes for enhanced cycle stability of lithium-ion batteries Yan, Pengfei; Zheng, Jianming; Liu, Jian Nature Energy, Vol. 3, Issue 7 https://doi.org/10.1038/s41560-018-0191-3	journal	June 2018
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
Fundamentals of inorganic solid-state electrolytes for batteries Famprikis, Theodosios; Canepa, Pieremanuele; Dawson, James A. Nature Materials, Vol. 18, Issue 12 https://doi.org/10.1038/s41563-019-0431-3	journal	August 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
Impact of air exposure and surface chemistry on Li–Li ₇ La ₃ Zr ₂ O ₁₂ interfacial resistance Sharafi, Asma; Yu, Seungho; Naguib, Michael Journal of Materials Chemistry A, Vol. 5, Issue 26 https://doi.org/10.1039/C7TA03162A	journal	January 2017
Optimizing Li+ conductivity in a garnet framework Li, Yutao; Han, Jian- Tao; Wang, Chang- An Journal of Materials Chemistry, Vol. 22, Issue 30 https://doi.org/10.1039/c2jm31413d	journal	January 2012
Morphology and conductivity study of solid electrolyte Li3PO4 Prayogi, Lugas Dwi; Faisal, Muhamad; Kartini, Evvy PROCEEDINGS OF INTERNATIONAL SEMINAR ON MATHEMATICS, SCIENCE, AND COMPUTER SCIENCE EDUCATION (MSCEIS 2015), AIP Conference Proceedings https://doi.org/10.1063/1.4941513	conference	January 2016
Atomic layer deposition of lithium phosphates as solid-state electrolytes for all-solid-state microbatteries Wang, Biqiong; Liu, Jian; Sun, Qian Nanotechnology, Vol. 25, Issue 50 https://doi.org/10.1088/0957-4484/25/50/504007	journal	November 2014
Structures, Li + mobilities, and interfacial properties of solid electrolytes Li 3 PS 4 and Li 3 PO 4 from first principles Lepley, N. D.; Holzwarth, N. A. W.; Du, Yaojun A. Physical Review B, Vol. 88, Issue 10 https://doi.org/10.1103/PhysRevB.88.104103	journal	September 2013
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
Review—Practical Challenges Hindering the Development of Solid State Li Ion Batteries Kerman, Kian; Luntz, Alan; Viswanathan, Venkatasubramanian Journal of The Electrochemical Society, Vol. 164, Issue 7 https://doi.org/10.1149/2.1571707jes	journal	January 2017

Similar Records

Stabilization of garnet/Li interphase by diluting the electronic conductor

Journal Article · Wed Oct 19 00:00:00 EDT 2022 · Science Advances · OSTI ID:1989365

Toward garnet electrolyte–based Li metal batteries: An ultrathin, highly effective, artificial solid-state electrolyte/metallic Li interface

Journal Article · Fri Apr 07 00:00:00 EDT 2017 · Science Advances · OSTI ID:1425393

In situ formation of polymer-inorganic solid-electrolyte interphase for stable polymeric solid-state lithium-metal batteries

Journal Article · Mon Jul 12 00:00:00 EDT 2021 · Chem · OSTI ID:1976954

Related Subjects

25 ENERGY STORAGE
garnet electrolytes
interfacial chemistry
lithium dendrites
solid electrolyte Interphase
solid-state batteries

Tuning the Anode–Electrolyte Interface Chemistry for Garnet-Based Solid-State Li Metal Batteries

Citation Formats

References (45)

Similar Records

Related Subjects