A universal wet-chemistry synthesis of solid-state halide electrolytes for all-solid-state lithium-metal batteries

Wang, Changhong; Liang, Jianwen; Luo, Jing; Liu, Jue; Li, Xiaona; Zhao, Feipeng; Li, Ruying; Huang, Huan; Zhao, Shangqian; Zhang, Li; Wang, Jiantao; Sun, Xueliang

doi:10.1126/sciadv.abh1896

Title: A universal wet-chemistry synthesis of solid-state halide electrolytes for all-solid-state lithium-metal batteries

Journal Article · 07 September 2021 · Science Advances

DOI: https://doi.org/10.1126/sciadv.abh1896 · OSTI ID:2471534

^[1];

^[1]; Luo, Jing ^[1]; Liu, Jue ^[2];

^[1];

^[1]; Li, Ruying ^[1];

^[3];

^[4]; Zhang, Li ^[4];

^[4];

^[1]

University of Western Ontario, London, ON (Canada)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Glabat Solid-State Battery Inc., London, ON (Canada)
China Automotive Battery Research Institute Co., Ltd., Beijing (China)

Solid-state halide electrolytes have gained revived research interests owing to their high ionic conductivity and high-voltage stability. However, synthesizing halide electrolytes from a liquid phase is extremely challenging because of the vulnerability of metal halides to hydrolysis. In this work, ammonium-assisted wet chemistry is reported to synthesize various solid-state halide electrolytes with an exceptional ionic conductivity (>1 microsiemens per centimeter). Microstrain-induced localized microstructure change is found to be beneficial to lithium ion transport in halide electrolytes. Furthermore, the interfacial incompatibility between halide electrolytes and lithium metal is alleviated by transforming the mixed electronic/ionic conductive interface into a lithium ion–conductive interface. Such all-solid-state lithium-metal batteries (ASSLMBs) demonstrate a high initial coulombic efficiency of 98.1% based on lithium cobalt oxide and a high discharge capacity of 166.9 microampere hours per gram based on single-crystal LiNi_0.6Mn_0.2Co_0.2O₂. This work provides universal approaches in both material synthesis and interface design for developing halide-based ASSLMBs.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2471534

Journal Information:: Science Advances, Journal Name: Science Advances Journal Issue: 37 Vol. 7; ISSN 2375-2548

Publisher:: AAASCopyright Statement

Country of Publication:: United States

Language:: English

References (53)

The Ammonium Chloride Route to Anhydrous Rare Earth Chlorides-The Example of Ycl ₃ Meyer, Gerd; Garcia, Eduardo; Corbett, John D. https://doi.org/10.1002/9780470132562.ch35	book	January 1989
Promises, Challenges, and Recent Progress of Inorganic Solid-State Electrolytes for All-Solid-State Lithium Batteries Gao, Zhonghui; Sun, Huabin; Fu, Lin Advanced Materials, Vol. 30, Issue 17 https://doi.org/10.1002/adma.201705702	journal	February 2018
Solid Halide Electrolytes with High Lithium-Ion Conductivity for Application in 4 V Class Bulk-Type All-Solid-State Batteries Asano, Tetsuya; Sakai, Akihiro; Ouchi, Satoru Advanced Materials, Vol. 30, Issue 44 https://doi.org/10.1002/adma.201803075	journal	September 2018
Sulfide‐Based Solid‐State Electrolytes: Synthesis, Stability, and Potential for All‐Solid‐State Batteries Zhang, Qing; Cao, Daxian; Ma, Yi Advanced Materials, Vol. 31, Issue 44 https://doi.org/10.1002/adma.201901131	journal	August 2019
Lithium/Sulfide All‐Solid‐State Batteries using Sulfide Electrolytes Wu, Jinghua; Liu, Sufu; Han, Fudong Advanced Materials, Vol. 33, Issue 6 https://doi.org/10.1002/adma.202000751	journal	August 2020
Kinetically Stabilized Cation Arrangement in Li ₃ YCl ₆ Superionic Conductor during Solid‐State Reaction Ito, Hiroaki; Shitara, Kazuki; Wang, Yongming Advanced Science, Vol. 8, Issue 15 https://doi.org/10.1002/advs.202101413	journal	June 2021
Lithium Fast-Ionic Conduction in Complex Hydrides: Review and Prospects Matsuo, Motoaki; Orimo, Shin-ichi Advanced Energy Materials, Vol. 1, Issue 2 https://doi.org/10.1002/aenm.201000012	journal	January 2011
Liquid‐Like Ionic Conduction in Solid Lithium and Sodium Monocarba‐ closo ‐Decaborates Near or at Room Temperature Tang, Wan Si; Matsuo, Motoaki; Wu, Hui Advanced Energy Materials, Vol. 6, Issue 8 https://doi.org/10.1002/aenm.201502237	journal	February 2016
A Lithium Amide-Borohydride Solid-State Electrolyte with Lithium-Ion Conductivities Comparable to Liquid Electrolytes Yan, Yigang; Kühnel, Ruben-Simon; Remhof, Arndt Advanced Energy Materials, Vol. 7, Issue 19 https://doi.org/10.1002/aenm.201700294	journal	June 2017
Stack Pressure Considerations for Room‐Temperature All‐Solid‐State Lithium Metal Batteries Doux, Jean‐Marie; Nguyen, Han; Tan, Darren H. S. Advanced Energy Materials, Vol. 10, Issue 1 https://doi.org/10.1002/aenm.201903253	journal	November 2019
Mechanochemical Synthesis: A Tool to Tune Cation Site Disorder and Ionic Transport Properties of Li ₃ MCl ₆ (M = Y, Er) Superionic Conductors Schlem, Roman; Muy, Sokseiha; Prinz, Nils Advanced Energy Materials, Vol. 10, Issue 6 https://doi.org/10.1002/aenm.201903719	journal	December 2019
Tailoring the Cation Lattice for Chloride Lithium‐Ion Conductors Liu, Yunsheng; Wang, Shuo; Nolan, Adelaide M. Advanced Energy Materials, Vol. 10, Issue 40 https://doi.org/10.1002/aenm.202002356	journal	September 2020
New Cost‐Effective Halide Solid Electrolytes for All‐Solid‐State Batteries: Mechanochemically Prepared Fe ³⁺ ‐Substituted Li ₂ ZrCl ₆ Kwak, Hiram; Han, Daseul; Lyoo, Jeyne Advanced Energy Materials, Vol. 11, Issue 12 https://doi.org/10.1002/aenm.202003190	journal	January 2021
Water‐Mediated Synthesis of a Superionic Halide Solid Electrolyte Li, Xiaona; Liang, Jianwen; Chen, Ning Angewandte Chemie, Vol. 131, Issue 46 https://doi.org/10.1002/ange.201909805	journal	September 2019
Lithium Chlorides and Bromides as Promising Solid‐State Chemistries for Fast Ion Conductors with Good Electrochemical Stability Wang, Shuo; Bai, Qiang; Nolan, Adelaide M. Angewandte Chemie International Edition, Vol. 58, Issue 24 https://doi.org/10.1002/anie.201901938	journal	June 2019
Lithium‐Metal Anode Instability of the Superionic Halide Solid Electrolytes and the Implications for Solid‐State Batteries Riegger, Luise M.; Schlem, Roman; Sann, Joachim Angewandte Chemie International Edition, Vol. 60, Issue 12 https://doi.org/10.1002/anie.202015238	journal	February 2021
Tern�re Halogenide vom Typ A3MX6. VI [1]. Tern�re Chloride der Selten-Erd-Elemente mit Lithium, Li3MCl6 (M ? Tb?Lu, Y, Sc): Synthese, Kristallstrukturen und Ionenbewegung Bohnsack, Andreas; Stenzel, Frauke; Zajonc, Armin Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 623, Issue 7 https://doi.org/10.1002/zaac.19976230710	journal	July 1997
Comprehensive Investigation into Garnet Electrolytes Toward Application-Oriented Solid Lithium Batteries Jia, Mengyang; Zhao, Ning; Huo, Hanyu Electrochemical Energy Reviews, Vol. 3, Issue 4 https://doi.org/10.1007/s41918-020-00076-1	journal	July 2020
Polymer Electrolytes for Lithium-Based Batteries: Advances and Prospects Zhou, Dong; Shanmukaraj, Devaraj; Tkacheva, Anastasia Chem, Vol. 5, Issue 9 https://doi.org/10.1016/j.chempr.2019.05.009	journal	September 2019
All solid-state polymer electrolytes for high-performance lithium ion batteries Yue, Liping; Ma, Jun; Zhang, Jianjun Energy Storage Materials, Vol. 5 https://doi.org/10.1016/j.ensm.2016.07.003	journal	October 2016
Single crystal cathodes enabling high-performance all-solid-state lithium-ion batteries Wang, Changhong; Yu, Ruizhi; Hwang, Sooyeon Energy Storage Materials, Vol. 30 https://doi.org/10.1016/j.ensm.2020.05.007	journal	September 2020
Practical evaluation of energy densities for sulfide solid-state batteries Liu, Lilu; Xu, Jieru; Wang, Shuo eTransportation, Vol. 1 https://doi.org/10.1016/j.etran.2019.100010	journal	August 2019
High-Throughput Screening of Solid-State Li-Ion Conductors Using Lattice-Dynamics Descriptors Muy, Sokseiha; Voss, Johannes; Schlem, Roman iScience, Vol. 16 https://doi.org/10.1016/j.isci.2019.05.036	journal	June 2019
Superionic conductivity in lithium argyrodite solid-state electrolyte by controlled Cl-doping Yu, Chuang; Li, Yong; Willans, Mathew Nano Energy, Vol. 69 https://doi.org/10.1016/j.nanoen.2019.104396	journal	March 2020
Interface-assisted in-situ growth of halide electrolytes eliminating interfacial challenges of all-inorganic solid-state batteries Wang, Changhong; Liang, Jianwen; Jiang, Ming Nano Energy, Vol. 76 https://doi.org/10.1016/j.nanoen.2020.105015	journal	October 2020
Halide-based solid-state electrolyte as an interfacial modifier for high performance solid-state Li–O2 batteries Zhao, Changtai; Liang, Jianwen; Li, Xiaona Nano Energy, Vol. 75 https://doi.org/10.1016/j.nanoen.2020.105036	journal	September 2020
Tuning ionic conductivity and electrode compatibility of Li3YBr6 for high-performance all solid-state Li batteries Yu, Chuang; Li, Yong; Adair, Keegan R. Nano Energy, Vol. 77 https://doi.org/10.1016/j.nanoen.2020.105097	journal	November 2020
Metal Halide Superionic Conductors for All-Solid-State Batteries Liang, Jianwen; Li, Xiaona; Adair, Keegan R. Accounts of Chemical Research, Vol. 54, Issue 4 https://doi.org/10.1021/acs.accounts.0c00762	journal	January 2021
Insights into the Lithium Sub-structure of Superionic Conductors Li ₃ YCl ₆ and Li ₃ YBr ₆ Schlem, Roman; Banik, Ananya; Ohno, Saneyuki Chemistry of Materials, Vol. 33, Issue 1 https://doi.org/10.1021/acs.chemmater.0c04352	journal	January 2021
Influence of Anion Charge on Li Ion Diffusion in a New Solid-State Electrolyte, Li ₃ LaI ₆ Xu, Zhenming; Chen, Xin; Liu, Ke Chemistry of Materials, Vol. 31, Issue 18 https://doi.org/10.1021/acs.chemmater.9b02075	journal	August 2019
Origin of Superionic Li ₃ Y _{1– x} In _x Cl ₆ Halide Solid Electrolytes with High Humidity Tolerance Li, Xiaona; Liang, Jianwen; Adair, Keegan R. Nano Letters, Vol. 20, Issue 6 https://doi.org/10.1021/acs.nanolett.0c01156	journal	May 2020
Lattice Dynamical Approach for Finding the Lithium Superionic Conductor Li ₃ ErI ₆ Schlem, Roman; Bernges, Tim; Li, Cheng ACS Applied Energy Materials, Vol. 3, Issue 4 https://doi.org/10.1021/acsaem.0c00147	journal	March 2020
Na _{3– x} Er _{1– x} Zr _x Cl ₆ —A Halide-Based Fast Sodium-Ion Conductor with Vacancy-Driven Ionic Transport Schlem, Roman; Banik, Ananya; Eckardt, Mirco ACS Applied Energy Materials, Vol. 3, Issue 10 https://doi.org/10.1021/acsaem.0c01870	journal	September 2020
Unlocking the Potential of Fluoride-Based Solid Electrolytes for Solid-State Lithium Batteries Feinauer, Max; Euchner, Holger; Fichtner, Maximilian ACS Applied Energy Materials, Vol. 2, Issue 10 https://doi.org/10.1021/acsaem.9b01166	journal	September 2019
Theoretical Design of Lithium Chloride Superionic Conductors for All-Solid-State High-Voltage Lithium-Ion Batteries Park, Dongsu; Park, Haesun; Lee, Yongheum ACS Applied Materials & Interfaces, Vol. 12, Issue 31 https://doi.org/10.1021/acsami.0c07003	journal	July 2020
High-Voltage Superionic Halide Solid Electrolytes for All-Solid-State Li-Ion Batteries Park, Kern-Ho; Kaup, Kavish; Assoud, Abdeljalil ACS Energy Letters, Vol. 5, Issue 2 https://doi.org/10.1021/acsenergylett.9b02599	journal	January 2020
Atomic Layer Deposition of Stable LiAlF ₄ Lithium Ion Conductive Interfacial Layer for Stable Cathode Cycling Xie, Jin; Sendek, Austin D.; Cubuk, Ekin D. ACS Nano, Vol. 11, Issue 7 https://doi.org/10.1021/acsnano.7b02561	journal	July 2017
Halide-Stabilized LiBH ₄ , a Room-Temperature Lithium Fast-Ion Conductor Maekawa, Hideki; Matsuo, Motoaki; Takamura, Hitoshi Journal of the American Chemical Society, Vol. 131, Issue 3 https://doi.org/10.1021/ja807392k	journal	January 2009
Site-Occupation-Tuned Superionic Li _x ScCl _{3+ x} Halide Solid Electrolytes for All-Solid-State Batteries Liang, Jianwen; Li, Xiaona; Wang, Shuo Journal of the American Chemical Society, Vol. 142, Issue 15 https://doi.org/10.1021/jacs.0c00134	journal	March 2020
Development of Microstrain in Aged Lithium Transition Metal Oxides Lee, Eung-Ju; Chen, Zonghai; Noh, Hyung-Ju Nano Letters, Vol. 14, Issue 8 https://doi.org/10.1021/nl5022859	journal	June 2014
Lithium battery chemistries enabled by solid-state electrolytes Manthiram, Arumugam; Yu, Xingwen; Wang, Shaofei Nature Reviews Materials, Vol. 2, Issue 4 https://doi.org/10.1038/natrevmats.2016.103	journal	February 2017
A complex hydride lithium superionic conductor for high-energy-density all-solid-state lithium metal batteries Kim, Sangryun; Oguchi, Hiroyuki; Toyama, Naoki Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09061-9	journal	March 2019
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
Liquid-phase syntheses of sulfide electrolytes for all-solid-state lithium battery Miura, Akira; Rosero-Navarro, Nataly Carolina; Sakuda, Atsushi Nature Reviews Chemistry, Vol. 3, Issue 3 https://doi.org/10.1038/s41570-019-0078-2	journal	February 2019
The oxidation of tantalum with ammonium chloride as an example of a novel route to early transitional metal–nitrogen cluster compounds. Synthesis and crystal structure of (NH₄)₆[Ta₅(NH)₄Cl₁₇] Simon, Marcus; Meyer, Gerd J. Chem. Soc., Chem. Commun., Issue 5 https://doi.org/10.1039/C39930000460	journal	January 1993
Single lithium-ion conducting solid polymer electrolytes: advances and perspectives Zhang, Heng; Li, Chunmei; Piszcz, Michal Chemical Society Reviews, Vol. 46, Issue 3 https://doi.org/10.1039/C6CS00491A	journal	January 2017
Interfacial behaviours between lithium ion conductors and electrode materials in various battery systems Wu, Bingbin; Wang, Shanyu; Evans IV, Willie J. Journal of Materials Chemistry A, Vol. 4, Issue 40 https://doi.org/10.1039/C6TA05439K	journal	January 2016
Air-stable Li ₃ InCl ₆ electrolyte with high voltage compatibility for all-solid-state batteries Li, Xiaona; Liang, Jianwen; Luo, Jing Energy & Environmental Science, Vol. 12, Issue 9 https://doi.org/10.1039/C9EE02311A	journal	January 2019
Progress and perspectives on halide lithium conductors for all-solid-state lithium batteries Li, Xiaona; Liang, Jianwen; Yang, Xiaofei Energy & Environmental Science, Vol. 13, Issue 5 https://doi.org/10.1039/C9EE03828K	journal	January 2020
A new halospinel superionic conductor for high-voltage all solid state lithium batteries Zhou, Laidong; Kwok, Chun Yuen; Shyamsunder, Abhinandan Energy & Environmental Science, Vol. 13, Issue 7 https://doi.org/10.1039/D0EE01017K	journal	January 2020
Garnet-type solid-state fast Li ion conductors for Li batteries: critical review Thangadurai, Venkataraman; Narayanan, Sumaletha; Pinzaru, Dana Chemical Society Reviews, Vol. 43, Issue 13 https://doi.org/10.1039/c4cs00020j	journal	January 2014
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data Momma, Koichi; Izumi, Fujio Journal of Applied Crystallography, Vol. 44, Issue 6 https://doi.org/10.1107/S0021889811038970	journal	October 2011
GSAS-II : the genesis of a modern open-source all purpose crystallography software package Toby, Brian H.; Von Dreele, Robert B. Journal of Applied Crystallography, Vol. 46, Issue 2 https://doi.org/10.1107/S0021889813003531	journal	March 2013

Similar Records

Unveiling the Role of Lithium Iodide in Stabilizing Solid Interfaces in All-Solid-State Li Metal Batteries

Journal Article · 2025 · ACS Energy Letters · OSTI ID:2997207

Huang, Di; Yuan, Suyue; Adelstein, Nicole; +3 more

Molecular Interlocking Multidimensional Modulations of Cathode‐Electrolyte Interface for Constructing High Energy Density Quasi‐Solid‐State Batteries

Journal Article · 2025 · Advanced Energy Materials · OSTI ID:2570187

He, Xinyou; Qin, Haozhe; Liu, Junxiang; +6 more

In-situ formation of stable interface towards Li-in anode for halide solid-state electrolyte

Journal Article · 2025 · Materials Today · OSTI ID:3018344

Fu, Jinzhao; Jin, Wenting; Yang, Songge; +8 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Science & Technology - Other Topics

Title: A universal wet-chemistry synthesis of solid-state halide electrolytes for all-solid-state lithium-metal batteries

Citation Formats

References (53)

Similar Records

Related Subjects