Li2.9Fe0.9Zr0.1Cl6 as Redox-Active Catholyte for Solid-State Li-Ion Batteries

Zhang, Guangxing; Liu, Zhantao; Ma, Yifan; Pepas, Jakub; Bai, Jianming; Zhong, Hui; Tang, Yuanzhi; Chen, Hailong

doi:10.1021/acs.chemmater.4c01385

Title: Li_2.9Fe_0.9Zr_0.1Cl₆ as Redox-Active Catholyte for Solid-State Li-Ion Batteries

Journal Article · 07 October 2024 · Chemistry of Materials

DOI: https://doi.org/10.1021/acs.chemmater.4c01385 · OSTI ID:2475346

Zhang, Guangxing ^[1];

^[1]; Ma, Yifan ^[1]; Pepas, Jakub ^[1];

^[2]; Zhong, Hui ^[2];

^[1];

^[1]

Georgia Institute of Technology, Atlanta, GA (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

Solid electrolytes are one of the key challenges that hinder the commercialization of all-solid-state batteries. Most efforts have been made to advance the development of solid electrolytes as separators, while the development of catholytes, particularly redox-active catholytes, has been less extensively studied. The high loading of catholytes in composite cathodes, while facilitating ionic conduction, drastically decreases the energy density of the battery. Here, we report an alternative strategy to improve the energy density by using Li_2.9Fe_0.9Zr_0.1Cl₆ as a redox-active catholyte. With a composite cathode containing uncoated LiCoO2 and Li_2.9Fe_0.9Zr_0.1Cl₆, the solid-state cell not only shows excellent rate capability and stable long-term cycling, benefiting from the high ionic conductivity of Li_2.9Fe_0.9Zr_0.1Cl₆, but also shows a high cathode specific capacity of ~153 mAh·g^–1. This study broadens the chemical space of the materials design for lithium-ion conductors with redox-active elements (e.g., Fe, Ti, V, and Cr), offering new opportunities to reduce the cost and improve the energy density for all-solid-state batteries.

View Accepted Manuscript (DOE)

Cite

Export

Save

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

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

Grant/Contract Number:: SC0012704

OSTI ID:: 2475346

Report Number(s):: BNL--226293-2024-JAAM

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 20 Vol. 36; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (42)

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
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
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
Single‐ or Poly‐Crystalline Ni‐Rich Layered Cathode, Sulfide or Halide Solid Electrolyte: Which Will be the Winners for All‐Solid‐State Batteries? Han, Yoonjae; Jung, Sung Hoo; Kwak, Hiram Advanced Energy Materials, Vol. 11, Issue 21 https://doi.org/10.1002/aenm.202100126	journal	April 2021
Composite Cathodes for Solid‐State Lithium Batteries: “Catholytes” the Underrated Giants Al-Salih, Hilal; Houache, Mohamed Seif Eddine; Baranova, Elena A. Advanced Energy and Sustainability Research, Vol. 3, Issue 8 https://doi.org/10.1002/aesr.202200032	journal	June 2022
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
Halide Layer Cathodes for Compatible and Fast‐Charged Halides‐Based All‐Solid‐State Li Metal Batteries Liang, Jianwen; Li, Xiaona; Kim, Jung Tae Angewandte Chemie International Edition, Vol. 62, Issue 13 https://doi.org/10.1002/anie.202217081	journal	February 2023
New Oxyhalide Solid Electrolytes with High Lithium Ionic Conductivity >10 mS cm⁻¹ for All‐Solid‐State Batteries Tanaka, Yoshiaki; Ueno, Koki; Mizuno, Keita Angewandte Chemie International Edition, Vol. 62, Issue 13 https://doi.org/10.1002/anie.202217581	journal	February 2023
Characterization of LiFeCl4 and AgFeCl4 ionic conductors Palvadeau, P.; Venien, J.; Spiesser, M. Solid State Ionics, Vol. 6, Issue 3 https://doi.org/10.1016/0167-2738(82)90044-3	journal	May 1982
Li+ conduction in aliovalent-substituted monoclinic Li2ZrCl6 for all-solid-state batteries: Li2+xZr1-xMxCl6 (M = In, Sc) Kwak, Hiram; Han, Daseul; Son, Jun Pyo Chemical Engineering Journal, Vol. 437 https://doi.org/10.1016/j.cej.2022.135413	journal	June 2022
Garnet-type solid-state mixed ionic and electronic conductor Jin, Zongzi; Kong, Xiangkun; Huang, Huang Energy Storage Materials, Vol. 59 https://doi.org/10.1016/j.ensm.2023.102788	journal	May 2023
Mechanical behavior of inorganic lithium-conducting solid electrolytes Papakyriakou, Marc; Lu, Mu; Liu, Yuhgene Journal of Power Sources, Vol. 516 https://doi.org/10.1016/j.jpowsour.2021.230672	journal	December 2021
Modeling assisted synthesis of Zr-doped Li3-xIn1-xZrxCl6 with ultrahigh ionic conductivity for lithium-ion batteries Fu, Jinzhao; Yang, Songge; Hou, Jiahui Journal of Power Sources, Vol. 556 https://doi.org/10.1016/j.jpowsour.2022.232465	journal	February 2023
Anion and cation co-doping of Na4SnS4 as sodium superionic conductors Xiong, Shan; Liu, Zhantao; Yang, Lufeng Materials Today Physics, Vol. 15 https://doi.org/10.1016/j.mtphys.2020.100281	journal	December 2020
Exploring Aliovalent Substitutions in the Lithium Halide Superionic Conductor Li _{3– x} In _{1– x} Zr _x Cl ₆ (0 ≤ x ≤ 0.5) Helm, Bianca; Schlem, Roman; Wankmiller, Björn Chemistry of Materials, Vol. 33, Issue 12 https://doi.org/10.1021/acs.chemmater.1c01348	journal	June 2021
Li ₁₅ P ₄ S ₁₆ Cl ₃ , a Lithium Chlorothiophosphate as a Solid-State Ionic Conductor Liu, Zhantao; Zinkevich, Tatiana; Indris, Sylvio Inorganic Chemistry, Vol. 59, Issue 1 https://doi.org/10.1021/acs.inorgchem.9b01751	journal	December 2019
High Ionic Conductivity Achieved in Li ₃ Y(Br ₃ Cl ₃ ) Mixed Halide Solid Electrolyte via Promoted Diffusion Pathways and Enhanced Grain Boundary Liu, Zhantao; Ma, Shuan; Liu, Jue ACS Energy Letters, Vol. 6, Issue 1 https://doi.org/10.1021/acsenergylett.0c01690	journal	December 2020
Composite Cathode Design for High-Energy All-Solid-State Lithium Batteries with Long Cycle Life Kim, Se Young; Cha, Hyungyeon; Kostecki, Robert ACS Energy Letters, Vol. 8, Issue 1 https://doi.org/10.1021/acsenergylett.2c02414	journal	December 2022
Atmospheric-Pressure Operation of All-Solid-State Batteries Enabled by Halide Solid Electrolyte Hennequart, Benjamin; Platonova, Maria; Chometon, Ronan ACS Energy Letters, Vol. 9, Issue 2 https://doi.org/10.1021/acsenergylett.3c02513	journal	January 2024
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
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
Amorphous Chloride Solid Electrolytes with High Li-Ion Conductivity for Stable Cycling of All-Solid-State High-Nickel Cathodes Li, Feng; Cheng, Xiaobin; Lu, Gongxun Journal of the American Chemical Society, Vol. 145, Issue 50 https://doi.org/10.1021/jacs.3c10602	journal	December 2023
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
Li3TiCl6 as ionic conductive and compressible positive electrode active material for all-solid-state lithium-based batteries Wang, Kai; Gu, Zhenqi; Xi, Zhiwei Nature Communications, Vol. 14, Issue 1 https://doi.org/10.1038/s41467-023-37122-7	journal	March 2023
A cost-effective, ionically conductive and compressible oxychloride solid-state electrolyte for stable all-solid-state lithium-based batteries Hu, Lv; Wang, Jinzhu; Wang, Kai Nature Communications, Vol. 14, Issue 1 https://doi.org/10.1038/s41467-023-39522-1	journal	June 2023
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
High areal capacity, long cycle life 4 V ceramic all-solid-state Li-ion batteries enabled by chloride solid electrolytes Zhou, Laidong; Zuo, Tong-Tong; Kwok, Chun Yuen Nature Energy, Vol. 7, Issue 1 https://doi.org/10.1038/s41560-021-00952-0	journal	January 2022
Challenges in speeding up solid-state battery development Janek, Jürgen; Zeier, Wolfgang G. Nature Energy, Vol. 8, Issue 3 https://doi.org/10.1038/s41560-023-01208-9	journal	February 2023
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
Understanding interface stability in solid-state batteries Xiao, Yihan; Wang, Yan; Bo, Shou-Hang Nature Reviews Materials, Vol. 5, Issue 2 https://doi.org/10.1038/s41578-019-0157-5	journal	December 2019
A LaCl3-based lithium superionic conductor compatible with lithium metal Yin, Yi-Chen; Yang, Jing-Tian; Luo, Jin-Da Nature, Vol. 616, Issue 7955 https://doi.org/10.1038/s41586-023-05899-8	journal	April 2023
Na3SbSe4−xS x as Sodium Superionic Conductors Xiong, Shan; Liu, Zhantao; Rong, Haibo Scientific Reports, Vol. 8, Issue 1 https://doi.org/10.1038/s41598-018-27301-8	journal	June 2018
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
All-solid-state lithium batteries enabled by sulfide electrolytes: from fundamental research to practical engineering design Wang, Changhong; Liang, Jianwen; Zhao, Yang Energy & Environmental Science, Vol. 14, Issue 5 https://doi.org/10.1039/D1EE00551K	journal	January 2021
Understanding the effect of lattice polarisability on the electrochemical properties of lithium tetrahaloaluminates, LiAlX₄ (X = Cl, Br, I) Flores-González, Nicolás; López, Martí; Minafra, Nicolò Journal of Materials Chemistry A, Vol. 10, Issue 25 https://doi.org/10.1039/D2TA02821B	journal	January 2022
High-areal-capacity and long-cycle-life all-solid-state battery enabled by freeze drying technology Ma, Tenghuan; Wang, Zhixuan; Wu, Dengxu Energy & Environmental Science, Vol. 16, Issue 5 https://doi.org/10.1039/D3EE00420A	journal	January 2023
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
Bond softness sensitive bond-valence parameters for crystal structure plausibility tests Chen, Haomin; Adams, Stefan IUCrJ, Vol. 4, Issue 5 https://doi.org/10.1107/S2052252517010211	journal	August 2017
SoftBV – a software tool for screening the materials genome of inorganic fast ion conductors Chen, Haomin; Wong, Lee Loong; Adams, Stefan Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 75, Issue 1 https://doi.org/10.1107/S2052520618015718	journal	January 2019
A universal wet-chemistry synthesis of solid-state halide electrolytes for all-solid-state lithium-metal batteries Wang, Changhong; Liang, Jianwen; Luo, Jing Science Advances, Vol. 7, Issue 37 https://doi.org/10.1126/sciadv.abh1896	journal	September 2021

Similar Records

Optimization of catholyte for halide-based all-solid-state batteries

Journal Article · 2025 · Journal of Power Sources · OSTI ID:2565276

Shen, Fengyu; McGahan, Michael; Pietras, John D.; +3 more

Effects of catholyte aging on high-nickel NMC cathodes in sulfide all-solid-state batteries

Journal Article · 2024 · Materials Horizons · OSTI ID:2569911

Li, Yuanshun; Cho, Yukio; Cai, Jiyu; +9 more

The impact of residual solvent on catholyte performance in solid-state batteries

Journal Article · 2022 · Journal of Materials Chemistry. A · OSTI ID:1904170

Shen, Fengyu; Jonson, Robert A.; Tucker, Michael C.

Related Subjects

36 MATERIALS SCIENCE

Title: Li2.9Fe0.9Zr0.1Cl6 as Redox-Active Catholyte for Solid-State Li-Ion Batteries

Citation Formats

References (42)

Similar Records

Related Subjects

Title: Li_2.9Fe_0.9Zr_0.1Cl₆ as Redox-Active Catholyte for Solid-State Li-Ion Batteries