Fast Room-Temperature Mg-Ion Conduction in Clay-Like Halide Glassy Electrolytes

Yang, Xiaochen; Gupta, Sunny; Chen, Yu; Sari, Dogancan; Hau, Han‐Ming; Cai, Zijian; Dun, Chaochao; Qi, Miao; Ma, Lu; Liu, Yi; Urban, Jeffrey J.; Ceder, Gerbrand

doi:10.1002/aenm.202400163

Title: Fast Room-Temperature Mg-Ion Conduction in Clay-Like Halide Glassy Electrolytes

Journal Article · 23 April 2024 · Advanced Energy Materials

DOI: https://doi.org/10.1002/aenm.202400163 · OSTI ID:2367441

^[1]; Gupta, Sunny ^[1]; Chen, Yu ^[1]; Sari, Dogancan ^[1]; Hau, Han‐Ming ^[1]; Cai, Zijian ^[1]; Dun, Chaochao ^[2]; Qi, Miao ^[2]; Ma, Lu ^[3]; Liu, Yi ^[2]; Urban, Jeffrey J. ^[2];

^[1]

Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)

The discovery of mechanically soft solid-state materials with fast Mg-ion conduction is crucial for the development of solid-state magnesium batteries. In this paper, novel magnesium gallium halide compounds are reported that achieve high ionic conductivity of 0.47 mS cm^-1 at room temperature. These Mg-ion conductors obtained by ball milling Mg and Ga salts exhibit clay-like mechanical properties, enabling intimate contact at the electrode–electrolyte interface during battery cycling. With a combination of experimental and computational analysis, this study identifies that the soft-clay formation is induced by partial anion exchange during milling. This partial anion exchange creates undercoordinated magnesium ions in a chlorine-rich environment, yielding fast Mg-ion conduction. This work demonstrates the potential of clay-like halide electrolytes for all-solid-state magnesium batteries, with possible further extension to other multivalent battery systems.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO)

Grant/Contract Number:: SC0012704; AC02-05CH11231

OSTI ID:: 2367441

Report Number(s):: BNL--225627-2024-JAAM

Journal Information:: Advanced Energy Materials, Journal Name: Advanced Energy Materials Journal Issue: 26 Vol. 14; ISSN 1614-6832

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (69)

Theoretical study on the initial stage of a magnesium battery based on a V ₂ O ₅ cathode Zhou, Bo; Shi, Hui; Cao, Rongfang Phys. Chem. Chem. Phys., Vol. 16, Issue 34 https://doi.org/10.1039/C4CP02230K	journal	January 2014
A rapid solid-state synthesis of electrochemically active Chevrel phases (Mo6T8; T = S, Se) for rechargeable magnesium batteries Saha, Partha; Jampani, Prashanth H.; Datta, Moni K. Nano Research, Vol. 10, Issue 12 https://doi.org/10.1007/s12274-017-1695-z	journal	August 2017
Toward Understanding the Different Influences of Grain Boundaries on Ion Transport in Sulfide and Oxide Solid Electrolytes Dawson, James A.; Canepa, Pieremanuele; Clarke, Matthew J. Chemistry of Materials, Vol. 31, Issue 14 https://doi.org/10.1021/acs.chemmater.9b01794	journal	June 2019
Design and Characterization of Host Frameworks for Facile Magnesium Transport Gao, Yirong; Mishra, Tara P.; Bo, Shou-Hang Annual Review of Materials Research, Vol. 52, Issue 1 https://doi.org/10.1146/annurev-matsci-081420-041617	journal	July 2022
Dynamic Ion Correlations in Solid and Liquid Electrolytes: How Do They Affect Charge and Mass Transport? Vargas‐Barbosa, N. M.; Roling, B. ChemElectroChem, Vol. 7, Issue 2 https://doi.org/10.1002/celc.201901627	journal	November 2019
Kinetic and Thermodynamic Studies of Mg[sup 2+] and Li[sup +] Ion Insertion into the Mo[sub 6]S[sub 8] Chevrel Phase Levi, M. D.; Lancry, E.; Gizbar, H. Journal of The Electrochemical Society, Vol. 151, Issue 7 https://doi.org/10.1149/1.1758811	journal	January 2004
Progress and perspective of the cathode/electrolyte interface construction in all‐solid‐state lithium batteries Su, Shiming; Ma, Jiabin; Zhao, Liang Carbon Energy, Vol. 3, Issue 6 https://doi.org/10.1002/cey2.129	journal	July 2021
Python Materials Genomics (pymatgen): A robust, open-source python library for materials analysis Ong, Shyue Ping; Richards, William Davidson; Jain, Anubhav Computational Materials Science, Vol. 68 https://doi.org/10.1016/j.commatsci.2012.10.028	journal	February 2013
Modulating Entropic Driving Forces to Promote High Lithium Mobility in Solid Organic Electrolytes McAlpine, Jack; Bloemendal, Alex; Dahl, Jeremy E. Chemistry of Materials, Vol. 35, Issue 9 https://doi.org/10.1021/acs.chemmater.3c00141	journal	April 2023
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Elucidating Solvation Structures for Rational Design of Multivalent Electrolytes—A Review Rajput, Nav Nidhi; Seguin, Trevor J.; Wood, Brandon M. Topics in Current Chemistry, Vol. 376, Issue 3 https://doi.org/10.1007/s41061-018-0195-2	journal	April 2018
Room Temperature Halide‐Eutectic Solid Electrolytes with Viscous Feature and Ultrahigh Ionic Conductivity Xu, Ruonan; Yao, Jingming; Zhang, Ziqi Advanced Science, Vol. 9, Issue 35 https://doi.org/10.1002/advs.202204633	journal	October 2022
Novel, electrolyte solutions comprising fully inorganic salts with high anodic stability for rechargeable magnesium batteries Doe, Robert E.; Han, Ruoban; Hwang, Jaehee Chemical Communications, Vol. 50, Issue 2, p. 243-245 https://doi.org/10.1039/C3CC47896C	journal	January 2014
Commentary: The Materials Project: A materials genome approach to accelerating materials innovation Jain, Anubhav; Ong, Shyue Ping; Hautier, Geoffroy APL Materials, Vol. 1, Issue 1 https://doi.org/10.1063/1.4812323	journal	July 2013
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Magnesium Borohydride Ammonia Borane as a Magnesium Ionic Conductor Kisu, Kazuaki; Kim, Sangryun; Inukai, Munehiro ACS Applied Energy Materials, Vol. 3, Issue 4 https://doi.org/10.1021/acsaem.0c00113	journal	March 2020
A Review of Magnesium Aluminum Chloride Complex Electrolytes for Mg Batteries Li, Yaqi; Guan, Shaoliang; Huo, Hua Advanced Functional Materials, Vol. 31, Issue 24 https://doi.org/10.1002/adfm.202100650	journal	March 2021
A family of oxychloride amorphous solid electrolytes for long-cycling all-solid-state lithium batteries Zhang, Shumin; Zhao, Feipeng; Chen, Jiatang Nature Communications, Vol. 14, Issue 1 https://doi.org/10.1038/s41467-023-39197-8	journal	June 2023
Effects of Mg2+ interstitial ion on the properties of Mg0.5+x/2Si2-xAlx(PO4)3 ceramic electrolytes Halim, Z. A.; Adnan, S. B. R. S.; Salleh, F. M. Journal of Magnesium and Alloys, Vol. 5, Issue 4 https://doi.org/10.1016/j.jma.2017.09.005	journal	December 2017
Interface Stability in Solid-State Batteries Richards, William D.; Miara, Lincoln J.; Wang, Yan Chemistry of Materials, Vol. 28, Issue 1 https://doi.org/10.1021/acs.chemmater.5b04082	journal	December 2015
Deep Potential Molecular Dynamics: A Scalable Model with the Accuracy of Quantum Mechanics Zhang, Linfeng; Han, Jiequn; Wang, Han Physical Review Letters, Vol. 120, Issue 14 https://doi.org/10.1103/PhysRevLett.120.143001	journal	April 2018
The Coupling between Stability and Ion Pair Formation in Magnesium Electrolytes from First-Principles Quantum Mechanics and Classical Molecular Dynamics Rajput, Nav Nidhi; Qu, Xiaohui; Sa, Niya Journal of the American Chemical Society, Vol. 137, Issue 9, p. 3411-3420 https://doi.org/10.1021/jacs.5b01004	journal	February 2015
High magnesium mobility in ternary spinel chalcogenides Canepa, Pieremanuele; Bo, Shou-Hang; Sai Gautam, Gopalakrishnan Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-01772-1	journal	November 2017
Promises and Challenges of Next-Generation “Beyond Li-ion” Batteries for Electric Vehicles and Grid Decarbonization Tian, Yaosen; Zeng, Guobo; Rutt, Ann Chemical Reviews, Vol. 121, Issue 3 https://doi.org/10.1021/acs.chemrev.0c00767	journal	December 2020
Strategies to Enable Reversible Magnesium Electrochemistry: From Electrolytes to Artificial Solid–Electrolyte Interphases Liang, Zhiming; Ban, Chunmei Angewandte Chemie International Edition, Vol. 60, Issue 20 https://doi.org/10.1002/anie.202006472	journal	January 2021
Processing liquid-feed flame spray pyrolysis synthesized Mg 0.5 Ce 0.2 Zr 1.8 (PO 4 ) 3 nanopowders to free standing thin films and pellets as potential electrolytes in all-solid-state Mg batteries Liang, B.; Keshishian, V.; Liu, S. Electrochimica Acta, Vol. 272 https://doi.org/10.1016/j.electacta.2018.04.015	journal	May 2018
Recent Development of Mg Ion Solid Electrolyte Zhan, Yi; Zhang, Wei; Lei, Bing Frontiers in Chemistry, Vol. 8 https://doi.org/10.3389/fchem.2020.00125	journal	February 2020
Pliable Lithium Superionic Conductor for All-Solid-State Batteries Jung, Sung-Kyun; Gwon, Hyeokjo; Yoon, Gabin ACS Energy Letters, Vol. 6, Issue 5 https://doi.org/10.1021/acsenergylett.1c00545	journal	May 2021
Ammine Magnesium Borohydride Nanocomposites for All-Solid-State Magnesium Batteries Yan, Yigang; Grinderslev, Jakob B.; Jo̷rgensen, Mathias ACS Applied Energy Materials, Vol. 3, Issue 9 https://doi.org/10.1021/acsaem.0c01599	journal	August 2020
Lithium Oxide Superionic Conductors Inspired by Garnet and NASICON Structures Xiao, Yihan; Jun, KyuJung; Wang, Yan Advanced Energy Materials, Vol. 11, Issue 37 https://doi.org/10.1002/aenm.202101437	journal	September 2021
High Li ⁺ and Mg ²⁺ Conductivity in a Cu-Azolate Metal–Organic Framework Miner, Elise M.; Park, Sarah S.; Dincă, Mircea Journal of the American Chemical Society, Vol. 141, Issue 10 https://doi.org/10.1021/jacs.8b13418	journal	February 2019
In Situ X-Ray Absorption Study of a Layered Manganese-Chromium Oxide-Based Cathode Material Balasubramanian, M.; McBreen, J.; Davidson, I. J. Journal of The Electrochemical Society, Vol. 149, Issue 2 https://doi.org/10.1149/1.1431962	journal	January 2002
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
Experimental investigations of an ionic-liquid-based, magnesium ion conducting, polymer gel electrolyte Pandey, G. P.; Hashmi, S. A. Journal of Power Sources, Vol. 187, Issue 2 https://doi.org/10.1016/j.jpowsour.2008.10.112	journal	February 2009
Statistical variances of diffusional properties from ab initio molecular dynamics simulations He, Xingfeng; Zhu, Yizhou; Epstein, Alexander npj Computational Materials, Vol. 4, Issue 1 https://doi.org/10.1038/s41524-018-0074-y	journal	April 2018
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
Solid electrolytes with multivalent cation conduction. 1. Conducting species in MgZrPO4 system Ikeda, S.; Takahashi, M.; Ishikawa, J. Solid State Ionics, Vol. 23, Issue 1-2 https://doi.org/10.1016/0167-2738(87)90091-9	journal	March 1987
Quest for Nonaqueous Multivalent Secondary Batteries: Magnesium and Beyond Muldoon, John; Bucur, Claudiu B.; Gregory, Thomas Chemical Reviews, Vol. 114, Issue 23 https://doi.org/10.1021/cr500049y	journal	October 2014
High‐Energy Lithium‐Ion Batteries: Recent Progress and a Promising Future in Applications Xu, Jingjing; Cai, Xingyun; Cai, Songming ENERGY & ENVIRONMENTAL MATERIALS, Vol. 6, Issue 5 https://doi.org/10.1002/eem2.12450	journal	January 2023
Magnesium Ethylenediamine Borohydride as Solid-State Electrolyte for Magnesium Batteries Roedern, Elsa; Kühnel, Ruben-Simon; Remhof, Arndt Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/srep46189	journal	April 2017
Effect of Electrolytic Properties of a Magnesium Organohaloaluminate Electrolyte on Magnesium Deposition Benmayza, Aadil; Ramanathan, Mayandi; Arthur, Timothy S. The Journal of Physical Chemistry C, Vol. 117, Issue 51, p. 26881-26888 https://doi.org/10.1021/jp4077068	journal	December 2013
To Be or Not to Be – Is MgSc₂Se₄ a Mg‐Ion Solid Electrolyte? Glaser, Clarissa; Wei, Zhixuan; Indris, Sylvio Advanced Energy Materials, Vol. 13, Issue 40 https://doi.org/10.1002/aenm.202301980	journal	September 2023
Solid-State Calcium-Ion Diffusion in Ca_1.5Ba_0.5Si₅O₃N₆ Chen, Yu; Bartel, Christopher J.; Avdeev, Maxim Chemistry of Materials, Vol. 34, Issue 1 https://doi.org/10.1021/acs.chemmater.1c02923	journal	December 2021
Simple method to determine electronic and ionic components of the conductivity in mixed conductors a review Huggins, R. A. Ionics, Vol. 8, Issue 3-4 https://doi.org/10.1007/BF02376083	journal	May 2002
The mechanism of Mg ²⁺ conduction in ammine magnesium borohydride promoted by a neutral molecule Yan, Yigang; Dononelli, Wilke; Jørgensen, Mathias Physical Chemistry Chemical Physics, Vol. 22, Issue 17 https://doi.org/10.1039/D0CP00158A	journal	January 2020
DeePMD-kit: A deep learning package for many-body potential energy representation and molecular dynamics Wang, Han; Zhang, Linfeng; Han, Jiequn Computer Physics Communications, Vol. 228 https://doi.org/10.1016/j.cpc.2018.03.016	journal	July 2018
Interface engineering of inorganic solid-state electrolytes for high-performance lithium metal batteries Miao, Xianguang; Wang, Huiyang; Sun, Rui Energy & Environmental Science, Vol. 13, Issue 11 https://doi.org/10.1039/D0EE01435D	journal	January 2020
Elucidating the structure of the magnesium aluminum chloride complex electrolyte for magnesium-ion batteries Canepa, Pieremanuele; Jayaraman, Saivenkataraman; Cheng, Lei Energy & Environmental Science, Vol. 8, Issue 12 https://doi.org/10.1039/C5EE02340H	journal	January 2015
Lithium superionic conductors with corner-sharing frameworks Jun, KyuJung; Sun, Yingzhi; Xiao, Yihan Nature Materials, Vol. 21, Issue 8 https://doi.org/10.1038/s41563-022-01222-4	journal	March 2022
How Is Charge Transport Different in Ionic Liquids and Electrolyte Solutions? Kashyap, Hemant K.; Annapureddy, Harsha V. R.; Raineri, Fernando O. The Journal of Physical Chemistry B, Vol. 115, Issue 45 https://doi.org/10.1021/jp204182c	journal	November 2011
Halide‐based solid electrolytes: The history, progress, and challenges Nie, Xianhui; Hu, Jiulin; Li, Chilin Interdisciplinary Materials, Vol. 2, Issue 3 https://doi.org/10.1002/idm2.12090	journal	May 2023
A study on blend polymer electrolyte based on poly(vinyl alcohol)-poly (acrylonitrile) with magnesium nitrate for magnesium battery Manjuladevi, R.; Selvasekarapandian, S.; Thamilselvan, M. Ionics, Vol. 24, Issue 11 https://doi.org/10.1007/s11581-018-2500-z	journal	March 2018
Structural and Compositional Factors That Control the Li-Ion Conductivity in LiPON Electrolytes Lacivita, Valentina; Artrith, Nongnuch; Ceder, Gerbrand Chemistry of Materials, Vol. 30, Issue 20 https://doi.org/10.1021/acs.chemmater.8b02812	journal	September 2018
Super Mg²⁺ Conductivity around 10^–3 S cm^–1 Observed in a Porous Metal–Organic Framework Yoshida, Yuto; Yamada, Teppei; Jing, Yuan Journal of the American Chemical Society, Vol. 144, Issue 19 https://doi.org/10.1021/jacs.2c01612	journal	May 2022
Robust Self‐Standing Single‐Ion Polymer Electrolytes Enabling High‐Safety Magnesium Batteries at Elevated Temperature Ge, Xuesong; Song, Fuchen; Du, Aobing Advanced Energy Materials, Vol. 12, Issue 31 https://doi.org/10.1002/aenm.202201464	journal	June 2022
Molecular Dynamics Investigation of Correlations in Ion Transport in MeTFSI/EMIM–TFSI (Me = Li, Na) Electrolytes Kubisiak, Piotr; Wróbel, Piotr; Eilmes, Andrzej The Journal of Physical Chemistry B, Vol. 124, Issue 2 https://doi.org/10.1021/acs.jpcb.9b10391	journal	December 2019
Thermodynamic Origin of Irreversible Magnesium Trapping in Chevrel Phase Mo ₆ S ₈ : Importance of Magnesium and Vacancy Ordering Ling, Chen; Suto, Koji Chemistry of Materials, Vol. 29, Issue 8 https://doi.org/10.1021/acs.chemmater.7b00772	journal	April 2017
Prototype systems for rechargeable magnesium batteries Aurbach, D.; Lu, Z.; Schechter, A. Nature, Vol. 407, Issue 6805, p. 724-727 https://doi.org/10.1038/35037553	journal	October 2000
A materials perspective on magnesium-ion-based solid-state electrolytes Jaschin, Prem Wicram; Gao, Yirong; Li, Yao Journal of Materials Chemistry A, Vol. 8, Issue 6 https://doi.org/10.1039/C9TA11729F	journal	January 2020
Ion Correlation and Collective Dynamics in BMIM/BF ₄ -Based Organic Electrolytes: From Dilute Solutions to the Ionic Liquid Limit McDaniel, Jesse G.; Son, Chang Yun The Journal of Physical Chemistry B, Vol. 122, Issue 28 https://doi.org/10.1021/acs.jpcb.8b04886	journal	June 2018
Halide Solid‐State Electrolytes: Stability and Application for High Voltage All‐Solid‐State Li Batteries Nikodimos, Yosef; Su, Wei‐Nien; Hwang, Bing Joe Advanced Energy Materials, Vol. 13, Issue 3 https://doi.org/10.1002/aenm.202202854	journal	November 2022
Structural, electronic, and dielectric properties of amorphous Zr O 2 from ab initio molecular dynamics Zhao, Xinyuan; Ceresoli, Davide; Vanderbilt, David Physical Review B, Vol. 71, Issue 8 https://doi.org/10.1103/PhysRevB.71.085107	journal	February 2005
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
MgSc ₂ Se ₄ —A Magnesium Solid Ionic Conductor for All‐Solid‐State Mg Batteries? Wang, Li‐Ping; Zhao‐Karger, Zhirong; Klein, Franziska ChemSusChem, Vol. 12, Issue 10 https://doi.org/10.1002/cssc.201900225	journal	April 2019
Halide solid-state electrolytes for all-solid-state batteries: structural design, synthesis, environmental stability, interface optimization and challenges Tao, Boran; Zhong, Dailin; Li, Hongda Chemical Science, Vol. 14, Issue 33 https://doi.org/10.1039/D3SC02093B	journal	January 2023
Ion Correlations and Their Impact on Transport in Polymer-Based Electrolytes Fong, Kara D.; Self, Julian; McCloskey, Bryan D. Macromolecules, Vol. 54, Issue 6 https://doi.org/10.1021/acs.macromol.0c02545	journal	February 2021
Strain Localization and Percolation of Stable Structure in Amorphous Solids Shi, Yunfeng; Falk, Michael L. Physical Review Letters, Vol. 95, Issue 9 https://doi.org/10.1103/PhysRevLett.95.095502	journal	August 2005
LAMMPS - a flexible simulation tool for particle-based materials modeling at the atomic, meso, and continuum scales Thompson, Aidan P.; Aktulga, H. Metin; Berger, Richard Computer Physics Communications, Vol. 271 https://doi.org/10.1016/j.cpc.2021.108171	journal	February 2022
What dictates soft clay-like lithium superionic conductor formation from rigid salts mixture Gupta, Sunny; Yang, Xiaochen; Ceder, Gerbrand Nature Communications, Vol. 14, Issue 1 https://doi.org/10.1038/s41467-023-42538-2	journal	October 2023

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36 MATERIALS SCIENCE
clay formation
magnesium-ion battery
MD simulations
solid state conductors

Title: Fast Room-Temperature Mg-Ion Conduction in Clay-Like Halide Glassy Electrolytes

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