Theoretical Design of Lithium Chloride Superionic Conductors for All-Solid-State High-Voltage Lithium-Ion Batteries

Park, Dongsu; Park, Haesun; Lee, Yongheum; Kim, Sang-Ok; Jung, Hun-Gi; Chung, Kyung Yoon; Shim, Joon Hyung; Yu, Seungho

doi:10.1021/acsami.0c07003

Theoretical Design of Lithium Chloride Superionic Conductors for All-Solid-State High-Voltage Lithium-Ion Batteries

Journal Article · Thu Jul 09 00:00:00 EDT 2020 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.0c07003· OSTI ID:1661692

Park, Dongsu ^[1]; ^[2]; Lee, Yongheum ^[1]; ^[1]; ^[1]; ^[1]; ^[3]; ^[4]

Korea Inst. of Science and Technology (Korea); Korea Univ., Seoul (Korea)
Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR)
School of Mechanical Engineering, Korea University, 145 Anam-ro, Seongbuk-gu, Seoul 02841, Republic of Korea
Korea Inst. of Science and Technology (Korea)

The development of solid electrolytes (SEs) is a promising pathway to improve the energy density and safety of conventional Li ion batteries. Several lithium chloride SEs, Li₃MCl₆ (M = Y, Er, In, and Sc), have gained popularity due to their high ionic conductivity, wide electrochemical window, and good chemical stability. This study systematically investigated 17 Li₃MCl₆ SEs to identify novel and promising lithium chloride SEs. Calculation results revealed that 12 Li₃MCl₆ (M = Bi, Dy, Er, Ho, In, Lu, Sc, Sm, Tb, TI, Tm, and Y) were stable phase with a wide electrochemical stability window and excellent chemical stability against cathode materials and moisture. Li-ion transport properties were examined using bond valence site energy (BVSE) and ab initio molecular dynamics (AIMD) calculation. Li₃MCl₆ showed the lower migration energy barrier in monoclinic structures, while orthorhombic and trigonal structures exhibited higher energy barriers due to the sluggish diffusion along the two-dimensional path based on the BVSE model. AIMD results confirmed the slower ion migration along the 2D path, exhibiting lower ionic diffusivity and higher activation energy in orthorhombic and trigonal structures. For the further increase of ionic conductivity in monoclinic structures, Li-ion vacancy was formed by the substitution of M³⁺ with Zr⁴⁺. Zr-substituted phase (Li_2.5M_0.5Zr_0.5Cl₆, M = In, Sc) exhibited up to a fourfold increase in ionic conductivity. This finding suggested that the optimization of Li vacancy in the Li₃MCl₆ SEs could lead to superionic Li₃MCl₆ SEs.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1661692

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 31 Vol. 12; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (55)

A Battery Made from a Single Material Han, Fudong; Gao, Tao; Zhu, Yujie Advanced Materials, Vol. 27, Issue 23 https://doi.org/10.1002/adma.201500180	journal	April 2015
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
Borohydride-Scaffolded Li/Na/Mg Fast Ionic Conductors for Promising Solid-State Electrolytes Cuan, Jing; Zhou, You; Zhou, Tengfei Advanced Materials, Vol. 31, Issue 1 https://doi.org/10.1002/adma.201803533	journal	October 2018
Lithium-Ion Batteries: Solid Electrolyte: the Key for High-Voltage Lithium Batteries (Adv. Energy Mater. 4/2015) Li, Juchuan; Ma, Cheng; Chi, Miaofang Advanced Energy Materials, Vol. 5, Issue 4 https://doi.org/10.1002/aenm.201570018	journal	February 2015
Rechargeable Solid-State Li-Air and Li-S Batteries: Materials, Construction, and Challenges Liu, Yijie; He, Ping; Zhou, Haoshen Advanced Energy Materials, Vol. 8, Issue 4 https://doi.org/10.1002/aenm.201701602	journal	September 2017
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
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
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
Water‐Mediated Synthesis of a Superionic Halide Solid Electrolyte Li, Xiaona; Liang, Jianwen; Chen, Ning Angewandte Chemie International Edition, Vol. 58, Issue 46 https://doi.org/10.1002/anie.201909805	journal	November 2019
Neue schnelle Ionenleiter vom Typ MI3MIIICl6 (MI = Li, Na, Ag; MIII = In, Y) Steiner, H. -J.; Lutz, H. D. Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 613, Issue 7 https://doi.org/10.1002/zaac.19926130104	journal	July 1992
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
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
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
Computational Screening of Cathode Coatings for Solid-State Batteries Xiao, Yihan; Miara, Lincoln J.; Wang, Yan Joule, Vol. 3, Issue 5 https://doi.org/10.1016/j.joule.2019.02.006	journal	May 2019
Effect of substitution (Ta, Al, Ga) on the conductivity of Li₇La₃Zr₂O₁₂ Allen, J. L.; Wolfenstine, J.; Rangasamy, E. Journal of Power Sources, Vol. 206, p. 315-319 https://doi.org/10.1016/j.jpowsour.2012.01.131	journal	May 2012
All-solid-state lithium batteries with Li3PS4 glass as active material Hakari, Takashi; Nagao, Motohiro; Hayashi, Akitoshi Journal of Power Sources, Vol. 293 https://doi.org/10.1016/j.jpowsour.2015.05.073	journal	October 2015
Development of the cold sintering process and its application in solid-state lithium batteries Liu, Yulong; Sun, Qian; Wang, Dawei Journal of Power Sources, Vol. 393 https://doi.org/10.1016/j.jpowsour.2018.05.015	journal	July 2018
Recent advances in all-solid-state rechargeable lithium batteries Sun, Chunwen; Liu, Jin; Gong, Yudong Nano Energy, Vol. 33 https://doi.org/10.1016/j.nanoen.2017.01.028	journal	March 2017
Structural change of Li2S–P2S5 sulfide solid electrolytes in the atmosphere Muramatsu, Hiromasa; Hayashi, Akitoshi; Ohtomo, Takamasa Solid State Ionics, Vol. 182, Issue 1 https://doi.org/10.1016/j.ssi.2010.10.013	journal	February 2011
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
Machine Learning-Assisted Discovery of Solid Li-Ion Conducting Materials Sendek, Austin D.; Cubuk, Ekin D.; Antoniuk, Evan R. Chemistry of Materials, Vol. 31, Issue 2 https://doi.org/10.1021/acs.chemmater.8b03272	journal	November 2018
Yttrium–Sodium Halides as Promising Solid-State Electrolytes with High Ionic Conductivity and Stability for Na-Ion Batteries Qie, Yu; Wang, Shuo; Fu, Sijie The Journal of Physical Chemistry Letters, Vol. 11, Issue 9 https://doi.org/10.1021/acs.jpclett.0c00010	journal	April 2020
Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations Zhu, Yizhou; He, Xingfeng; Mo, Yifei ACS Applied Materials & Interfaces, Vol. 7, Issue 42 https://doi.org/10.1021/acsami.5b07517	journal	October 2015
Mitigating the Interfacial Degradation in Cathodes for High-Performance Oxide-Based Solid-State Lithium Batteries Wang, Dawei; Sun, Qian; Luo, Jing ACS Applied Materials & Interfaces, Vol. 11, Issue 5 https://doi.org/10.1021/acsami.8b17881	journal	January 2019
Thermodynamic Assessment of Coating Materials for Solid-State Li, Na, and K Batteries Yu, Seungho; Park, Haesun; Siegel, Donald J. ACS Applied Materials & Interfaces, Vol. 11, Issue 40 https://doi.org/10.1021/acsami.9b11001	journal	September 2019
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
Li−Fe−P−O ₂ Phase Diagram from First Principles Calculations Ong, Shyue Ping; Wang, Lei; Kang, Byoungwoo Chemistry of Materials, Vol. 20, Issue 5 https://doi.org/10.1021/cm702327g	journal	February 2008
Challenges for Rechargeable Li Batteries Goodenough, John B.; Kim, Youngsik Chemistry of Materials, Vol. 22, Issue 3, p. 587-603 https://doi.org/10.1021/cm901452z	journal	February 2010
Data Mined Ionic Substitutions for the Discovery of New Compounds Hautier, Geoffroy; Fischer, Chris; Ehrlacher, Virginie Inorganic Chemistry, Vol. 50, Issue 2 https://doi.org/10.1021/ic102031h	journal	January 2011
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
Issues and challenges facing rechargeable lithium batteries Tarascon, J.-M.; Armand, M. Nature, Vol. 414, Issue 6861, p. 359-367 https://doi.org/10.1038/35104644	journal	November 2001
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
Towards greener and more sustainable batteries for electrical energy storage Larcher, D.; Tarascon, J-M. Nature Chemistry, Vol. 7, Issue 1 https://doi.org/10.1038/nchem.2085	journal	November 2014
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
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
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
Status and challenges in enabling the lithium metal electrode for high-energy and low-cost rechargeable batteries Albertus, Paul; Babinec, Susan; Litzelman, Scott Nature Energy, Vol. 3, Issue 1 https://doi.org/10.1038/s41560-017-0047-2	journal	December 2017
A map of the inorganic ternary metal nitrides Sun, Wenhao; Bartel, Christopher J.; Arca, Elisabetta Nature Materials, Vol. 18, Issue 7 https://doi.org/10.1038/s41563-019-0396-2	journal	June 2019
Clarifying the relationship between redox activity and electrochemical stability in solid electrolytes Schwietert, Tammo K.; Arszelewska, Violetta A.; Wang, Chao Nature Materials, Vol. 19, Issue 4 https://doi.org/10.1038/s41563-019-0576-0	journal	January 2020
High-throughput design and optimization of fast lithium ion conductors by the combination of bond-valence method and density functional theory Xiao, Ruijuan; Li, Hong; Chen, Liquan Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep14227	journal	September 2015
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 unified formulation of the constant temperature molecular dynamics methods Nosé, Shuichi The Journal of Chemical Physics, Vol. 81, Issue 1 https://doi.org/10.1063/1.447334	journal	July 1984
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
Alloying effects on superionic conductivity in lithium indium halides for all-solid-state batteries Zevgolis, Alysia; Wood, Brandon C.; Mehmedović, Zerina APL Materials, Vol. 6, Issue 4 https://doi.org/10.1063/1.5011378	journal	April 2018
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
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Oxidation energies of transition metal oxides within the GGA + U framework Wang, Lei; Maxisch, Thomas; Ceder, Gerbrand Physical Review B, Vol. 73, Issue 19 https://doi.org/10.1103/PhysRevB.73.195107	journal	May 2006
Formation enthalpies by mixing GGA and GGA + U calculations Jain, Anubhav; Hautier, Geoffroy; Ong, Shyue Ping Physical Review B, Vol. 84, Issue 4 https://doi.org/10.1103/PhysRevB.84.045115	journal	July 2011
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
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
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

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