Highly Conductive Iodine and Fluorine Dual-Doped Argyrodite Solid Electrolyte for Lithium Metal Batteries

Arnold, William; Shreyas, Varun; Akter, Sharmin; Li, Yang; Halacoglu, Selim; Kalutara Koralalage, Milinda B.; Guo, Xiaolin; Vithanage, Dinushika; Wei, Wei; Sumanasekera, Gamini; Jasinski, Jacek B.; Narayanan, Badri; Wang, Hui

doi:10.1021/acs.jpcc.3c00962

Highly Conductive Iodine and Fluorine Dual-Doped Argyrodite Solid Electrolyte for Lithium Metal Batteries

Journal Article · Fri Jun 16 04:00:00 EDT 2023 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.3c00962· OSTI ID:2370131

Arnold, William ^[1]; Shreyas, Varun ^[2]; ^[2]; ^[2]; Halacoglu, Selim ^[2]; Kalutara Koralalage, Milinda B. ^[2]; Guo, Xiaolin ^[2]; Vithanage, Dinushika ^[2]; Wei, Wei ^[3]; Sumanasekera, Gamini ^[2]; ^[2]; Narayanan, Badri ^[2]; ^[2]

University of Louisville, KY (United States); University of Louisville
University of Louisville, KY (United States)
Wichita State University, KS (United States)

Sulfide-type argyrodite solid electrolytes (SEs) with halide doping have attracted serious interest. Although other halides such as Cl and Br have been found to enhance Li-ion transport in argyrodites, the direct synthesis of efficiently conductive Li₆PS₅I without postprocessing has rarely been investigated. In this work, we report the one-step synthesis of highly conductive Li₆PS₅I with an impressive ionic conductivity of 2.5 × 10^–4 S cm^–1 at room temperature through a solvent-based method. Moreover, by introducing F^– to partially replace I^–, hybrid-doped argyrodites Li₆PS₅F_xI_1–x (x = 0.25, 0.5, 0.75) have been synthesized. Li₆PS₅F_0.25I_0.75 achieves the highest conductivity of 3.5 × 10^–4 S cm^–1 due to the energetic preference for anion-disordering among F^–/I^– and S^2–, which facilitate faster Li transport as supported by density functional theory (DFT) calculations. With higher F content in argyrodites, Li₆PS₅F_0.75I_0.25 displays the best electrochemical stability toward Li metal, as evidenced by long-term stable cycling in Li symmetric cells up to 1100 h. Solid-state Li metal batteries with an active cathode of Li₄Ti₅O₁₂ (LTO) display an initial specific capacity of 140 mAh g^–1 and remain at 105 mAh g^–1 after 200 cycles, suggesting great battery cycling performance. Furthermore, this research has developed new compositions in the argyrodite SE family which could lead to advancements in the development of solid-state Li metal batteries.

View Accepted Manuscript (DOE)

Research Organization:: University of Louisville, KY (United States)

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

Grant/Contract Number:: EE0008866; AC02-05CH11231

OSTI ID:: 2370131

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 25 Vol. 127; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (55)

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
A Highly Reversible, Dendrite‐Free Lithium Metal Anode Enabled by a Lithium‐Fluoride‐Enriched Interphase Cui, Chunyu; Yang, Chongyin; Eidson, Nico Advanced Materials, Vol. 32, Issue 12 https://doi.org/10.1002/adma.201906427	journal	March 2020
Sustained Release‐Driven Formation of Ultrastable SEI between Li ₆ PS ₅ Cl and Lithium Anode for Sulfide‐Based Solid‐State Batteries Chen, Ya; Li, Wenwen; Sun, Changzhi Advanced Energy Materials, Vol. 11, Issue 4 https://doi.org/10.1002/aenm.202002545	journal	December 2020
Impact of Solvent Treatment of the Superionic Argyrodite Li ₆ PS ₅ Cl on Solid‐State Battery Performance Ruhl, Justine; Riegger, Luise M.; Ghidiu, Michael Advanced Energy and Sustainability Research, Vol. 2, Issue 2 https://doi.org/10.1002/aesr.202000077	journal	January 2021
Studies of lithium argyrodite solid electrolytes for all-solid-state batteries Rao, R. P.; Adams, S. physica status solidi (a), Vol. 208, Issue 8 https://doi.org/10.1002/pssa.201001117	journal	June 2011
Li7PS6 and Li6PS5X (X: Cl, Br, I): Possible Three-dimensional Diffusion Pathways for Lithium Ions and Temperature Dependence of the Ionic Conductivity by Impedance Measurements Deiseroth, Hans-Jörg; Maier, Joachim; Weichert, Katja Zeitschrift für anorganische und allgemeine Chemie, Vol. 637, Issue 10 https://doi.org/10.1002/zaac.201100158	journal	August 2011
Variation in structure and Li+-ion migration in argyrodite-type Li6PS5X (X = Cl, Br, I) solid electrolytes Rayavarapu, Prasada Rao; Sharma, Neeraj; Peterson, Vanessa K. Journal of Solid State Electrochemistry, Vol. 16, Issue 5 https://doi.org/10.1007/s10008-011-1572-8	journal	October 2011
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
Interface control for high-performance all-solid-state Li thin-film batteries Kim, Jong Heon; Xiao, Cheng-Fan; Han, Jonghyun Ceramics International, Vol. 46, Issue 12 https://doi.org/10.1016/j.ceramint.2020.05.063	journal	August 2020
Interface stability of LiCl-rich argyrodite Li6PS5Cl with propylene carbonate boosts high-performance lithium batteries Li, Yang; Arnold, William; Jasinski, Jacek B. Electrochimica Acta, Vol. 363 https://doi.org/10.1016/j.electacta.2020.137128	journal	December 2020
Li metal batteries and solid state batteries benefiting from halogen-based strategies Yang, Qifan; Li, Chilin Energy Storage Materials, Vol. 14 https://doi.org/10.1016/j.ensm.2018.02.017	journal	September 2018
Enabling ultrafast ionic conductivity in Br-based lithium argyrodite electrolytes for solid-state batteries with different anodes Yu, Chuang; Li, Yong; Li, Weihan Energy Storage Materials, Vol. 30 https://doi.org/10.1016/j.ensm.2020.04.014	journal	September 2020
Regulated lithium ionic flux through well-aligned channels for lithium dendrite inhibition in solid-state batteries Li, Yang; Cao, Daxian; Arnold, William Energy Storage Materials, Vol. 31 https://doi.org/10.1016/j.ensm.2020.06.029	journal	October 2020
All-solid-state batteries with slurry coated LiNi0.8Co0.1Mn0.1O2 composite cathode and Li6PS5Cl electrolyte: Effect of binder content Zhang, Jun; Zhong, Haoyue; Zheng, Chao Journal of Power Sources, Vol. 391 https://doi.org/10.1016/j.jpowsour.2018.04.069	journal	July 2018
A lithium argyrodite Li6PS5Cl0.5Br0.5 electrolyte with improved bulk and interfacial conductivity Wang, Heng; Yu, Chuang; Ganapathy, Swapna Journal of Power Sources, Vol. 412 https://doi.org/10.1016/j.jpowsour.2018.11.029	journal	February 2019
Poly(ethylene oxide) reinforced Li6PS5Cl composite solid electrolyte for all-solid-state lithium battery: Enhanced electrochemical performance, mechanical property and interfacial stability Zhang, Jun; Zheng, Chao; Lou, Jiatao Journal of Power Sources, Vol. 412 https://doi.org/10.1016/j.jpowsour.2018.11.036	journal	February 2019
Enhancing ionic conductivity of solid electrolyte by lithium substitution in halogenated Li-Argyrodite Zhang, Zhuoran; Zhang, Jianxing; Jia, Huanhuan Journal of Power Sources, Vol. 450 https://doi.org/10.1016/j.jpowsour.2019.227601	journal	February 2020
Halide doping effect on solvent-synthesized lithium argyrodites Li6PS5X (X= Cl, Br, I) superionic conductors Arnold, William; Buchberger, Dominika A.; Li, Yang Journal of Power Sources, Vol. 464 https://doi.org/10.1016/j.jpowsour.2020.228158	journal	July 2020
Mechanochemical synthesis of Li-argyrodite Li6PS5X (X=Cl, Br, I) as sulfur-based solid electrolytes for all solid state batteries application Boulineau, Sylvain; Courty, Matthieu; Tarascon, Jean-Marie Solid State Ionics, Vol. 221 https://doi.org/10.1016/j.ssi.2012.06.008	journal	August 2012
Interfacial reactivity and interphase growth of argyrodite solid electrolytes at lithium metal electrodes Wenzel, Sebastian; Sedlmaier, Stefan J.; Dietrich, Christian Solid State Ionics, Vol. 318 https://doi.org/10.1016/j.ssi.2017.07.005	journal	May 2018
Achieving superior ionic conductivity of Li6PS5I via introducing LiCl Liao, Cong; Yu, Chuang; Peng, Linfeng Solid State Ionics, Vol. 377 https://doi.org/10.1016/j.ssi.2022.115871	journal	April 2022
Understanding the Origin of Enhanced Li-Ion Transport in Nanocrystalline Argyrodite-Type Li ₆ PS ₅ I Brinek, Marina; Hiebl, Caroline; Wilkening, H. Martin R. Chemistry of Materials, Vol. 32, Issue 11 https://doi.org/10.1021/acs.chemmater.0c01367	journal	May 2020
Diffusion Mechanism of Li Argyrodite Solid Electrolytes for Li-Ion Batteries and Prediction of Optimized Halogen Doping: The Effect of Li Vacancies, Halogens, and Halogen Disorder de Klerk, Niek J. J.; Rosłoń, Irek; Wagemaker, Marnix Chemistry of Materials, Vol. 28, Issue 21 https://doi.org/10.1021/acs.chemmater.6b03630	journal	October 2016
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
Ionic Conductivity and Its Dependence on Structural Disorder in Halogenated Argyrodites Li ₆ PS ₅ X (X = Br, Cl, I) Stamminger, Andreas R.; Ziebarth, Benedikt; Mrovec, Matous Chemistry of Materials, Vol. 31, Issue 21 https://doi.org/10.1021/acs.chemmater.9b02047	journal	October 2019
Garnet-Type Solid-State Electrolytes: Materials, Interfaces, and Batteries Wang, Chengwei; Fu, Kun; Kammampata, Sanoop Palakkathodi Chemical Reviews, Vol. 120, Issue 10 https://doi.org/10.1021/acs.chemrev.9b00427	journal	April 2020
Tailoring Solution-Processable Li Argyrodites Li _{6+ x} P _{1– x} M _x S ₅ I (M = Ge, Sn) and Their Microstructural Evolution Revealed by Cryo-TEM for All-Solid-State Batteries Song, Yong Bae; Kim, Dong Hyeon; Kwak, Hiram Nano Letters, Vol. 20, Issue 6 https://doi.org/10.1021/acs.nanolett.0c01028	journal	May 2020
Lithium-Ion-Conducting Argyrodite-Type Li ₆ PS ₅ X (X = Cl, Br, I) Solid Electrolytes Prepared by a Liquid-Phase Technique Using Ethanol as a Solvent Yubuchi, So; Uematsu, Miwa; Deguchi, Minako ACS Applied Energy Materials, Vol. 1, Issue 8 https://doi.org/10.1021/acsaem.8b00280	journal	July 2018
Silicon-Doped Argyrodite Solid Electrolyte Li ₆ PS ₅ I with Improved Ionic Conductivity and Interfacial Compatibility for High-Performance All-Solid-State Lithium Batteries Zhang, Jun; Li, Lujie; Zheng, Chao ACS Applied Materials & Interfaces, Vol. 12, Issue 37 https://doi.org/10.1021/acsami.0c11683	journal	August 2020
Robust Li₆PS₅I Interlayer to Stabilize the Tailored Electrolyte Li_9.95SnP₂S_11.95F_0.05/Li Metal Interface Jiang, Zhao; Li, Zhongxu; Wang, Xiuli ACS Applied Materials & Interfaces, Vol. 13, Issue 26 https://doi.org/10.1021/acsami.1c07947	journal	June 2021
Synthesis of Fluorine-Doped Lithium Argyrodite Solid Electrolytes for Solid-State Lithium Metal Batteries Arnold, William; Shreyas, Varun; Li, Yang ACS Applied Materials & Interfaces, Vol. 14, Issue 9 https://doi.org/10.1021/acsami.1c24468	journal	February 2022
Rapid and Economic Synthesis of a Li ₇ PS ₆ Solid Electrolyte from a Liquid Approach Ziolkowska, Dominika A.; Arnold, William; Druffel, Thad ACS Applied Materials & Interfaces, Vol. 11, Issue 6 https://doi.org/10.1021/acsami.8b19181	journal	January 2019
Ultrastable Anode Interface Achieved by Fluorinating Electrolytes for All-Solid-State Li Metal Batteries Zhao, Feipeng; Sun, Qian; Yu, Chuang ACS Energy Letters, Vol. 5, Issue 4 https://doi.org/10.1021/acsenergylett.0c00207	journal	March 2020
Solvent-Engineered Design of Argyrodite Li ₆ PS ₅ X (X = Cl, Br, I) Solid Electrolytes with High Ionic Conductivity Zhou, Laidong; Park, Kern-Ho; Sun, Xiaoqi ACS Energy Letters, Vol. 4, Issue 1 https://doi.org/10.1021/acsenergylett.8b01997	journal	November 2018
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
Thermal Stability between Sulfide Solid Electrolytes and Oxide Cathode Wang, Shuo; Wu, Yujing; Ma, Tenghuan ACS Nano, Vol. 16, Issue 10 https://doi.org/10.1021/acsnano.2c04905	journal	October 2022
Superionic Si-Substituted Lithium Argyrodite Sulfide Electrolyte Li _{6+ x} Sb _{1– x} Si _x S ₅ I for All-Solid-State Batteries Lee, Yongheum; Jeong, Jiwon; Lim, Hee-Dae ACS Sustainable Chemistry & Engineering, Vol. 9, Issue 1 https://doi.org/10.1021/acssuschemeng.0c05549	journal	December 2020
Influence of Lattice Polarizability on the Ionic Conductivity in the Lithium Superionic Argyrodites Li ₆ PS ₅ X (X = Cl, Br, I) Kraft, Marvin A.; Culver, Sean P.; Calderon, Mario Journal of the American Chemical Society, Vol. 139, Issue 31 https://doi.org/10.1021/jacs.7b06327	journal	July 2017
Accessing the bottleneck in all-solid state batteries, lithium-ion transport over the solid-electrolyte-electrode interface Yu, Chuang; Ganapathy, Swapna; Eck, Ernst R. H. van Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-01187-y	journal	October 2017
Diffusion of lithium ions in Lithium-argyrodite solid-state electrolytes Baktash, Ardeshir; Reid, James C.; Roman, Tanglaw npj Computational Materials, Vol. 6, Issue 1 https://doi.org/10.1038/s41524-020-00432-1	journal	October 2020
New horizons for inorganic solid state ion conductors Zhang, Zhizhen; Shao, Yuanjun; Lotsch, Bettina Energy & Environmental Science, Vol. 11, Issue 8 https://doi.org/10.1039/C8EE01053F	journal	January 2018
An argyrodite sulfide-based superionic conductor synthesized by a liquid-phase technique with tetrahydrofuran and ethanol Yubuchi, So; Uematsu, Miwa; Hotehama, Chie Journal of Materials Chemistry A, Vol. 7, Issue 2 https://doi.org/10.1039/C8TA09477B	journal	January 2019
Substitutional disorder: structure and ion dynamics of the argyrodites Li 6 PS 5 Cl, Li 6 PS 5 Br and Li 6 PS 5 I Hanghofer, I.; Brinek, M.; Eisbacher, S. L. Physical Chemistry Chemical Physics, Vol. 21, Issue 16 https://doi.org/10.1039/C9CP00664H	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
Quantitative analysis of crystallinity in an argyrodite sulfide-based solid electrolyte synthesized via solution processing Yubuchi, So; Tsukasaki, Hirofumi; Sakuda, Atsushi RSC Advances, Vol. 9, Issue 25 https://doi.org/10.1039/C9RA00949C	journal	January 2019
High-performance Li ₆ PS ₅ Cl-based all-solid-state lithium-ion batteries Wang, Shuo; Xu, Xiaofu; Zhang, Xue Journal of Materials Chemistry A, Vol. 7, Issue 31 https://doi.org/10.1039/C9TA04289J	journal	January 2019
In situ formation of a LiF and Li–Al alloy anode protected layer on a Li metal anode with enhanced cycle life Wang, Lili; Fu, Shiyang; Zhao, Teng Journal of Materials Chemistry A, Vol. 8, Issue 3 https://doi.org/10.1039/C9TA10965J	journal	January 2020
Design of a LiF-rich solid electrolyte interface layer through salt-additive chemistry for boosting fast-charging phosphorus-based lithium ion battery performance Han, Xinpeng; Sun, Jie Chemical Communications, Vol. 56, Issue 45 https://doi.org/10.1039/D0CC01853H	journal	January 2020
Facile ex situ formation of a LiF–polymer composite layer as an artificial SEI layer on Li metal by simple roll-press processing for carbonate electrolyte-based Li metal batteries Sun, Seho; Myung, Seungcheol; Kim, Gaeun Journal of Materials Chemistry A, Vol. 8, Issue 33 https://doi.org/10.1039/D0TA05372D	journal	January 2020
The intrinsic behavior of lithium fluoride in solid electrolyte interphases on lithium He, Mingfu; Guo, Rui; Hobold, Gustavo M. Proceedings of the National Academy of Sciences, Vol. 117, Issue 1 https://doi.org/10.1073/pnas.1911017116	journal	December 2019
Visualization and analysis of atomistic simulation data with OVITO–the Open Visualization Tool Stukowski, Alexander Modelling and Simulation in Materials Science and Engineering, Vol. 18, Issue 1 https://doi.org/10.1088/0965-0393/18/1/015012	journal	December 2009
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
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
Fluorinated solid electrolyte interphase enables highly reversible solid-state Li metal battery Fan, Xiulin; Ji, Xiao; Han, Fudong Science Advances, Vol. 4, Issue 12 https://doi.org/10.1126/sciadv.aau9245	journal	December 2018

Similar Records

Synthesis of Fluorine-Doped Lithium Argyrodite Solid Electrolytes for Solid-State Lithium Metal Batteries

Journal Article · Tue Feb 22 23:00:00 EST 2022 · ACS Applied Materials and Interfaces · OSTI ID:1867866

Li-Rich and Halide-Deficient Argyrodite Fast Ion Conductors

Journal Article · Tue Oct 25 00:00:00 EDT 2022 · Chemistry of Materials · OSTI ID:1896963

Lowering the Activation Barriers for Lithium-Ion Conductivity through Orientational Disorder in the Cyanide Argyrodite Li6PS5CN

Journal Article · Thu Jun 24 00:00:00 EDT 2021 · Chemistry of Materials · OSTI ID:1809039

Related Subjects

25 ENERGY STORAGE
36 MATERIALS SCIENCE
42 ENGINEERING
Anions
Batteries
Electrochemical cells
Ionic conductivity
Metals

Highly Conductive Iodine and Fluorine Dual-Doped Argyrodite Solid Electrolyte for Lithium Metal Batteries

Citation Formats

References (55)

Similar Records

Related Subjects