Li15P4S16Cl3, a Lithium Chlorothiophosphate as a Solid-State Ionic Conductor

Liu, Zhantao; Zinkevich, Tatiana; Indris, Sylvio; He, Xingfeng; Liu, Jue; Xu, Wenqian; Bai, Jianming; Xiong, Shan; Mo, Yifei; Chen, Hailong

doi:10.1021/acs.inorgchem.9b01751

Title: Li₁₅P₄S₁₆Cl₃, a Lithium Chlorothiophosphate as a Solid-State Ionic Conductor

Journal Article · 11 December 2019 · Inorganic Chemistry

DOI: https://doi.org/10.1021/acs.inorgchem.9b01751 · OSTI ID:1601340

Liu, Zhantao ^[1]; Zinkevich, Tatiana ^[2];

^[2]; He, Xingfeng ^[3];

^[4]; Xu, Wenqian ^[5]; Bai, Jianming ^[6]; Xiong, Shan ^[1];

^[3];

^[1]

Georgia Inst. of Technology, Atlanta, GA (United States)
Karlsruhe Inst. of Technology, Eggenstein-Leopoldshafen (Germany). Inst. for Applied Materials
Univ. of Maryland, College Park, MD (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source

Tremendous efforts have been devoted to the design of solid Li⁺ electrolytes and the development of all-solid-state batteries. Compared with conventional Li-ion batteries, which use flammable liquid organic electrolytes, all-solid-state batteries show significant advantages in safety. In this work, a novel lithium chlorothiophosphate compound, Li₁₅P₄S₁₆Cl₃, is discovered. The crystal structure and electrochemical properties are investigated. Li₁₅P₄S₁₆Cl₃ can be synthesized as a pure phase via a facile solid-state reaction by heating a ball-milled mixture of Li₂S, P₂S₅, and LiCl at 360 °C. The crystal structure of Li₁₅P₄S₁₆Cl₃ was refined against neutron and synchrotron powder X-ray diffraction data, revealing that it crystallizes in the space group $$I\bar{4}3d$$. Furthermore, the Li⁺ transport in Li₁₅P₄S₁₆Cl₃ was also investigated by multiple solid-state NMR methods, including variable-temperature NMR line-shape analysis, NMR relaxometry, and pulsed-field-gradient NMR. Li₁₅P₄S₁₆Cl₃ shows good thermodynamic stability and can be synthesized at relatively low temperature. Although it exhibits a low ionic conductivity at room temperature, it can serve as a new motif crystal structure for the design and development of new solid-state electrolytes.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-06CH11357; SC0012704

OSTI ID:: 1601340

Report Number(s):: BNL--213644-2020-JAAM

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 1 Vol. 59; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (49)

Pulsed-field gradient nuclear magnetic resonance as a tool for studying translational diffusion: Part 1. Basic theory Price, William S. Concepts in Magnetic Resonance, Vol. 9, Issue 5 https://doi.org/10.1002/(SICI)1099-0534(1997)9:5<299::AID-CMR2>3.0.CO;2-U	journal	January 1997
Design Strategies, Practical Considerations, and New Solution Processes of Sulfide Solid Electrolytes for All-Solid-State Batteries Park, Kern Ho; Bai, Qiang; Kim, Dong Hyeon Advanced Energy Materials, Vol. 8, Issue 18 https://doi.org/10.1002/aenm.201800035	journal	April 2018
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
Cathode-electrolyte material interactions during manufacturing of inorganic solid-state lithium batteries Uhlenbruck, Sven; Dornseiffer, Jürgen; Lobe, Sandra Journal of Electroceramics, Vol. 38, Issue 2-4 https://doi.org/10.1007/s10832-016-0062-x	journal	December 2016
Computer modeling of lithium phosphate and thiophosphate electrolyte materials Holzwarth, N. A. W.; Lepley, N. D.; Du, Yaojun A. Journal of Power Sources, Vol. 196, Issue 16 https://doi.org/10.1016/j.jpowsour.2010.08.042	journal	August 2011
Ag5PS4Cl2 and Ag15(PS4)4Cl3 – Crystal structures and their relation to Ag3PS4 Jörgens, Stefan; Mewis, Albrecht Solid State Sciences, Vol. 9, Issue 2 https://doi.org/10.1016/j.solidstatesciences.2006.09.003	journal	February 2007
Material design of new lithium ionic conductor, thio-LISICON, in the Li2S–P2S5 system Murayama, M.; Sonoyama, N.; Yamada, A. Solid State Ionics, Vol. 170, Issue 3-4 https://doi.org/10.1016/j.ssi.2004.02.025	journal	May 2004
Crystal structure of a superionic conductor, Li7P3S11 Yamane, H.; Shibata, M.; Shimane, Y. Solid State Ionics, Vol. 178, Issue 15-18 https://doi.org/10.1016/j.ssi.2007.05.020	journal	June 2007
Inorganic solid Li ion conductors: An overview Knauth, Philippe Solid State Ionics, Vol. 180, Issue 14-16, p. 911-916 https://doi.org/10.1016/j.ssi.2009.03.022	journal	June 2009
Crystal structure and phase transitions of the lithium ionic conductor Li3PS4 Homma, Kenji; Yonemura, Masao; Kobayashi, Takeshi Solid State Ionics, Vol. 182, Issue 1 https://doi.org/10.1016/j.ssi.2010.10.001	journal	February 2011
Redox activity of argyrodite Li6PS5Cl electrolyte in all-solid-state Li-ion battery: An XPS study Auvergniot, Jérémie; Cassel, Alice; Foix, Dominique Solid State Ionics, Vol. 300 https://doi.org/10.1016/j.ssi.2016.11.029	journal	February 2017
Data-Driven First-Principles Methods for the Study and Design of Alkali Superionic Conductors Deng, Zhi; Zhu, Zhuoying; Chu, Iek-Heng Chemistry of Materials, Vol. 29, Issue 1 https://doi.org/10.1021/acs.chemmater.6b02648	journal	September 2016
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
Li ₃ Y(PS ₄ ) ₂ and Li ₅ PS ₄ Cl ₂ : New Lithium Superionic Conductors Predicted from Silver Thiophosphates using Efficiently Tiered Ab Initio Molecular Dynamics Simulations Zhu, Zhuoying; Chu, Iek-Heng; Ong, Shyue Ping Chemistry of Materials, Vol. 29, Issue 6 https://doi.org/10.1021/acs.chemmater.6b04049	journal	November 2016
Local Structural Investigations, Defect Formation, and Ionic Conductivity of the Lithium Ionic Conductor Li ₄ P ₂ S ₆ Dietrich, Christian; Sadowski, Marcel; Sicolo, Sabrina Chemistry of Materials, Vol. 28, Issue 23 https://doi.org/10.1021/acs.chemmater.6b04175	journal	November 2016
Interface Stability of Argyrodite Li ₆ PS ₅ Cl toward LiCoO ₂ , LiNi _1/3 Co _1/3 Mn _1/3 O ₂ , and LiMn ₂ O ₄ in Bulk All-Solid-State Batteries Auvergniot, Jérémie; Cassel, Alice; Ledeuil, Jean-Bernard Chemistry of Materials, Vol. 29, Issue 9 https://doi.org/10.1021/acs.chemmater.6b04990	journal	April 2017
Li ₄ PS ₄ I: A Li ⁺ Superionic Conductor Synthesized by a Solvent-Based Soft Chemistry Approach Sedlmaier, Stefan J.; Indris, Sylvio; Dietrich, Christian Chemistry of Materials, Vol. 29, Issue 4 https://doi.org/10.1021/acs.chemmater.7b00013	journal	February 2017
Synthesis and Electrochemical Properties of I 4̅-Type Li _{1+2 x} Zn _{1– x} PS ₄ Solid Electrolyte Suzuki, Naoki; Richards, William D.; Wang, Yan Chemistry of Materials, Vol. 30, Issue 7 https://doi.org/10.1021/acs.chemmater.7b03833	journal	March 2018
Mechanism of Formation of Li ₇ P ₃ S ₁₁ Solid Electrolytes through Liquid Phase Synthesis Wang, Yuxing; Lu, Dongping; Bowden, Mark Chemistry of Materials, Vol. 30, Issue 3 https://doi.org/10.1021/acs.chemmater.7b04842	journal	January 2018
Correlation of Structure and Fast Ion Conductivity in the Solid Solution Series Li _{1+2 x} Zn _{1– x} PS ₄ Kaup, Kavish; Lalère, Fabien; Huq, Ashfia Chemistry of Materials, Vol. 30, Issue 3 https://doi.org/10.1021/acs.chemmater.7b05108	journal	January 2018
Crystal Structures, Local Atomic Environments, and Ion Diffusion Mechanisms of Scandium-Substituted Sodium Superionic Conductor (NASICON) Solid Electrolytes Deng, Yue; Eames, Christopher; Nguyen, Long H. B. Chemistry of Materials, Vol. 30, Issue 8 https://doi.org/10.1021/acs.chemmater.7b05237	journal	March 2018
Synthesis, Structural Characterization, and Lithium Ion Conductivity of the Lithium Thiophosphate Li ₂ P ₂ S ₆ Dietrich, Christian; Weber, Dominik A.; Culver, Sean Inorganic Chemistry, Vol. 56, Issue 11 https://doi.org/10.1021/acs.inorgchem.7b00751	journal	May 2017
Solid-State NMR Investigations on the Structure and Dynamics of the Ionic Conductor Li _{1+ x} Al _x Ti _{2– x} (PO ₄ ) ₃ (0.0 ≤ x ≤ 1.0) Vinod Chandran, C.; Pristat, Sylke; Witt, Elena The Journal of Physical Chemistry C, Vol. 120, Issue 16 https://doi.org/10.1021/acs.jpcc.6b00318	journal	April 2016
About the Compatibility between High Voltage Spinel Cathode Materials and Solid Oxide Electrolytes as a Function of Temperature Miara, Lincoln; Windmüller, Anna; Tsai, Chih-Long ACS Applied Materials & Interfaces, Vol. 8, Issue 40 https://doi.org/10.1021/acsami.6b09059	journal	September 2016
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
Fast Lithium Ion Conduction in Li ₂ SnS ₃ : Synthesis, Physicochemical Characterization, and Electronic Structure Brant, Jacilynn A.; Massi, Danielle M.; Holzwarth, N. A. W. Chemistry of Materials, Vol. 27, Issue 1 https://doi.org/10.1021/cm5037524	journal	December 2014
Li ₂ OHCl Crystalline Electrolyte for Stable Metallic Lithium Anodes Hood, Zachary D.; Wang, Hui; Samuthira Pandian, Amaresh Journal of the American Chemical Society, Vol. 138, Issue 6 https://doi.org/10.1021/jacs.5b11851	journal	January 2016
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
Inducing High Ionic Conductivity in the Lithium Superionic Argyrodites Li _{6+ x} P _{1– x} Ge _x S ₅ I for All-Solid-State Batteries Kraft, Marvin A.; Ohno, Saneyuki; Zinkevich, Tatiana Journal of the American Chemical Society, Vol. 140, Issue 47 https://doi.org/10.1021/jacs.8b10282	journal	October 2018
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
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
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
A sulphide lithium super ion conductor is superior to liquid ion conductors for use in rechargeable batteries Seino, Yoshikatsu; Ota, Tsuyoshi; Takada, Kazunori Energy Environ. Sci., Vol. 7, Issue 2 https://doi.org/10.1039/C3EE41655K	journal	January 2014
Revealing the relation between the structure, Li-ion conductivity and solid-state battery performance of the argyrodite Li ₆ PS ₅ Br solid electrolyte Yu, Chuang; Ganapathy, Swapna; van Eck, Ernst R. H. J. Mater. Chem. A, Vol. 5, Issue 40 https://doi.org/10.1039/C7TA05031C	journal	January 2017
Elucidating the mobility of H ⁺ and Li ⁺ ions in (Li _6.25−x H _x Al _0.25 )La ₃ Zr ₂ O ₁₂ via correlative neutron and electron spectroscopy Liu, Xiaoming; Chen, Yan; Hood, Zachary D. Energy & Environmental Science, Vol. 12, Issue 3 https://doi.org/10.1039/C8EE02981D	journal	January 2019
Spin Diffusion Measurements: Spin Echoes in the Presence of a Time‐Dependent Field Gradient Stejskal, E. O.; Tanner, J. E. The Journal of Chemical Physics, Vol. 42, Issue 1 https://doi.org/10.1063/1.1695690	journal	January 1965
Rationale for mixing exact exchange with density functional approximations Perdew, John P.; Ernzerhof, Matthias; Burke, Kieron The Journal of Chemical Physics, Vol. 105, Issue 22, p. 9982-9985 https://doi.org/10.1063/1.472933	journal	December 1996
PDFfit2 and PDFgui: computer programs for studying nanostructure in crystals Farrow, C. L.; Juhas, P.; Liu, J. W. Journal of Physics: Condensed Matter, Vol. 19, Issue 33 https://doi.org/10.1088/0953-8984/19/33/335219	journal	July 2007
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
Li jump process in h − Li 0.7 Ti S 2 studied by two-time Li 7 spin-alignment echo NMR and comparison with results on two-dimensional diffusion from nuclear magnetic relaxation Wilkening, M.; Heitjans, P. Physical Review B, Vol. 77, Issue 2 https://doi.org/10.1103/PhysRevB.77.024311	journal	January 2008
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
PDFgetX3 : a rapid and highly automatable program for processing powder diffraction data into total scattering pair distribution functions Juhás, P.; Davis, T.; Farrow, C. L. Journal of Applied Crystallography, Vol. 46, Issue 2 https://doi.org/10.1107/S0021889813005190	journal	March 2013
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides Shannon, R. D. Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767 https://doi.org/10.1107/S0567739476001551	journal	September 1976
TOPAS: An innovative proton Monte Carlo platform for research and clinical applications: TOPAS: An innovative proton Monte Carlo platform Perl, J.; Shin, J.; Schümann, J. Medical Physics, Vol. 39, Issue 11 https://doi.org/10.1118/1.4758060	journal	October 2012
Constant Temperature Molecular Dynamics Methods Nosé, Shuichi Progress of Theoretical Physics Supplement, Vol. 103 https://doi.org/10.1143/PTPS.103.1	journal	January 1991
Lithium Ionic Conductor Thio-LISICON: The Li₂S-GeS₂-P₂S₅ System Kanno, Ryoji; Murayama, Masahiro Journal of The Electrochemical Society, Vol. 148, Issue 7, p. A742-A746 https://doi.org/10.1149/1.1379028	journal	January 2001
The Electrochemical Characteristics and Applicability of an Amorphous Sulfide-Based Solid Ion Conductor for the Next-Generation Solid-State Lithium Secondary Batteries Aihara, Yuichi; Ito, Seitaro; Omoda, Ryo Frontiers in Energy Research, Vol. 4 https://doi.org/10.3389/fenrg.2016.00018	journal	May 2016
Development of Sulfide Solid Electrolytes and Interface Formation Processes for Bulk-Type All-Solid-State Li and Na Batteries Hayashi, Akitoshi; Sakuda, Atsushi; Tatsumisago, Masahiro Frontiers in Energy Research, Vol. 4 https://doi.org/10.3389/fenrg.2016.00025	journal	July 2016

Similar Records

Li_0.625Al_0.125H_0.25Cl_0.75O_0.25 Superionic Conductor with Disordered Rock-Salt Structure

Journal Article · 2021 · ACS Applied Energy Materials · OSTI ID:1839969

Zhang, Qian; Arnold, William; Hood, Zachary D.; +6 more

Li _3.6 In ₇ S _11.8 Cl: an air- and moisture-stable superionic conductor

Journal Article · 2024 · Chemical Science · OSTI ID:2565019

Oyekunle, Ifeoluwa P.; Truong, Erica; Poudel, Tej P.; +12 more

Li₂GeS₃: Lithium Ionic Conductor with an Unprecedented Structural Type

Journal Article · 2023 · Inorganic Chemistry · OSTI ID:2007703

Roh, Jihun; Do, Namgyu; Manjón-Sanz, Alicia; +1 more

Related Subjects

25 ENERGY STORAGE
Crystal structure
Electrical conductivity
Ions
Materials
Physical and chemical processes

Title: Li15P4S16Cl3, a Lithium Chlorothiophosphate as a Solid-State Ionic Conductor

Citation Formats

References (49)

Linked Research (1)

Similar Records

Related Subjects

Title: Li₁₅P₄S₁₆Cl₃, a Lithium Chlorothiophosphate as a Solid-State Ionic Conductor