An Entropically Stabilized Fast-Ion Conductor: Li 3.25[Si 0.25P 0.75]S4

Zhou, Laidong; Assoud, Abdeljalil; Shyamsunder, Abhinandan; Huq, Ashfia; Zhang, Qiang; Hartmann, Pascal; Kulisch, Joern; Nazar, Linda F.

doi:10.1021/acs.chemmater.9b00657

An Entropically Stabilized Fast-Ion Conductor: Li _3.25[Si _0.25P _0.75]S₄

Journal Article · Wed Sep 04 00:00:00 EDT 2019 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.9b00657· OSTI ID:1606882

^[1]; Assoud, Abdeljalil ^[1]; Shyamsunder, Abhinandan ^[1]; ^[2]; ^[2]; Hartmann, Pascal ^[3]; Kulisch, Joern ^[3]; ^[1]

Univ. of Waterloo, ON (Canada). Waterloo Inst. for Nanotechnology
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
BASF SE, Ludwigshafen (Germany)

We report on a family of lithium fast ion conductors, Li_3+x[Si_xP_1–x]S₄, that exhibit an entropically stabilized structure type in a solid solution regime (0.15 < x < 0.33) with superionic conductivity above 1 mS·cm^–1. Exploration of the influence of aliovalent substitution in the thermodynamically unstable β-Li₃PS₄ lattice using a combination of single crystal X-ray and powder neutron diffraction, the maximum entropy method, and impedance spectroscopy reveals that substitution induces structural splitting of the localized Li sites, effectively stabilizing bulk β-Li₃PS₄ at room temperature and delocalizing lithium ion density. The optimal material, Li_3.25[S_i0.25P_0.75]S₄, exhibits inherent entropic site disorder and a frustrated energy landscape, resulting in a high conductivity of 1.22 mS·cm^–1 that represents an increase of three orders of magnitude compared to bulk β-Li₃PS₄ and one order of magnitude higher than the nanoporous form. The enhanced ion conduction and lowered activation barrier with increasing site disorder as a result of aliovalent “tuning” reveals an important strategy toward the design of fast ion conductors that are vital as solid state electrolytes.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

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

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1606882

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 19 Vol. 31; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (57)

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
Compliant Yet Brittle Mechanical Behavior of Li ₂ S-P ₂ S ₅ Lithium-Ion-Conducting Solid Electrolyte McGrogan, Frank P.; Swamy, Tushar; Bishop, Sean R. Advanced Energy Materials, Vol. 7, Issue 12 https://doi.org/10.1002/aenm.201602011	journal	January 2017
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
Li6PS5X: A Class of Crystalline Li-Rich Solids With an Unusually High Li+ Mobility Deiseroth, Hans-Jörg; Kong, Shiao-Tong; Eckert, Hellmut Angewandte Chemie International Edition, Vol. 47, Issue 4 https://doi.org/10.1002/anie.200703900	journal	January 2008
Synthesis of New Lithium Ionic Conductor Thio-LISICON—Lithium Silicon Sulfides System Murayama, M. Journal of Solid State Chemistry, Vol. 168, Issue 1 https://doi.org/10.1006/jssc.2002.9701	journal	October 2002
Glass formation in non-oxide chalcogenide systems. Structural elucidation of Li2SSiS2LiI solid electrolytes by quantitative 29Si, 6Li and 7Li high resolution solid state NMR methods Eckert, Hellmut; Zhang, Zhengming; Kennedy, John H. Journal of Non-Crystalline Solids, Vol. 107, Issue 2-3 https://doi.org/10.1016/0022-3093(89)90472-9	journal	January 1989
Ionic conductivity of and phase transition in lithium thiophosphate Li3PS4 Tachez, M.; Malugani, J.; Mercier, R. Solid State Ionics, Vol. 14, Issue 3 https://doi.org/10.1016/0167-2738(84)90097-3	journal	November 1984
Defect clustering in lisicon solid electrolytes Bruce, P. Solid State Ionics, Vol. 40-41 https://doi.org/10.1016/0167-2738(90)90344-Q	journal	August 1990
First-principles study of lithium-ion diffusion in β -Li 3 PS 4 for solid-state electrolytes Lim, Myung-Soo; Jhi, Seung-Hoon Current Applied Physics, Vol. 18, Issue 5 https://doi.org/10.1016/j.cap.2018.03.002	journal	May 2018
An In Vivo Formed Solid Electrolyte Surface Layer Enables Stable Plating of Li Metal Pang, Quan; Liang, Xiao; Shyamsunder, Abhinandan Joule, Vol. 1, Issue 4 https://doi.org/10.1016/j.joule.2017.11.009	journal	December 2017
Lithium ion conductive oxysulfide, Li3PO4–Li3PS4 Takada, Kazunori; Osada, Minoru; Ohta, Narumi Solid State Ionics, Vol. 176, Issue 31-34 https://doi.org/10.1016/j.ssi.2005.03.023	journal	October 2005
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
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
Chemical synthesis of Li3PS4 precursor suspension by liquid-phase shaking Phuc, Nguyen Huu Huy; Morikawa, Kei; Totani, Mitsuhiro Solid State Ionics, Vol. 285 https://doi.org/10.1016/j.ssi.2015.11.019	journal	February 2016
Dysnomia, a computer program for maximum-entropy method (MEM) analysis and its performance in the MEM-based pattern fitting Momma, Koichi; Ikeda, Takuji; Belik, Alexei A. Powder Diffraction, Vol. 28, Issue 3 https://doi.org/10.1017/S088571561300002X	journal	May 2013
Elastic Properties of the Solid Electrolyte Li ₇ La ₃ Zr ₂ O ₁₂ (LLZO) Yu, Seungho; Schmidt, Robert D.; Garcia-Mendez, Regina Chemistry of Materials, Vol. 28, Issue 1 https://doi.org/10.1021/acs.chemmater.5b03854	journal	December 2015
Direct Observation of the Interfacial Instability of the Fast Ionic Conductor Li ₁₀ GeP ₂ S ₁₂ at the Lithium Metal Anode Wenzel, Sebastian; Randau, Simon; Leichtweiß, Thomas Chemistry of Materials, Vol. 28, Issue 7 https://doi.org/10.1021/acs.chemmater.6b00610	journal	March 2016
Superionic Conductors: Li 10+δ [Sn y Si 1– y ] 1+δ P 2−δ S 12 with a Li 10 GeP 2 S 12 -type Structure in the Li 3 PS 4 –Li 4 SnS 4 –Li 4 SiS 4 Quasi-ternary System Sun, Yulong; Suzuki, Kota; Hori, Satoshi Chemistry of Materials, Vol. 29, Issue 14 https://doi.org/10.1021/acs.chemmater.7b00886	journal	July 2017
Structural, Chemical, and Dynamical Frustration: Origins of Superionic Conductivity in closo -Borate Solid Electrolytes Kweon, Kyoung E.; Varley, Joel B.; Shea, Patrick Chemistry of Materials, Vol. 29, Issue 21 https://doi.org/10.1021/acs.chemmater.7b02902	journal	October 2017
Superion Conductor Na _11.1 Sn _2.1 P _0.9 Se ₁₂ : Lowering the Activation Barrier of Na ⁺ Conduction in Quaternary 1–4–5–6 Electrolytes Duchardt, Marc; Neuberger, Sven; Ruschewitz, Uwe Chemistry of Materials, Vol. 30, Issue 12 https://doi.org/10.1021/acs.chemmater.8b01656	journal	May 2018
Nuclear Spin Relaxation in Nanocrystalline β-Li ₃ PS ₄ Reveals Low-Dimensional Li Diffusion in an Isotropic Matrix Prutsch, Denise; Gadermaier, Bernhard; Brandstätter, Harald Chemistry of Materials, Vol. 30, Issue 21 https://doi.org/10.1021/acs.chemmater.8b02753	journal	October 2018
Influence of the Lithium Substructure on the Diffusion Pathways and Transport Properties of the Thio-LISICON Li ₄ Ge _{1– x} Sn _x S ₄ Minafra, Nicolò; Culver, Sean P.; Li, Cheng Chemistry of Materials, Vol. 31, Issue 10 https://doi.org/10.1021/acs.chemmater.9b01059	journal	April 2019
Li ⁺ -Ion Dynamics in β-Li ₃ PS ₄ Observed by NMR: Local Hopping and Long-Range Transport Stöffler, Heike; Zinkevich, Tatiana; Yavuz, Murat The Journal of Physical Chemistry C, Vol. 122, Issue 28 https://doi.org/10.1021/acs.jpcc.8b05431	journal	June 2018
Analysis of Diffusion in Solid-State Electrolytes through MD Simulations, Improvement of the Li-Ion Conductivity in β-Li ₃ PS ₄ as an Example de Klerk, Niek J. J.; van der Maas, Eveline; Wagemaker, Marnix ACS Applied Energy Materials, Vol. 1, Issue 7 https://doi.org/10.1021/acsaem.8b00457	journal	June 2018
Elastic Properties, Defect Thermodynamics, Electrochemical Window, Phase Stability, and Li ⁺ Mobility of Li ₃ PS ₄ : Insights from First-Principles Calculations Yang, Yanhan; Wu, Qu; Cui, Yanhua ACS Applied Materials & Interfaces, Vol. 8, Issue 38 https://doi.org/10.1021/acsami.6b06754	journal	September 2016
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
Structural Evolution and Li Dynamics in Nanophase Li ₃ PS ₄ by Solid-State and Pulsed-Field Gradient NMR Gobet, Mallory; Greenbaum, Steve; Sahu, Gayatri Chemistry of Materials, Vol. 26, Issue 11 https://doi.org/10.1021/cm5012058	journal	May 2014
Anomalous High Ionic Conductivity of Nanoporous β-Li₃PS₄ Liu, Zengcai; Fu, Wujun; Payzant, E. Andrew Journal of the American Chemical Society, Vol. 135, Issue 3, p. 975-978 https://doi.org/10.1021/ja3110895	journal	January 2013
Li ₁₀ SnP ₂ S ₁₂ : An Affordable Lithium Superionic Conductor Bron, Philipp; Johansson, Sebastian; Zick, Klaus Journal of the American Chemical Society, Vol. 135, Issue 42 https://doi.org/10.1021/ja407393y	journal	October 2013
Structural and Mechanistic Insights into Fast Lithium-Ion Conduction in Li ₄ SiO ₄ –Li ₃ PO ₄ Solid Electrolytes Deng, Yue; Eames, Christopher; Chotard, Jean-Noël Journal of the American Chemical Society, Vol. 137, Issue 28 https://doi.org/10.1021/jacs.5b04444	journal	July 2015
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
Is Geometric Frustration-Induced Disorder a Recipe for High Ionic Conductivity? Düvel, Andre; Heitjans, Paul; Fedorov, Pavel Journal of the American Chemical Society, Vol. 139, Issue 16 https://doi.org/10.1021/jacs.7b00502	journal	April 2017
Dendrite-Free Li-Metal Battery Enabled by a Thin Asymmetric Solid Electrolyte with Engineered Layers Duan, Hui; Yin, Ya-Xia; Shi, Yang Journal of the American Chemical Society, Vol. 140, Issue 1 https://doi.org/10.1021/jacs.7b10864	journal	December 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
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
The crystallography of correlated disorder Keen, David A.; Goodwin, Andrew L. Nature, Vol. 521, Issue 7552 https://doi.org/10.1038/nature14453	journal	May 2015
Origin of fast ion diffusion in super-ionic conductors He, Xingfeng; Zhu, Yizhou; Mo, Yifei Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15893	journal	June 2017
Entropy-stabilized oxides Rost, Christina M.; Sachet, Edward; Borman, Trent Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9485	journal	September 2015
A solid future for battery development Janek, Jürgen; Zeier, Wolfgang G. Nature Energy, Vol. 1, Issue 9 https://doi.org/10.1038/nenergy.2016.141	journal	September 2016
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
Batteries: Getting solid Hu, Yong-Sheng Nature Energy, Vol. 1, Issue 4 https://doi.org/10.1038/nenergy.2016.42	journal	April 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
Design principles for solid-state lithium superionic conductors Wang, Yan; Richards, William Davidson; Ong, Shyue Ping Nature Materials, Vol. 14, Issue 10 https://doi.org/10.1038/nmat4369	journal	August 2015
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
A new ultrafast superionic Li-conductor: ion dynamics in Li ₁₁ Si ₂ PS ₁₂ and comparison with other tetragonal LGPS-type electrolytes Kuhn, Alexander; Gerbig, Oliver; Zhu, Changbao Phys. Chem. Chem. Phys., Vol. 16, Issue 28 https://doi.org/10.1039/C4CP02046D	journal	January 2014
Synthesis, structure, and ionic conductivity of solid solution, Li _10+δ M _1+δ P _2−δ S ₁₂ (M = Si, Sn) Hori, Satoshi; Suzuki, Kota; Hirayama, Masaaki Faraday Discuss., Vol. 176 https://doi.org/10.1039/C4FD00143E	journal	January 2014
The pursuit of solid-state electrolytes for lithium batteries: from comprehensive insight to emerging horizons Chen, Renjie; Qu, Wenjie; Guo, Xing Materials Horizons, Vol. 3, Issue 6 https://doi.org/10.1039/C6MH00218H	journal	January 2016
Li-ion site disorder driven superionic conductivity in solid electrolytes: a first-principles investigation of β-Li ₃ PS ₄ Phani Dathar, Gopi Krishna; Balachandran, Janakiraman; Kent, Paul R. C. Journal of Materials Chemistry A, Vol. 5, Issue 3 https://doi.org/10.1039/C6TA07713G	journal	January 2017
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
Solution-based synthesis of lithium thiophosphate superionic conductors for solid-state batteries: a chemistry perspective Ghidiu, Michael; Ruhl, Justine; Culver, Sean P. Journal of Materials Chemistry A, Vol. 7, Issue 30 https://doi.org/10.1039/C9TA04772G	journal	January 2019
Correlation of anisotropy and directional conduction in β-Li ₃ PS ₄ fast Li ⁺ conductor Chen, Yan; Cai, Lu; Liu, Zengcai Applied Physics Letters, Vol. 107, Issue 1 https://doi.org/10.1063/1.4926725	journal	July 2015
Elastic and Li-ion–percolating hybrid membrane stabilizes Li metal plating Pang, Quan; Zhou, Laidong; Nazar, Linda F. Proceedings of the National Academy of Sciences, Vol. 115, Issue 49 https://doi.org/10.1073/pnas.1809187115	journal	November 2018
Defect clustering in the superionic conductor lithium germanium vanadate Abrahams, I.; Bruce, P. G. Acta Crystallographica Section B Structural Science, Vol. 47, Issue 5 https://doi.org/10.1107/S0108768191004548	journal	October 1991
Structure du tetrathiophosphate de lithium Mercier, R.; Malugani, J. -P.; Fahys, B. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 38, Issue 7 https://doi.org/10.1107/S0567740882007535	journal	July 1982
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
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

Similar Records

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

New Family of Argyrodite Thioantimonate Lithium Superionic Conductors

Journal Article · Wed Oct 23 00:00:00 EDT 2019 · Journal of the American Chemical Society · OSTI ID:1606830

Synthesis and structure of novel lithium-ion conductor Li{sub 7}Ge{sub 3}PS{sub 12}

Journal Article · Tue Feb 14 23:00:00 EST 2017 · Journal of Solid State Chemistry · OSTI ID:22658202

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Crystal structure
Diffusion
Electrical conductivity
Ions
Physical and chemical processes

CSD 1960741: Experimental Crystal Structure Determination Laidong, Zhou,; Abdeljalil, Assoud,; Abhinandan, Shyamsunder, https://doi.org/10.25505/fiz.icsd.cc23t9qz The current record is supplemented by this dataset	dataset	January 2019
CSD 1960742: Experimental Crystal Structure Determination Laidong, Zhou,; Abdeljalil, Assoud,; Abhinandan, Shyamsunder, https://doi.org/10.25505/fiz.icsd.cc23t9r0 The current record is supplemented by this dataset	dataset	January 2019
CSD 1960743: Experimental Crystal Structure Determination Laidong, Zhou,; Abdeljalil, Assoud,; Abhinandan, Shyamsunder, https://doi.org/10.25505/fiz.icsd.cc23t9s1 The current record is supplemented by this dataset	dataset	January 2019
CSD 1960744: Experimental Crystal Structure Determination Laidong, Zhou,; Abdeljalil, Assoud,; Abhinandan, Shyamsunder, https://doi.org/10.25505/fiz.icsd.cc23t9t2 The current record is supplemented by this dataset	dataset	January 2019
CSD 1960745: Experimental Crystal Structure Determination Laidong, Zhou,; Abdeljalil, Assoud,; Abhinandan, Shyamsunder, https://doi.org/10.25505/fiz.icsd.cc23t9v3 The current record is supplemented by this dataset	dataset	January 2019
CSD 1960746: Experimental Crystal Structure Determination Laidong, Zhou,; Abdeljalil, Assoud,; Abhinandan, Shyamsunder, https://doi.org/10.25505/fiz.icsd.cc23t9w4 The current record is supplemented by this dataset	dataset	January 2019
CSD 1960747: Experimental Crystal Structure Determination Laidong, Zhou,; Abdeljalil, Assoud,; Abhinandan, Shyamsunder, https://doi.org/10.25505/fiz.icsd.cc23t9x5 The current record is supplemented by this dataset	dataset	January 2019

An Entropically Stabilized Fast-Ion Conductor: Li 3.25[Si 0.25P 0.75]S4

Citation Formats

References (57)

Linked Research (7)

Similar Records

Related Subjects

An Entropically Stabilized Fast-Ion Conductor: Li _3.25[Si _0.25P _0.75]S₄