Heavily Tungsten-Doped Sodium Thioantimonate Solid-State Electrolytes with Exceptionally Low Activation Energy for Ionic Diffusion

Xuyong Feng; Hong Fang; Pengcheng Liu; Nan Wu; Ethan C. Self; Liang Yin; Pengbo Wang; Xiang Li; Puru Jena; Jagjit Nanda; David Mitlin

doi:10.1002/anie.202110699

Heavily Tungsten-Doped Sodium Thioantimonate Solid-State Electrolytes with Exceptionally Low Activation Energy for Ionic Diffusion

Xuyong Feng, Hong Fang, Pengcheng Liu, Nan Wu, Ethan C. Self, Liang Yin, Pengbo Wang, Xiang Li, Puru Jena, Jagjit Nanda, David Mitlin

Energy Storage & Conversion

Research output: Contribution to journal › Article › peer-review

32 Scopus citations

Abstract

A strategy for modifying the structure of solid-state electrolytes (SSEs) to reduce the cation diffusion activation energy is presented. Two heavily W-doped sodium thioantimonate SSEs, Na_2.895W_0.3Sb_0.7S₄ and Na_2.7W_0.3Sb_0.7S₄ are designed, both exhibiting exceptionally low activation energy and enhanced room temperature (RT) ionic conductivity; 0.09 eV, 24.2 mS/cm and 0.12 eV, 14.5 mS/cm. At −15 °C the Na_2.895W_0.3Sb_0.7S₄ displays a total ionic conductivity of 5.5 mS/cm. The 30 % W content goes far beyond the 10–12 % reported in the prior studies, and results in novel pseudo-cubic or orthorhombic structures. Calculations reveal that these properties result from a combination of multiple diffusion mechanisms, including vacancy defects, strongly correlated modes and excessive Na-ions. An all-solid-state battery (ASSB) using Na_2.895W_0.3Sb_0.7S₄ as the primary SSE and a sodium sulfide (Na₂S) cathode achieves a reversible capacity of 400 mAh g⁻¹.

Original language	English
Pages (from-to)	26158-26166
Number of pages	9
Journal	Angewandte Chemie - International Edition
Volume	60
Issue number	50
DOIs	https://doi.org/10.1002/anie.202110699
State	Published - Dec 6 2021

Funding

X.F., E.C.S., P.L., N.W., J.N. and D.M. (conception of research, experimental work, preparation of manuscript) were supported by Energy Storage Program, Office of Electricity (Grant Numbers: DE-AC05 00OR22725). H.F. and P.J. (co-conception of research, theoretical work and analysis, co-preparation of manuscript) were supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under Award No.DE-FG02-96ER45579 and U.S. Department of Energy under Award No. DE-EE0008865. This research used resources of the National Energy Research Scientific Computing Center; a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. This manuscript has been authored in part by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US Department of Energy (DOE). The publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doepublic-access-plan) X.F., E.C.S., P.L., N.W., J.N. and D.M. (conception of research, experimental work, preparation of manuscript) were supported by Energy Storage Program, Office of Electricity (Grant Numbers: DE‐AC05 00OR22725). H.F. and P.J. (co‐conception of research, theoretical work and analysis, co‐preparation of manuscript) were supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under Award No.DE‐FG02‐96ER45579 and U.S. Department of Energy under Award No. DE‐EE0008865. This research used resources of the National Energy Research Scientific Computing Center; a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE‐AC02‐05CH11231. This manuscript has been authored in part by UT‐Battelle, LLC, under contract DE‐AC05‐00OR22725 with the US Department of Energy (DOE). The publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid‐up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doepublic‐access‐plan )

Keywords

NaSbS
sodium metal batteries
sodium–sulfur batteries
solid-state batteries
superionic conductors

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1002/anie.202110699

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title = "Heavily Tungsten-Doped Sodium Thioantimonate Solid-State Electrolytes with Exceptionally Low Activation Energy for Ionic Diffusion",

abstract = "A strategy for modifying the structure of solid-state electrolytes (SSEs) to reduce the cation diffusion activation energy is presented. Two heavily W-doped sodium thioantimonate SSEs, Na2.895W0.3Sb0.7S4 and Na2.7W0.3Sb0.7S4 are designed, both exhibiting exceptionally low activation energy and enhanced room temperature (RT) ionic conductivity; 0.09 eV, 24.2 mS/cm and 0.12 eV, 14.5 mS/cm. At −15 °C the Na2.895W0.3Sb0.7S4 displays a total ionic conductivity of 5.5 mS/cm. The 30 % W content goes far beyond the 10–12 % reported in the prior studies, and results in novel pseudo-cubic or orthorhombic structures. Calculations reveal that these properties result from a combination of multiple diffusion mechanisms, including vacancy defects, strongly correlated modes and excessive Na-ions. An all-solid-state battery (ASSB) using Na2.895W0.3Sb0.7S4 as the primary SSE and a sodium sulfide (Na2S) cathode achieves a reversible capacity of 400 mAh g−1.",

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AU - Feng, Xuyong

AU - Fang, Hong

AU - Liu, Pengcheng

AU - Wu, Nan

AU - Self, Ethan C.

AU - Yin, Liang

AU - Wang, Pengbo

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AU - Jena, Puru

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AB - A strategy for modifying the structure of solid-state electrolytes (SSEs) to reduce the cation diffusion activation energy is presented. Two heavily W-doped sodium thioantimonate SSEs, Na2.895W0.3Sb0.7S4 and Na2.7W0.3Sb0.7S4 are designed, both exhibiting exceptionally low activation energy and enhanced room temperature (RT) ionic conductivity; 0.09 eV, 24.2 mS/cm and 0.12 eV, 14.5 mS/cm. At −15 °C the Na2.895W0.3Sb0.7S4 displays a total ionic conductivity of 5.5 mS/cm. The 30 % W content goes far beyond the 10–12 % reported in the prior studies, and results in novel pseudo-cubic or orthorhombic structures. Calculations reveal that these properties result from a combination of multiple diffusion mechanisms, including vacancy defects, strongly correlated modes and excessive Na-ions. An all-solid-state battery (ASSB) using Na2.895W0.3Sb0.7S4 as the primary SSE and a sodium sulfide (Na2S) cathode achieves a reversible capacity of 400 mAh g−1.

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Heavily Tungsten-Doped Sodium Thioantimonate Solid-State Electrolytes with Exceptionally Low Activation Energy for Ionic Diffusion

Abstract

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Keywords

UN SDGs

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