Experimental Corroboration of Lithium Orthothioborate Superionic Conductor by Systematic Elemental Manipulation

Xiang Zhu; Pushun Lu; Dengxu Wu; Qifa Gao; Tenghuan Ma; Ming Yang; Liquan Chen; Hong Li; Fan Wu

doi:10.1021/acs.nanolett.3c02861

Experimental Corroboration of Lithium Orthothioborate Superionic Conductor by Systematic Elemental Manipulation

Nano Lett. 2023 Nov 22;23(22):10290-10296. doi: 10.1021/acs.nanolett.3c02861. Epub 2023 Nov 9.

Authors

Xiang Zhu^{1

2

3}, Pushun Lu^{1

4}, Dengxu Wu^{1

4}, Qifa Gao^{1

2

3}, Tenghuan Ma^{1

2

3}, Ming Yang^{1

2

3}, Liquan Chen^{1

2

5

4}, Hong Li^{1

2

5

4}, Fan Wu^{1

2

5

4

3

6}

Affiliations

¹ Tianmu Lake Institute of Advanced Energy Storage Technologies, Liyang, Jiangsu 213300, China.
² Nano Science and Technology Institute, University of Science and Technology of China, Suzhou 215123, China.
³ Yangtze River Delta Physics Research Center, Liyang, Jiangsu 213300, China.
⁴ University of Chinese Academy of Sciences, Beijing 100049, China.
⁵ Key Laboratory for Renewable Energy, Beijing Key Laboratory for New Energy Materials and Devices, Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China.
⁶ CASOL Energy, Co. Ltd. Liyang, Jiangsu 213300, China.

PMID: 37943577
DOI: 10.1021/acs.nanolett.3c02861

Abstract

The Li superionic conductor Li₃BS₃ has been theoretically predicted as an ideal solid electrolyte (SE) due to its low Li⁺ migration energy barrier and high ionic conductivity. However, the experimentally synthesized Li₃BS₃ has a 10⁴ times lower ionic conductivity. Herein, we investigate the effect of a series of cation and anion substitutions in Li₃BS₃ SE on its ionic conductivity, including Li_3-xM_0.05BS₃ (M = Cu, Zn, Sn, P, W, x = 0.05, 0.1, 0.2, 0.25), Li_3-yBS_2.95X_0.05 (X = O, Cl, Br, I, y = 0.05, 0.1) and Li_2.75-xP_0.05BS_3-xCl_x (x = 0.05, 0.1, 0.15, 0.2, 0.4, 0.6). Amorphous ionic conductor Li_2.55P_0.05BS_2.8Cl_0.2 has a high ion conductivity of 0.52 mS cm^-1 at room temperature with an activation energy of 0.41 eV. The electrochemical performance of all-solid-state batteries with Li_2.55P_0.05BS_2.8Cl_0.2 SEs show stable cycling with a discharge capacity retention of >97% after 200 cycles at 1C under 55 °C.

Keywords: all-solid-state batteries; lithium ionic conductor; lithium thioborate materials; solid-state electrolytes.