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Research Article

Constructing stable Li-solid electrolyte interphase to achieve dendrites-free solid-state battery: A nano-interlayer/Li pre-reduction strategy

Yajun Niu1,2, Zhaozhe Yu1( ), Yongjian Zhou2, Jiawen Tang2, Maoxin Li2, Zechao Zhuang3, Yan Yang4, Xiao Huang2( ), Bingbing Tian2( )
Guangxi Key Laboratory of Manufacturing Systems and Advanced Manufacturing Technology, Guilin University of Electronic Technology, Guilin 541004, China
International Collaborative Laboratory of 2D Materials for Optoelectronics Science and Technology of Ministry of Education, Institute of Microscale Optoelectronics, Shenzhen University, Shenzhen 518060, China
Department of Chemistry, Tsinghua University, Beijing 100084, China
Collaborative Innovation Center for Vessel Pollution Monitoring and Control, Dalian Maritime University, Dalian 116026, China
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Graphical Abstract

The Li phosphorus oxynitride (LiPON) layer deposited on the surface of non-stable SE in-situ reacts with Li to form a lithiophilic, electronically insulating, and ionic conductive layer. This layer effectively inhibits the reduction of non-stable solid electrolyte (SE) against Li, thus improving interfacial stability and suppressing the formation of Li dendrites.

Abstract

Solid-state batteries based on Li and nonflammable solid-state electrolytes (SSEs) have aroused the attention of numerous researchers because of their absolute safety and potentially high energy density. Most SSEs after coming into contact with Li are reduced, which leads to high interfacial charge-transfer impedance and dendrites formation. In this study, an “interlayer-Li pre-reduction strategy” was proposed to solve the above problem of reduction. An intermediate layer was introduced between solid electrolyte and Li, and it reacted with Li to produce a stable and ion-conductive interphase. Cubic garnet-type Nb-doped Li7La3Zr2O12 (Nb-LLZO) was selected as an example solid electrolyte since it is characterized by high ionic conductivity, feasible preparation under ambient conditions, as well as low cost. The high impedance arising from the reduction at the Nb-LLZO|Li interface has limited its application. In this paper, a nano-scale Li phosphorus oxynitride (LiPON) layer was deposited on the Nb-LLZO pellets through radio frequency (RF) magnetron sputtering, which pre-reacted with Li in-situ to produce a lithiophilic, electronically insulating, and ionic conductive interphase. The produced interphase significantly inhibited the reduction of Nb5+ against Li and the formation and propagation of Li dendrites. It is noteworthy that Li|LiPON|Nb-LLZO|LiPON|Li cells stably cycled for over 2,000 h without any short circuit. This study emphasizes and demonstrates the significance of the pre-conversion of modification layer between unstable SSE and Li metal to improve interfacial stability.

Keywords

Nb-doped Li7La3Zr2O12 (Nb-LLZO) conversion reactionLi phosphorus oxynitride (LiPON)interfacial reductionsolid-state battery

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Nano Research
Volume 15 Issue 8,
August 2022
Pages 7180-7189
DOI: 10.1007/s12274-022-4362-y
Cite this article:
Niu Y, Yu Z, Zhou Y, et al. Constructing stable Li-solid electrolyte interphase to achieve dendrites-free solid-state battery: A nano-interlayer/Li pre-reduction strategy. Nano Research, 2022, 15(8): 7180-7189. https://doi.org/10.1007/s12274-022-4362-y
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Received: 24 February 2022
Revised: 17 March 2022
Accepted: 24 March 2022
Published: 19 May 2022
© Tsinghua University Press 2022
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