12.6 μm-Thick Asymmetric Composite Electrolyte with Superior Interfacial Stability for Solid-State Lithium-Metal Batteries

doi:10.1007/s40820-024-01389-2

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Abstract

Solid-state lithium metal batteries (SSLMBs) show great promise in terms of high-energy-density and high-safety performance. However, there is an urgent need to address the compatibility of electrolytes with high-voltage cathodes/Li anodes, and to minimize the electrolyte thickness to achieve high-energy-density of SSLMBs. Herein, we develop an ultrathin (12.6 µm) asymmetric composite solid-state electrolyte with ultralight areal density (1.69 mg cm⁻²) for SSLMBs. The electrolyte combining a garnet (LLZO) layer and a metal organic framework (MOF) layer, which are fabricated on both sides of the polyethylene (PE) separator separately by tape casting. The PE separator endows the electrolyte with flexibility and excellent mechanical properties. The LLZO layer on the cathode side ensures high chemical stability at high voltage. The MOF layer on the anode side achieves a stable electric field and uniform Li flux, thus promoting uniform Li⁺ deposition. Thanks to the well-designed structure, the Li symmetric battery exhibits an ultralong cycle life (5000 h), and high-voltage SSLMBs achieve stable cycle performance. The assembled pouch cells provided a gravimetric/volume energy density of 344.0 Wh kg⁻¹/773.1 Wh L⁻¹. This simple operation allows for large-scale preparation, and the design concept of ultrathin asymmetric structure also reveals the future development direction of SSLMBs.

Key words： Solid-state lithium metal batteries Composite solid-state electrolyte Ultrathin asymmetric structure Pouch cells

Received: 05 December 2023 Published: 26 April 2024

Corresponding Authors: Suqing Wang, Haihui Wang

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	Articles by authors
	Zheng Zhang
	Jingren Gou
	Kaixuan Cui
	Xin Zhang
	Yujian Yao
	Suqing Wang
	Haihui Wang

Cite this article:

Zheng Zhang,Jingren Gou,Kaixuan Cui, et al. 12.6 μm-Thick Asymmetric Composite Electrolyte with Superior Interfacial Stability for Solid-State Lithium-Metal Batteries[J]. Nano-Micro Letters, 2024, 16(1): 181-.

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https://www.qk.sjtu.edu.cn/nml/EN/10.1007/s40820-024-01389-2 OR https://www.qk.sjtu.edu.cn/nml/EN/Y2024/V16/I1/181

Fig. 1 a Fabrication process of the ultrathin asymmetric PLM electrolyte using tape casting. b Cross-sectional SEM images of PLM and EDS mapping

Fig. 2 a XRD patterns of PEO, MOF layer and LLZO layer. b DSC curves of PEO and PLM. c Stress-strain curve of PLM. The inset of c shows that PLM can pull up a 100 g weight. d Ion conductivity of PEO and PLM. e Thickness and ionic conductivity (25 and 30 °C) of ultrathin PLM electrolytes compared with recently reported electrolytes. f Li+ transference number of PLM

Fig. 3 a Li plating/stripping curves of PEO, PLS and PMI. b TOF-SIMS depth profiles for the PMI/Li interface and the corresponding 3D view. c Snapshots of the PEO and PEO-PE electrolyte order parameters and potential distributions as a function of time. d Distribution of Li+, anion and potential in PEO and PMI (P: pristine state, I: intermediate state, S: steady state). e Comparison of electrolyte thickness and cumulative capacity with previous reported. f Schematic diagram of the stability to Li metal (The left side represents the Li/PEO interface and the right side represents the Li/PMI interface)

Fig. 4 Electrochemical performances of LFP-based SSLMBs at 60 °C. a Rate performance. b Cycling performance at 0.2, 0.5 and 1.0 C. Electrochemical performances of LFP-based SSLMBs at 25 °C. c Rate performance. d Cycling performance at 0.5 C. e Cycling performance at 0.1 C with LFP loading ~ 10.5 mg cm−2. f Relationship between LFP loading and areal capacity, and compared with previous studies. g Cycling performance at 0 °C (0.2 C)

Fig. 5 Electrochemical performances of NCM811-based SSLMBs at 25 °C. a Cycling performance of NCM811/CSEs/Li at 0.2 C. b Cycling performance of NCM811/PLM/Li at 0.2 C. c The comparison of NCM811/PLM/Li cycling performance with previous reports. d Schematic diagram of pouch cell. e Galvanostatic charge/discharg curves of NCM811/PLM/Li pouch cell. f Cycling performance of NCM811/CSEs/Li pouch cells. g The pouch cell light up the LED sign in different states (Flatting, pressuring, bending, nail penetration, cutting and ice bath)

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