Citation: Bin Wang, Qingqing Zhou, Junjie Lu, Chuyang Li, Mengmeng Fan, Wenwei Ding, Bifu Sheng, Wenjuan Zhu, Qian Ni, Huixin Chen, Xiang Han. Fluorinate localized solvation PVDF-HFP-based polymer electrolyte producing LiF-rich interface for solid-state lithium metal batteries[J]. Chinese Chemical Letters, ;2026, 37(10): 111557. doi: 10.1016/j.cclet.2025.111557 shu

Fluorinate localized solvation PVDF-HFP-based polymer electrolyte producing LiF-rich interface for solid-state lithium metal batteries

Bin Wang ^a ,
Qingqing Zhou ^a ,
Junjie Lu ^a ,
Chuyang Li ^a ,
Mengmeng Fan ^{b, d} ,
Wenwei Ding ^a ,
Bifu Sheng ^a ,
Wenjuan Zhu ^a ,
Qian Ni ^a ,
Huixin Chen ^{c, e} ,
Xiang Han ^{a, *,}

a.
College of Materials Science and Engineering, Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University, Nanjing 210037, China
b.
Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, International Innovation Center for Forest Chemicals and Materials, College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, China
c.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
d.
Key Lab of Biomass Energy and Material, Jiangsu Province; Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, Nanjing 210042, China
e.
Xiamen Key Laboratory of Rare Earth Photoelectric Functional Materials, Xiamen Institute of Rare Earth Materials, Haixi institutes, Chinese Academy of Sciences, Xiamen 361021, China

hanxiang@njfu.edu.cn

Received Date: 22 April 2025
Revised Date: 2 July 2025
Accepted Date: 8 July 2025
Available Online: 8 July 2025

Figures(4)

Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP)-based solid polymer electrolytes show great potential for high energy lithium metal batteries, however, the residual solvent and related severe side reactions limit its development. Herein, a PVDF-HFP-based solid polymer electrolyte modified by fluorobenzene (FB) co-solvent is designed to address these problems. The introduced FB with weak solvation interaction regulates the coordination environment and induces anions to enter the solvation structure, generating more contact ion pairs (CIPs) and aggregates (AGGs). In addition, the anions-derived LiF-rich interphases help to improve the interface stability against Li metal. As a result, the FB-PVDF-HFP achieves high ionic conductivity (4.1 × 10⁻⁴ S/cm) and low activation energy (0.125 eV) at room temperature. In addition, Li||Li symmetric cells using FB-PVDF-HFP electrolyte can achieve uniform and dendrite-free lithium deposition/stripping in the long-term cycling over 2300 h. The assembled solid-state Li|FB-PVDF-HFP|LFP full cell shows improved rate performance and cycling performance (600 cycles at 0.5 C and 450 cycles at 3 C) at room temperature. This work verifies the feasibility of fluorinated terminated solid polymer electrolytes on its lithium-ion transport and interfacial stability in lithium metal batteries.
- Solid-state battery,
- PVDF-HFP based solid polymer electrolyte,
- Fluorinate localized solvation structure,
- Lithium-ion transport,
- Interface stability
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