Nonflammable PVDF-based gel polymer electrolytes modified by dimethyl methylphosphate for wide temperature range, long cycle-life and high-safety lithium metal batteries

IF 6.8 2区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Science China Materials Pub Date : 2024-09-26 DOI:10.1007/s40843-024-3130-y

Yuanjun Zhao (, ), Xinyu Da (, ), Yanyang Qin (, ), Xin Jia (, ), Xuetian Deng (, ), Shujiang Ding (, ), Junqiao Xiong (, ), Qiang Rong (, ), Xiangpeng Kong (, ), Guoxin Gao (, )

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引用次数: 0

Abstract

Gel polymer electrolytes (GPEs) has been considered as a promising candidate for the development of lithium metal batteries (LMBs) with high energy density and high safety, yet most reported GPEs is flammable, making the LMBs still facing great safety hazards. Herein, we used dimethyl methylphosphate (DMMP) as the functional flame retardant and plasticizer for poly(vinylidene fluoride) (PVDF) matrix to develop a novel nonflammable PVDF-DMMP GPEs for LMBs. The DMMP not only highly enhances the flame resistance of PVDF-DMMP GPEs, the efficient dissociation of lithium salt and the rapid transport of lithium ions, but also helps to form stable and robust CEI/SEI layers. As a result, the ultrathin PVDF-DMMP GPEs (∼20 µm) present superb flame resistance, high ionic conductivity (1.34 × 10⁻³ S cm⁻¹ at 30°C), fast lithium ion transport (\(t_{\text{Li}^{+}}=0.59\) at 30°C), high electrochemical stability voltage window (over 4 V) at 30–80°C and uniform lithium deposition. When used in Li∥Li symmetric cells, Li∥LiFePO₄ (LFP) and Li∥LiNi_0.8Co_0.1Mn_0.1O₂ full cells, the nonflammable PVDF-DMMP GPEs could endow these cells with long-term cycle stability, high rate capability, wide-temperature operation ranges (from −20 to 80°C) and high safety simultaneously. Even when suffering from harsh deconstructive tests, the Li∣PVDF-DMMP GPEs∣LFP pouch cells still work normally without any safety hazards. The actual energy density of the packed pouch cell is as high as 508 Wh kg⁻¹. Therefore, our work can provide a promising strategy for the design of high safety and high-energy-density LMBs.

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经甲基磷酸二甲酯改性的不易燃 PVDF 基凝胶聚合物电解质可用于宽温度范围、长循环寿命和高安全性锂金属电池

凝胶聚合物电解质（GPEs）一直被认为是开发高能量密度和高安全性锂金属电池（LMBs）的理想候选材料，然而大多数报道的 GPEs 都是易燃的，这使得 LMBs 仍然面临很大的安全隐患。在此，我们采用甲基磷酸二甲酯（DMMP）作为聚偏二氟乙烯（PVDF）基体的功能性阻燃剂和增塑剂，开发出一种新型的用于锂金属电池的不易燃 PVDF-DMMP GPEs。DMMP 不仅能增强 PVDF-DMMP GPE 的阻燃性、锂盐的高效解离和锂离子的快速传输，还有助于形成稳定而坚固的 CEI/SEI 层。因此，超薄 PVDF-DMMP GPEs（20 µm）具有优异的阻燃性、高离子电导率（30°C 时为 1.34 × 10-3 S cm-1）、快速锂离子传输（30°C 时为 0.59）、30-80°C 时具有高电化学稳定性电压窗口（超过 4 V）和均匀的锂沉积。当用于锂∥锂对称电池、Li∥LiFePO4（LFP）和Li∥LiNi0.8Co0.1Mn0.1O2全电池时，不易燃的PVDF-DMMP GPE可同时赋予这些电池长期循环稳定性、高倍率能力、宽温度工作范围（从-20到80°C）和高安全性。即使在严苛的解构测试中，锂离子∣PVDF-DMMP GPEs∣LFP 袋式电池仍能正常工作，没有任何安全隐患。包装袋电池的实际能量密度高达 508 Wh kg-1。因此，我们的工作为设计高安全性和高能量密度的 LMB 提供了一种可行的策略。

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来源期刊

Science China Materials Materials Science-General Materials Science

CiteScore

11.40

自引率

7.40%

发文量

949

期刊介绍： Science China Materials (SCM) is a globally peer-reviewed journal that covers all facets of materials science. It is supervised by the Chinese Academy of Sciences and co-sponsored by the Chinese Academy of Sciences and the National Natural Science Foundation of China. The journal is jointly published monthly in both printed and electronic forms by Science China Press and Springer. The aim of SCM is to encourage communication of high-quality, innovative research results at the cutting-edge interface of materials science with chemistry, physics, biology, and engineering. It focuses on breakthroughs from around the world and aims to become a world-leading academic journal for materials science.