用于金属锂电池的磷腈基阻燃人工界面层

引用本文: 金彩云, 吴泽轩, 李国鹏, 罗战, 李念武. 用于金属锂电池的磷腈基阻燃人工界面层[J]. 物理化学学报, 2025, 41(8): 100094. doi: 10.1016/j.actphy.2025.100094 shu

Citation: Caiyun Jin, Zexuan Wu, Guopeng Li, Zhan Luo, Nian-Wu Li. Phosphazene-based flame-retardant artificial interphase layer for lithium metal batteries[J]. Acta Physico-Chimica Sinica, 2025, 41(8): 100094. doi: 10.1016/j.actphy.2025.100094 shu

用于金属锂电池的磷腈基阻燃人工界面层

北京化工大学, 有机无机复合材料全国重点实验室, 北京 100029

通讯作者: 李念武, linianwu@mail.buct.edu.cn

基金项目:
国家自然科学基金 21975015

摘要: 金属锂负极(LMA)因具有高的比容量(3860 mAh·g⁻¹)和最低的氧化还原电位(−3.04 V vs.标准氢电极)，而被认为是下一代高能量密度可充电电池的理想负极材料。然而，金属锂电池存在着锂负极枝晶不可控生长和容易热失控等难题。为此，本论文通过傅克烷基化反应设计合成了一种新型的倍半硅氧烷功能化的六苯氧基环三磷腈基多孔聚合物(SHPP)人工界面层用于保护LMA。SHPP分子链扭曲堆叠可形成大量纳米孔，这些具备独特限域效应的纳米孔能够限制阴离子的通过，提高锂离子迁移数，进而抑制锂枝晶生长。SHPP可以在受热时释放PO•自由基，可用于湮灭酯类电解液受热分解产生的高活性HO•和O•自由基，以减少电池热失控风险。另外，SHPP使得LMA界面中产生Li₃P和LiF成分，有助于提高界面锂离子传导和化学稳定性。因此，SHPP-Li对称电池在酯类电解液中能够稳定循环1600 h，且SHPP-Li||LiNi_0.8Co_0.1Mn_0.1O₂全电池在500次循环后的容量保持率高达76.8%。这种阻燃型人工界面层为安全且无枝晶的锂金属负极提供新的设计思路。

关键词:

English

Phosphazene-based flame-retardant artificial interphase layer for lithium metal batteries

State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029, China

Corresponding author: Nian-Wu Li, Email: linianwu@mail.buct.edu.cn

Received Date: 14 February 2025
Accepted Date: 11 April 2025
Revised Date: 31 March 2025
Available Online: 15 August 2025
Fund Project:
the National Natural Science Foundation of China

Abstract: The rapid development of emerging fields such as electric vehicles, drones, and robotics has driven the demand for secondary batteries with higher energy density and enhanced safety. The lithium metal anode (LMA) is widely regarded as an ideal anode material for next-generation rechargeable batteries due to its high specific capacity (3860 mAh·g⁻¹) and low redox potential (−3.04 V vs. standard hydrogen electrode). However, LMA faces significant challenges, primarily the uncontrollable growth of dendrites and its inherent propensity for thermal runaway. To address these issues, this study proposes a novel silsesquioxane-functionalized hexaphenoxycyclotriphosphazene (HPCTP)-based porous polymer (SHPP) artificial interphase layer, synthesized via Friedel-Crafts alkylation, to achieve highly stable LMA performance. N₂ adsorption/desorption analysis confirms that SHPP features a hierarchical nanoporous structure, with pores of approximately 0.5 and 0.6 nm that effectively restrict the mobility of PF₆⁻ anions. As a result, the Li-ion transference number increases from 0.29 in liquid electrolytes to 0.60, which helps suppress Li dendrite growth. Additionally, the rich nanoporous structure of SHPP significantly improves its wettability with the electrolyte. In situ thermogravimetric analysis coupled with Fourier transform infrared spectroscopy (TG-FTIR) reveals that SHPP decomposes at approximately 410 ℃, generating phosphate radicals (PO•) that quench highly reactive hydroxyl (HO•) and oxygen (O•) radicals produced during the thermal decomposition of ester-based electrolytes, effectively mitigating thermal runaway risks. Thermal analysis and ignition tests confirm the outstanding thermal stability and flame-retardant properties of SHPP. Semi-in situ X-ray photoelectron spectroscopy (XPS) analysis indicates that the solid electrolyte interphase (SEI) on bare Li metal is predominantly organic and undergoes significant compositional fluctuations during cycling. In contrast, the SEI formed on SHPP-Li is enriched with Li phosphide (Li₃P), which enhances ionic conductivity, and Li fluoride (LiF), which improves chemical stability, resulting in a compositionally stable SEI throughout cycling. SHPP not only facilitates interfacial Li-ion transport but also promotes the formation of a chemically robust interphase. In situ optical microscopy and semi-in situ field-emission scanning electron microscopy (FE-SEM) images demonstrate that the SHPP artificial interphase effectively suppresses Li dendrite growth, enabling uniform Li deposition. As a result, SHPP-Li||SHPP-Li symmetric cells exhibit stable cycling for 1,600 h at 0.5 mA·cm⁻² and 0.5 mAh·cm⁻². Furthermore, SHPP-Li||LiNi_0.8Co_0.1Mn_0.1O₂ full cells maintain a high capacity retention of 76.8% after 500 cycles at 1C (1C = 190 mA·g⁻¹). This flame-retardant artificial interphase layer offers a promising strategy for designing dendrite-free and safe LMAs.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

用于金属锂电池的磷腈基阻燃人工界面层

通讯作者: 李念武, linianwu@mail.buct.edu.cn

English

Phosphazene-based flame-retardant artificial interphase layer for lithium metal batteries

Corresponding author: Nian-Wu Li, Email: linianwu@mail.buct.edu.cn

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

用于金属锂电池的磷腈基阻燃人工界面层

通讯作者: 李念武, linianwu@mail.buct.edu.cn

English

Phosphazene-based flame-retardant artificial interphase layer for lithium metal batteries

Corresponding author: Nian-Wu Li, Email: linianwu@mail.buct.edu.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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