文献类型：期刊文献

英文题名：Breaking the Trade-Off: A Phosphorylated Interpenetrating Network Bridging Ion-Conduction Pathways for Safe and High-Energy Solid-State Batteries

作者：Wang, Yuyang[1]; Wang, Linlin[2]; Yang, Jie[1]; Wang, Qiuya[1]; Zhang, Junye[1]; Liu, Cheng[3]; Zhang, Zaichao[3]; Xu, Le[3]; Chen, Rundong[1]; Shen, Tianchen[2]; Lu, Shigang[2]; Chen, Luyang[1]

机构：[1] Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai, 200237, China; [2] Institute for Sustainable Energy, College of Science, Shanghai University, Shanghai, 200444, China; [3] Jiangsu Key Laboratory for Chemistry of Low-Dimensional Materials, School of Chemistry & Chemical Engineering, Huaiyin Normal University, Huaian, 223300, China

年份：2026

外文期刊名：SSRN

收录：EI(收录号：20260061131)

语种：英文

外文关键词：Additives - Crystallinity - Flame retardants - High temperature applications - High temperature operations - Interpenetrating polymer networks - Ion exchange - Ionic conduction in solids - Ionic conductivity - Ions - Lithium compounds - Lithium-ion batteries - Phosphorus compounds - Phosphorylation - Solid electrolytes - Solid state devices - Solid-State Batteries

摘要：The development of solid-state polymer electrolytes is severely hampered by the persistent trade-off among ionic conductivity, flame retardancy, and electrochemical stability. While poly(ethylene oxide) (PEO) offers good Li+ solvation, its high crystallinity impedes room-temperature ion transport, and its inherent flammability poses safety risks. Existing modification strategies often improve one property at the expense of others. Herein, we break this long-standing three-way conflict through the molecular/structural design of a phosphorylated poly(vinyl alcohol) (PVA)/PEO semi-interpenetrating polymer network (PPB-FR). Our first key innovation lies in the construction of this unique architecture, which simultaneously suppresses the crystallinity of PEO (from 84.5% to 24.8%) and establishes a continuous flame-retardant framework, thereby bypassing the issue of additive-blocked ion pathways. The second, mechanistic innovation is the creation of a "phosphoryl-group-bridged" dual-ion conduction mechanism. Combined DFT calculations and solid-state 7Li NMR reveal that while Li+ migrates along amorphous PEO chains, the phosphoryl groups act as critical "relay stations" (lowering the local hopping barrier) to bridge transport across otherwise obstructed regions. This synergistic mechanism enables a high near-room-temperature ionic conductivity of 2.25 × 10-4 S cm-1 and a high Li+ transference number of 0.547. The third innovation is the multi-functionality of the phosphoryl groups, which integrate intrinsic flame retardancy (LOI of 32.4%), structural reinforcement (tensile strength of 59 MPa), and in situ formation of a LiF/Li3PO4-rich stable solid electrolyte interphase. Consequently, Li symmetric cells demonstrate exceptional durability over 600 h under step-increased current densities up to 1.5 mA cm-2, and LiFePO4 full cells deliver remarkable rate capability and cycling stability. ? 2026, The Authors. All rights reserved.