Wang Hao, Xiong Xin, Hu Huie, Liu Sijie
Foundation Department, Naval University of Engineering, Wuhan 430033, China.
Research Institute of Tsinghua University in Shenzhen, Shenzhen 518000, China.
Polymers (Basel). 2025 Aug 30;17(17):2369. doi: 10.3390/polym17172369.
High-performance batteries for military and extreme environment applications require alternatives to conventional liquid lithium-ion batteries (LIBs), which suffer from poor low-temperature performance and safety risks. All-solid-state lithium batteries (ASSLBs) offer enhanced safety and superior low-temperature capability. In this work, we designed and fabricated composite solid-state electrolytes using polyvinylidene fluoride (PVDF) and polyacrylic acid (PAA) as polymer matrices, N,N-dimethylformamide (DMF) as the solvent, and lithium bis(trifluoromethane sulfonimide) (LiTFSI) as the lithium salt. Composite solutions with varying PAA mass ratios were prepared. Advanced three-dimensional (3D) printing technology enabled the rapid and precise fabrication of electrolyte membranes. An ionic conductivity of about 2.71 × 10 S cm at 25 °C, high mechanical strength, and good thermal properties can be achieved through component and 3D printing process optimization. Assembled LiCoO||PVDF@PAA||Li ASSLBs delivered an initial discharge capacity of 165.3 mAh/g at 0.1 mA cm (room temperature), maintaining 98% capacity retention after 300 cycles. At 0 °C, these cells provided 157.4 mAh/g initial capacity with 85% retention over 100 cycles at 0.1 mA cm. This work identifies the optimal PAA ratio for enhanced electrochemical performance and demonstrates the viability of 3D printing for advanced ASSLB manufacturing.
用于军事和极端环境应用的高性能电池需要传统液态锂离子电池（LIBs）的替代品，因为传统液态锂离子电池存在低温性能差和安全风险。全固态锂电池（ASSLBs）具有更高的安全性和卓越的低温性能。在这项工作中，我们以聚偏氟乙烯（PVDF）和聚丙烯酸（PAA）作为聚合物基体，N，N-二甲基甲酰胺（DMF）作为溶剂，双（三氟甲烷磺酰）亚胺锂（LiTFSI）作为锂盐，设计并制备了复合固态电解质。制备了具有不同PAA质量比的复合溶液。先进的三维（3D）打印技术能够快速、精确地制造电解质膜。通过优化组分和3D打印工艺，可以实现25℃下约2.71×10 S cm的离子电导率、高机械强度和良好的热性能。组装的LiCoO||PVDF@PAA||Li全固态锂电池在0.1 mA cm（室温）下的初始放电容量为165.3 mAh/g，300次循环后容量保持率为98%。在0℃下，这些电池在0.1 mA cm下的初始容量为157.4 mAh/g，100次循环后的保持率为85%。这项工作确定了提高电化学性能的最佳PAA比例，并证明了3D打印用于先进全固态锂电池制造的可行性。
