固态锂电池具有优异的安全性，有潜力代替传统液态电池实现高能量密度，成为理想的能源存储解决方案。然而，固态电解质自身离子输运能力相对较弱且与电极存在较大的界面接触阻抗，不利于固态电池在室温下运行。本论文研究了固态电解质及正极中高效离子输运网络的构筑方法，揭示了固态电解质及其与电极界面以及固态正极内部的离子输运机制，有效提升电池的离子传输能力，获得室温性能优异的固态电池。首先，通过静电纺丝制备了聚丙烯腈（PAN）和聚碳酸丙烯酯（PPC）并排结构电解质，利用微量电解液选择性溶解PPC，使其在PAN三维骨架表面形成固液混合离子传输通道，显著增强了电解质离子传输能力并构筑了高稳定低阻抗的电解质/电极界面，抑制了电解液界面副反应。进而利用微量电解液蒸汽的润湿作用，在聚氧化乙烯（PEO）/PAN三维骨架复合电解质界面以及电解质/电极界面上构筑了高效离子输运通道，制备出室温性能优异的聚合物固态电池。该研究对设计高性能准固态电池提出新方法。其次，论文设计制备了介电钛酸钡（BaTiO3）与快离子导体锂镧钛氧（LLTO）平行耦合结构纳米线，与聚偏氟乙烯（PVDF）固态电解质复合后，发现BaTiO3的极化电场削弱了PVDF和LLTO界面的空间电荷层，提升聚合物内部自由锂离子浓度，LLTO促进了复合电解质及其界面离子传输效率。由于BaTiO3/LLTO对锂盐的解离和促进离子输运的协同效应，使复合电解质的室温离子电导率提升到8.2×10-4 S cm-1，匹配高镍三元正极的电池在室温下高性能稳定循环1500次。该工作创新地提出高介电性能的固态电解质，为高性能锂金属固态电池设计提供新的解决方案。最后，针对固态电池快充性能的需求，设计了PVDF基介电聚合物与快离子导体LLTO复合的新型正极离子传输和粘结集成网络（PTCL），不但削弱了正极活性物质颗粒与粘结剂之间的电势梯度，而且介电聚合物对LiTFSI锂盐具有良好的解离作用，在固态正极内部产生了高浓度自由锂离子，协同快离子导体LLTO，在正极内部构建高效锂盐解离和离子输运网络，使得匹配PVDF基固态电解质的固态电池在室温和较大电流密度下展示出优异的循环性能。该研究成为构筑固态正极内部导电网络提供了新方法。

Solid-state lithium batteries with safety and thermal stability have the potential to achieve higher energy density, making them an ideal energy storage technology solution. However, solid-state electrolyte has relatively weak ion transport and large contact impedance with electrode, which limits the performance of solid-state battery at room temperature. In this work, the construction method of efficient ion transport network in solid-state electrolyte and cathode was studied, and the ion transport mechanism in solid-state electrolyte, at the electrolyte/electrode interface and in cathode was also revealed, which effectively improve the ion transport in solid-state battery and achieve excellent performance of solid-state battery at room temperature.Firstly, a side-by-side electrolyte of polyacrylonitrile (PAN) and polypropylene carbonate (PPC) was prepared by electrospinning. With the selective dissolution of PPC by a small amount of liquid electrolyte, the PPC coated on the surface of PAN three-dimensional skeleton to form a solid-liquid mixed ion transport channel, which significantly enhanced the ion transport in electrolyte, realizing a stable and low impedance electrolyte/electrode interface and inhibit the interfacial reaction. Furthermore, a high efficiency ion transport channel was constructed on both the polyvinyl oxide (PEO)/PAN three-dimensional skeleton composite electrolyte interface and electrolyte/electrode interface by the wetting effect of trace electrolyte steam, and a PEO-based solid-state battery with excellent room temperature performance was prepared. This study provides a new idea for the design of high performance quasi-solid-state batteries. Secondly, BaTiO3 and LLTO nanowires were prepared in side-by-side structure and combined with polyvinylidene fluoride (PVDF) solid electrolyte. It was found that the polarization electric field of BaTiO3 weaken the space charge layer at the interface between PVDF and LLTO, promoting the transport efficiency of lithium ions at the interface between the composite solid electrolyte and LLTO and also increase the concentration of free lithium ions in the polymer matrix. Due to the synergistic effect of BaTiO3/LLTO on lithium salts dissociation and ion transport, the ionic conductivity of the composite electrolyte increased to 8.2×10-4 S cm-1 at room temperature, and the battery matched with LiNi0.8Co0.1Mn0.1O2 can stably cycle 1500 times at room temperature with high performance. This work innovatively proposed a solid-state electrolyte with high dielectric, providing a new solution for the design of high-performance lithium metal solid-state batteries.Finally, based on the demand for fast charging performance of solid-state battery, a new ion transport and bonding integrated network composed of PVDF dielectric polymer and fast ionic conductor LLTO in cathode was designed. This network weakens the electric potential gradient between active particles and binder in cathode. In addition, the dielectric polymer has a good dissociation effect on LiTFSI lithium salt, and a high concentration of free lithium ion is generated in the solid cathode. In collaboration with the fast ion conductor LLTO, an efficient dissociation of lithium salt and ion transport network is constructed in the cathode. Thus, solid-state batteries matching PVDF solid state electrolyte show excellent cycling performance at room temperature and high current density. This study provides a new method for the construction of conductive network inside the cathode of solid-state battery.