Advances in solid polymer electrolyte matrices for lithium-ion batteries
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摘要: 固态聚合物电解质(SPE)因具有安全性高、机械强度高与电极界面接触性良好等优势，在固态锂离子电池有更广泛的应用前景。聚合物基质在SPE中作主体，起着骨架支撑和促进锂离子的解离和运输作用，是SPE中不可缺少的部分。本文综述了目前对聚合物基质最新的改性策略，以提升SPE的电化学性能和力学性能。通过调节聚合物基质结构、形貌、制备工艺以及添加无机填料方面来改善聚合物基质的结晶度和锂离子传输通道，提升SPE的电化学性能，有望为固态锂离子电池商业化做出贡献。Abstract: Solid state polymer electrolyte (SPE) has a wider application prospect in solid state lithium ion batteries due to its advantages of high safety, high mechanical strength and good contact with electrode interface. Polymer matrix is an indispensable part of SPE as the main body, which plays the roles of skeleton support and promotion of lithium ion dissociation and transport. This paper reviews the latest modification strategies of polymer matrix to enhance the electrochemical and mechanical properties of SPEs. Improving the crystallinity and lithium ion transport channels of the polymer matrix by modifying its structure, morphology, preparation process, and addition of inorganic fillers to enhance the electrochemical performance of SPEs is expected to contribute to the commercialisation of solid-state lithium-ion batteries.
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图 4 无机填料LLZO与PEO形成CPE示意图(a)[52]、Li+分布在PEO基体中；PEO基体和PEO/陶瓷界面处；PEO基体和陶瓷相及PEO/陶瓷界面处的传导途径示意图(b)[51]、Li+在LLZO -PEO -LiTFSI不同比例的复合电解质中的路径示意图(c)[52]
Figure 4. Inorganic filler LLZO and PEO form CPE diagram(a)[52], Li+ is distributed in the PEO matrix; PEO matrix and PEO / ceramic interface; the conduction pathway diagram of PEO matrix and ceramic phase and PEO / ceramic interface(b)[51], the path diagram of Li+ in LLZO-PEO-LiTFSI composite electrolyte with different proportions(c) [52]
图 5 采用溶液浇铸法制备PEO- LiClO4-LLZTO复合固态电解质流程示意图(a)[46]制备三维多孔导LATP骨架和抑制锂枝晶生长示意图(b)[50]
Figure 5. Preparation of PEO-LiClO4-LLZTO composite solid electrolyte by solution casting process schematic diagram(a)[53], preparation of three-dimensional porous LATP skeleton and inhibition of lithium dendrite growth schematic diagram(b)[50]
图 9 AAO -聚合物复合电解质的结构设计和电化学性能测试: 内部锂离子传输通道示意图(a)、复合电解质的制备工艺示意图(b)、APCE的在0.25 mA / cm2电流密度下测得的锂对称电池中锂沉积/剥离示意图(c)[62]
Figure 9. The structure design and electrochemical performance test of AAO-polymer composite electrolyte: schematic diagram of internal lithium ion transport channel (a), schematic diagram of preparation process of composite electrolyte (b), schematic diagram of lithium deposition / stripping in lithium symmetric battery measured by APCE at a current density of 0.25 mA / cm2 (c)[62]
表 1 PEO与其他聚合物共混后离子电导率[13]
Table 1. The ionic conductivity of PEO after blending with other polymers was studied [13]
polymer matrix lithium salt temperature/
℃Ionic conductivity/
(S·cm−1)PEO/MEEP LiBF4 25 4 × 10−6 PEO/PES LiClO4 25 1.0 × 10−5 PEO/PET LiClO4 25 2.0 × 10−5 PEO/PVDF LiClO4 30 2.6 × 10−5 PEO/PVDF LiTFSI 30 4.9 × 10−3 
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