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摘要: 固态电解质是全固态锂电池的关键组分，其室温离子电导率和可加工性是影响电解质性能的关键指标。聚阴离子型固态电解质具有较高的锂离子迁移率，与其它类型陶瓷电解质相比，该电解质对水氧不敏感、成本低廉且原料无毒等特殊优点，明显降低了后期产业化的难度。本文首先总结了聚阴离子型固态电解质的分类和离子传输机制，然后介绍了提高材料本体锂离子传输性的原理和方法，最后介绍了通过表面修饰和复合改性提高电解质界面稳定性和可加工性方面的进展。结合全固态电池产业化对电解质膜片的需求，探索了目前聚阴离子型固态电池存在的问题和未来发展方向。作为一种具有优异的水氧稳定性和高离子电导率的电解质材料，聚阴离子电解质在下一代全固态电池中有着巨大的应用潜力。Abstract: Due to the urgent need for high-safety and high-energy density energy storage devices, all-solid-state lithium batteries have become a current research focus, with a solid electrolyte being a key component that determines their performance. Compared with other solid electrolytes, polyanions have a unique three-dimensional open framework for conducting lithium ions and an ultra-stability to water and oxygen, which gives them many potential applications. However, their poor room temperature ionic conductivity, the unstable interfacial structure of the electrode/electrolyte and their processability has hindered practical applications. To address these issues, recent progress in using polyanions as solid electrolytes is reviewed. First, ion transport mechanisms within polyanionic crystals and in the electrode/electrolyte interlayer are elaborated. Then, the principles and methods to improve lithium-ion transport in polyanionic electrolytes are summarized, and various surface modification methods to improve the stability and processability of the electrode/electrolyte interfaces are discussed. Finally, the processing and equipment that need to be developed and improved for all-solid-state battery fabrication are outlined, and developing trends to achieve the practical use of polyanions in all-solid-state batteries are discussed.
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Key words:
- Polyanions /
- Solid electrolyte /
- Interface layer /
- Composite electrolyte /
- Element doping
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图 1 液体、陶瓷、固体聚合物和复合电解质的物理和电化学特性
Figure 1. Physical and electrochemical characteristics of liquids, ceramics, solid polymers and composite electrolytes.
图 3 LiTi2(PO4)3、Li1.3Ti1.7M0.33+(PO4)3、LiTi1.7M0.34+(PO4)3和Li0.7Ti1.7M0.35+(PO4)3在30 ℃下的（a）体电导、（b）离子迁移的活化能和（c）晶胞体积[40]
Figure 3. (a) The volume conductance at 30 ℃, (b) the activation energy of ion migration and (c) the unit cell volume of LiTi2(PO4)3, Li1.3Ti1.7M0.33+(PO4)3, LiTi1.7M0.34+(PO4)3 and Li0.7Ti1.7M0.35+(PO4)3[40]. Reprinted with permission.
图 5 （a）Al(C3H7O)3和（b）Al(NO3)3中提取烧结球团的Arrhenius图，（c）陶瓷中Li离子传导的示意图[59]，（d, e）AlOOH样品的SEM照片[57]，（f）LAGP试样和（g）LAGP 20%L试样晶界特性示意图[60]
Figure 5. Arrhenius diagram of sintered pellets extracted from (a) Al(C3H7O)3 and (b) Al(NO3)3. (c) Schematic diagram of Li ion conduction in ceramics[59]. (d, e) SEM image of AlOOH sample[57]. Grain boundary characteristics of (f) LAGP and (g) LAGP 20%L[60]. Reprinted with permission.
图 6 （a）BN保护机理[64]，（b）磁控溅射制备超薄ZnO层包覆的LATP[20]，（c）LATP和DPCE的全固态电池结构[66]，（d）陶瓷粒子随机分布在聚合物基体中和垂直排列的结构[67]
Figure 6. (a) Protection mechanism of BN coating[64]. (b) Ultra-thin ZnO layer coated LATP through magnetron sputtering[20]. (c) Structure of all-solid-state battery with LATP and DPCE[66]. (d) The ceramic particles are randomly distributed in the polymer matrix and the structure of the vertical arrangement[67]. Reprinted with permission.
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