Brief overview of microscopic physical image of ion transport in electrolytes

Ren Yuan; Zou Zhe-Yi; Zhao Qian; Wang Da; Yu Jia; Shi Si-Qi

doi:10.7498/aps.69.20201519

Abstract

Analyzing the microscopic physical image of the ion transport characteristics has important guiding significance for improving the ion conduction behavior in the electrolytes. In this article, we summarize the factors influencing the physical images of ion transport in liquid, organic polymer and inorganic solid electrolytes. The descriptive factors relating to the ion transport physical image are refined by analyzing various transport physical models and comparing the ion transport mechanisms in the three types of electrolytes. In the evolution of the physical state from continuous fluid to flexible carrier to rigid framework, the ion transport image is characterized by the inherent properties of various electrolytes and external conditions, in which the disorder of the medium plays a dominant role. Revealing the relationships between the electrolyte structure and dynamic behaviors with the ion conductivity and transport process is conducive to the development of the method of controlling the dynamic performance of conducting ion based on the microphysical image of ion transport.

Keywords:

Authors and contacts

1.
School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China
2.
School of Mechanical Engineering, Inner Mongolia University of Science & Technology, Baotou, Inner Mongolia 014010, China
3.
School of Materials Science and Engineering, Xiangtan University, Xiangtan, Hunan 411105, China
4.
Materials Genome Institute, Shanghai University, Shanghai 200444, China

Corresponding author: Shi Si-Qi, sqshi@shu.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 11874254, 51702170, 51802187, 51622207), the Sailing Program of Shanghai, China (Grant No. 18YF1408700), and the Natural Science Foundation of Inner Mongolia Autonomous Region, China (Grant No. 2020MS05036)

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图 1 可供离子输运的电解质, 包括: 液态电解质、聚合物基固态电解质、无机固态电解质以及复合固态电解质

Figure 1. The electrolytes for ion transport: liquid electrolyte, polymer-based solid electrolyte, inorganic solid electrolyte and composite solid electrolyte.

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图 2 影响离子输运微观物理图像的因素包括输运机制与描述因子. 如: 左上角knock-off离子输运^[21]; 右上角: BVSE方法描述离子输运通道^[22]; 左下角: NASICON中多离子协同输运^[23]; 复合结构电解质离子输运^[8]

Figure 2. The factors affecting the microscopic physical image of ion transport: transport mechanism and description factors. For example: knock-off ion transport^[21], BVSE method based ion transport channel description^[22], multi-ion coordinated transport in NASICON^[23], mobile ion in composite solids^[8].

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图 3 液态电解质溶剂化与去溶剂化动力学过程中携带式离子输运方式示意图

Figure 3. The schematic diagram of portable ion transport in the kinetic process of solvation and desolvation of liquid electrolyte.

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图 4 有机聚合物基固态电解质中离子在配位之间传递输运方式示意图

Figure 4. The schematic diagram of ion transport between coordination in the organic polymer-based solid electrolyte.

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图 5 无机固态电解质中离子输运方式:　(a)传导离子在晶体内输运方式示意图; (b)传导离子沿晶界输运方式示意图; (c)传导离子跨晶界输运方式示意图

Figure 5. The ion transport in the inorganic solid electrolytes: (a) The ion transport in the bulk; (b) the ion transport along the grain boundaries; (c) the ion transport across the grain boundaries.

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图 6 无机固态电解质中晶体内离子间隙扩散输运方式：(a)离子直接在间隙中迁移示意图; (b)离子在空位之间迁移示意图

Figure 6. The ion interstitial diffusion transport in the inorganic solid electrolytes: (a) The interstitial ion transport; (b) the vacant ion transport.

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图 7 无机固态电解质中输运离子与骨架离子换位协同输运示意图

Figure 7. The concerted and coordinated diffusion of transport ion and skeleton ion in the inorganic solid electrolytes.

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图 8 电解质中主导离子输运微观物理图像的因素由结构主导作用到介质主导作用的演变过程^[10]

Figure 8. The evolution process between structural and vehicular effect the microscopic physical image of the contribution to the ion transport in the electrolytes^[10].

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图 9 “聚合物陶瓷”和“陶瓷聚合物”电解质系统中可能的离子传输机制^[82]

Figure 9. The schematic diagram of possible ion transport mechanisms in "ceramic-in-polymer" and "polymer-in-ceramic" electrolyte system^[82].

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图 10 传导离子在LTMH (Li₃TMCl₆)中输运特性　(a) Li⁺在$ P\bar 3 m1$ Li₃YCl₆中输运路径^[110]; (b) Li⁺在hcp阴离子晶格Li₃YCl₆中输运路径^[111]; (c) Li⁺在Li₃ErCl₆和Li₃YCl₆中的输运行为^[112]; (d) Li⁺在ccp阴离子晶格Li₃ScCl₆中输运路径^[113]

Figure 10. Transport characteristics of conductive ions in LTMH (Li₃TMCl₆): (a) The ion transport in Li₃YCl₆ with space group $P\bar 3 m1$^[110]; (b) the ion transport in Li₃YCl₆ with hcp-like Anion lattice^[111]; (c) the ion transport in Li₃MCl₆ (M = Y, Er) with space group $P\bar 3 m1$^[112]; (d) the ion transport in Li₃ScCl₆ with ccp Anion lattice^[113].

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图 11 液态、聚合物以及无机固态电解质离子运输形式　(a) 液态电解质中溶剂分子协调离子输运^[115]; (b) 聚合物基电解质中链段运动与离子输运^[116]; (c) 具有骨架通道NASICON中多离子协同输运^[23]

Figure 11. Transport form of ion in the liquid, organic polymer and inorganic solid electrolytes: (a) Li⁺ coordination in electrolyte^[115]; (b) Ion coordinated transport in the single-ion solid-state polymer electrolytes^[116]; (c) Concerted migration of multi-ion in NASICON with framework channels^[23].

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Vol. 69, Issue 22 - 2020-11-20

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