固态电解质中锂离子传输机理研究进展

doi:10.13208/j.electrochem.201244

摘要/Abstract

摘要：

固态电解质在室温下表现出非凡的离子导电性,使其有潜力应用于全固态锂离子电池。开发新的高性能固态电解质需要对锂离子传输机理及其规律进行深入研究。本文论述了近期研究中锂离子传输机理方面的研究进展,包括离子传输理论基础的概述;总结Li₁₀GeP₂S₁₂、Li₇La₃Zr₂O₁₂和Li₁₊_xAl_xTi_2-_x(PO₄)₃固态电解质材料中晶体结构、离子传输和研究进展;阐述锂离子传输中结构特征、传输机理（单离子跳跃传输和多离子协同传输）以及构效关系;总结（反）Meyer-Neldel规则的关键问题和相关电解质材料。最后,展望了给出电解质材料的设计策略和未来机理研究的重点,为无机固态电解质材料的探索提供新的思路和方向。

关键词: 固态电解质, 离子传输机理, 协同传输, 构效关系, Meyer-Neldel规则

Abstract:

Inorganic crystalline solid electrolytes exhibit exceptional room-temperature ionic conductivities, giving them the potential to enable all-solid-state lithium (Li) - ion batteries. Developing new high-performance electrolytes is one of the most critical challenges to realize solid-state batteries, which requires understanding how chemistry facilitates fast ionic conduction and what the Li-ion migration mechanism is in inorganic solid electrolytes. In this review, we aim to summarize recent fundamental research progress in Li-ion transport, including crystal structure, behavior of ion migration (i.e., single-ion jump and multi-ions cooperative migration), and the relationship between ion migration and microstructure.
Generally, ion transport in crystalline structure can be categorized into vacancy and non-vacancy mechanism. For Li-ion conduction, the migration can be achieved through single-ion hopping and collective diffusion mechanism. For single-ion hopping mechanism, the diffusivity is determined by the depth of potential well (activation energy) and lattice dynamics; whereas in the later mechanism Li-ion moving from high potential to low potential could partially offset the energy required for Li-ion moving from low potential to high potential. By studying the collective diffusion from the perspective of local structures, it is believed that collective diffusion in fast ion conductor originates from the local “dual Li-S/O” structure units, which can be characterized by the “nearest Li-Li distance”.
Next, the paradigm of ion transport in solids is summarized. It is pointed out that most ion conductors follow Meyer-Neldel rule, where the activation energy and pre-exponential factor are mutual compensating. As a result, a balance should be adapted between these two values to achieve high Li-ion conductivity. However, for some fast ion conductors, the relationship does not follow the Meyer-Neldel rule (i.e., anti-Meyer-Neldel rule). Therefore, the physical significance of anti-Meyer-Neldel rule should be understood to develop next-generation lithium ion conductors.
In the end, future perspectives and open questions are proposed to design and develop high-performance inorganic solid electrolytes.

Key words: solid-sate electrolytes, Li-ion transport mechanism, cooperative transport, structure-function relationship, Meyer-Neldel rule

张丙凯, 杨卢奕, 李舜宁, 潘锋. 固态电解质中锂离子传输机理研究进展[J]. 电化学（中英文）, 2021, 27(3): 269-277.

Bing-Kai Zhang, Lu-Yi Yang, Shun-Ning Li, Feng Pan. Progress of Lithium-Ion Transport Mechanism in Solid-State Electrolytes[J]. Journal of Electrochemistry, 2021, 27(3): 269-277.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.201244

https://electrochem.xmu.edu.cn/CN/Y2021/V27/I3/269

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Solid-state electrolyte	Room-temperature conductivity/(S·cm^-1)	Lattice parameters/Å			Space group	Ref.
Solid-state electrolyte	Room-temperature conductivity/(S·cm^-1)	a	b	c	Space group	Ref.
Li₁₀GeP₂S₁₂	1.20 × 10 ^-2	8.69	8.69	12.60	P42/nmc	[8]
Li_1.3Al_0.3Ti_1.7(PO₄)₃	3.00 × 10 ^-3	8.50	8.50	20.82	R-3c	[11]
Li₇La₃Zr₂O₁₂	3.10 × 10 ^-4	12.97	12.97	12.97	Ia-3d	[13]

Mechanism	Description	Feature
Vacancy mechanism
Vacancy	Self-diffusion in single element crystals, metals or alloys	Li-ions’ migration gain energy to break chemical bonds with neighboring atoms. The jump of Li-ions will cause that the energy breaking chemical bonds comes from the heat of atomic vibration (E_av - k_BT).
Divacancy	Diffusion through the accumulation of vacancies
Non-Vacancy
Interstitial	Interstitial ions are much smaller than the host lattice ones (such as C, H, O), and the ions are incorporated into the interstitial positions of the host lattice to form interstitial solid solutions.	Interstitial diffusion is usually faster than vacancy diffusion because of the weaker bonds between the interstitial ions and surrounding ones.
Collective migration		The following three types of mechanisms have the characteristic of cooperative transmission, that is, multiple ions transport is collective.
Interstitialcy	A collective mechanism important for radiation-induced diffusion. At least two atoms move simultaneously; however, this mechanism is negligible for thermal diffusion
Interstitial-substitutional exchange	Solute atoms are dissolved on both interstitial and substitutional sitesand diffuse via interstitial or substitutional exchange mechanisms