中国科学院青岛生物能源与过程研究所崔光磊团队揭示了共晶结晶激活固态锌离子传导。相关研究成果发表在2021年10月19日出版的《德国应用化学》。

固态锌电池为为体积、安全性和成本敏感的新兴应用提供了新的理想选择。然而，目前的固体聚合物或陶瓷电解质结构对二价Zn²⁺的导电性较差，尤其是在室温下。构建一个允许Zn²⁺渗透的异质界面是一个可行的选择，但其在多价体系中很少涉及。

该文中，研究人员开发了一条新的途径，通过诱导由有机锌盐和双极配体形成的定制共晶液体结晶来构建固体Zn²⁺离子导体。高熵共晶网络有助于削弱离子缔合，并在成核剂表面形成界面Zn²⁺渗流通道，从而形成对Zn²⁺传输具有特殊选择性（t_Zn²⁺=0.64）和可观的Zn²⁺电导率的固态晶体（30°C下σ_Zn²⁺=3.84×10^-5 Scm^-1，超过2个数量级的常规聚合物），最终实现了实际环境温度下的Zn/V₂O₅金属固体电池。

由共晶凝固所提供的设计原理为遭受缓慢离子迁移的多价固体电化学提供了新的见解。

附：英文原文

Title: Eutectic Crystallization Activates Solid-State Zinc-Ion Conduction

Author: Guanglei Cui, Huayu Qiu, Rongxiang Hu, Xiaofan Du, Zhou Chen, Jingwen Zhao, Guoli Lu, Meifang Jiang, Qingyu Kong, Yiyuan Yan, Junzhe Du, Xinhong Zhou

Issue&Volume: 2021-10-19

Abstract: Solid-state zinc (Zn) batteries offer new desirable candidate for emerging applications sensitive to volume, safety and cost. However, current solid polymeric or ceramic electrolyte structures remain poorly conductive for the divalent Zn2+, especially at room temperature. Constructing a heterogeneous interface which allows Zn2+ percolation is a viable option, but this is rarely involved in multivalent systems. Herein, we split a new path to construct solid  Zn2+-ion conductor via  inducing crystallization of tailored eutectic liquids formed by organic Zn salts and bipolar ligands. High-entropy eutectic-networks avail to weaken the ion-association and form interfacial Zn2+ percolated channels on the nucleator surfaces, resulting in a solid crystal with exceptional selectivity for Zn2+ transport (tZn2+ = 0.64) and appreciable Zn2+ conductivity (σZn2+ = 3.84 ×10-5 Scm-1 at 30°C, over 2 orders of magnitude conventional polymers), and finally enabling practical ambient-temperature Zn/V2O5 metal solid cells. This design principle leveraged by the eutectic solidification affords new insights on the multivalent solid electrochemistry suffering from slow ion migration.

DOI: 10.1002/anie.202113086

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202113086