Zhou Xunzhu, Chen Xiaomin, Kuang Wenxi, Zhu Wenqing, Zhang Xiaosa, Liu Xiaohao, Wu Xingqiao, Zhang Longhai, Zhang Chaofeng, Li Lin, Wang Jiazhao, Chou Shu-Lei
School of Materials Science and Engineering, Institutes of Physical Science and Information Technology, Leibniz Joint Research Center of Materials Sciences, Key Laboratory of Structure and Functional Regulation of Hybrid Material (Ministry of Education), Anhui University, Hefei, Anhui, 230601, China.
Institute for Carbon Neutralization Technology, College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang, 325035, China.
Angew Chem Int Ed Engl. 2024 Oct 14;63(42):e202410494. doi: 10.1002/anie.202410494. Epub 2024 Sep 12.
Anion-reinforced solvation structure favors the formation of inorganic-rich robust electrode-electrolyte interface, which endows fast ion transport and high strength modulus to enable improved electrochemical performance. However, such a unique solvation structure inevitably injures the ionic conductivity of electrolytes and limits the fast-charging performance. Herein, a trade-off in tuning anion-reinforced solvation structure and high ionic conductivity is realized by the entropy-assisted hybrid ester-ether electrolyte. Anion-reinforced solvation sheath with more anions occupying the inner Na shell is constructed by introducing the weakly coordinated ether tetrahydrofuran into the commonly used ester-based electrolyte, which merits the accelerated desolvation energy and gradient inorganic-rich electrode-electrolyte interface. The improved ionic conductivity is attributed to the weakly diverse solvation structures induced by entropy effect. These enable the enhanced rate performance and cycling stability of Prussian blue||hard carbon full cells with high electrode mass loading. More importantly, the practical application of the designed electrolyte was further demonstrated by industry-level 18650 cylindrical cells.
阴离子增强溶剂化结构有利于形成富含无机成分的坚固电极-电解质界面,这赋予了快速离子传输和高强度模量,从而实现了电化学性能的提升。然而,这种独特的溶剂化结构不可避免地损害了电解质的离子电导率,并限制了快速充电性能。在此,通过熵辅助混合酯-醚电解质实现了在调节阴离子增强溶剂化结构和高离子电导率之间的权衡。通过将弱配位的醚类四氢呋喃引入常用的酯基电解质中,构建了具有更多阴离子占据内层钠壳的阴离子增强溶剂化鞘层,这有利于加速去溶剂化能和梯度富含无机成分的电极-电解质界面。离子电导率的提高归因于熵效应诱导的弱多样化溶剂化结构。这些使得具有高电极质量负载的普鲁士蓝||硬碳全电池的倍率性能和循环稳定性得到增强。更重要的是,工业级18650圆柱形电池进一步证明了所设计电解质的实际应用。