构建富氟杂化界面实现水性锌电池负极的防腐和均匀锌沉积  

Fluorinated hybrid interphases enable anti-corrosion and uniform zinc deposition for aqueous zinc metal batteries

作　　者：王乐泉 张隆 孟宇寰 张逸翔 康峻铭 李华晶 张佳佳 赵则栋 卢红斌 Lequan Wang;Long Zhang;Yuhuan Meng;Yixiang Zhang;Junming Kang;Huajing Li;Jiajia Zhang;Zedong Zhao;Hongbin Lu(State Key Laboratory of Molecular Engineering of Polymers,Department of Macromolecular Science,Fudan University,Shanghai 200438,China;Yiwu Research Institute of Fudan University,Yiwu 322000,China;School of Materials Science and Engineering,University of Science and Technology Beijing,Beijing 100083,China;Xiaomi EV Technology Co.,Ltd.,Beijing 100176,China)

机构地区：[1]State Key Laboratory of Molecular Engineering of Polymers,Department of Macromolecular Science,Fudan University,Shanghai 200438,China [2]Yiwu Research Institute of Fudan University,Yiwu 322000,China [3]School of Materials Science and Engineering,University of Science and Technology Beijing,Beijing 100083,China [4]Xiaomi EV Technology Co.,Ltd.,Beijing 100176,China

出　　处：《Science China Materials》2023年第12期4595-4604,共10页中国科学（材料科学）（英文版）

基　　金：financially supported by the National Natural Science Foundation of China(22075048 and 52201201);Shaanxi Yanchang Petroleum Co.,Ltd.(18529);Yiwu Research Institute of Fudan University(20-1-06);Shanghai International Collaboration Research Project(19520713900);the State Key Lab of Advanced Metals and Materials(2022Z-11).

摘　　要：使用低成本、高安全性的水系电解液使二次锌金属电池(AZMBs)成为大规模储能系统是最有前途的选择.然而,锌金属负极在水系电解液中热力学稳定性较差,严重阻碍了AZMBs的实际应用.在此,我们通过在锌表面涂覆氟化石墨并利用氟化石墨和锌之间原位的界面反应开发了一种富氟的杂化人工固体电解质界面来解决上述问题.疏水的氟化石墨可以有效地限制电解液和电极之间的接触,从而显著提高锌负极的抗腐蚀能力.同时,由氟化石墨和锌原位反应生成的ZnF_(2)共同组成的富氟杂化界面可以促进Zn2+的脱溶剂化作用,并均匀化锌离子通量,从而有效地抑制了副反应发生和枝晶生长.因此,在苛刻的测试条件下(10 mA cm^(−2),1 mA h cm^(−2)和30 mA cm^(−2),10 mA h cm^(−2)),对称电池可以分别稳定地循环1400和200小时以上,远远超过了裸锌的性能.此外,使用载量为6 mg cm^(−2)的MnO_(2)正极组装的Zn/MnO_(2)全电池在1 A g^(−1)的条件下经过2000次循环,仍能保持80%以上的容量.本文提出的这种构建富氟杂化ASEI的方法可以为设计高性能AZMBs提供一种有效的潜在策略.Rechargeable aqueous zinc(Zn)metal batteries(AZMBs)have become the most promising option for largescale energy storage systems because they utilize low-cost,high-safety aqueous electrolytes.However,the poor reversibility of the Zn anode due to inferior stability in aqueous electrolytes has severely impeded the practical applications of AZMBs.Herein,we propose a fluorine(F)-rich hybrid artificial solid electrolyte interphase(ASEI)to solve the above issue by coating Zn surface with fluorinated graphite and exploiting the interfacial reaction between fluorinated graphite and Zn.The interaction between the electrolyte and Zn was effectively restricted by the hydrophobic fluorinated graphite,thereby improving the corrosion resistance of the Zn anode.Furthermore,the F-rich hybrid interphase comprising fluorinated graphite and in situ generated ZnF2 facilitated the desolvation of Zn2+and homogenized the Zn2+flux,effectively inhibiting side reactions and dendrite growth.Consequently,the symmetric cell showed stable cycle performance for over 1400 h at 10 mA cm^(−2)and 1 mA h cm^(−2)and for 200 h at 30 mA cm^(−2)and 10 mA h cm^(−2),significantly exceeding the performance of the cell with a bare Zn anode.Moreover,the Zn/MnO_(2)full cell with the MnO_(2)loading of 6 mg cm^(−2)maintained more than 80%capacity after 2000 cycles at 1 A g^(−1).This strategy for constructing fluorinated hybrid ASEI is a promising approach for the design of high-performance AZMBs.

关 键 词：Zn metal anode hybrid interphase corrosion DENDRITES aqueous Zn battery 

分 类 号：TM912[电气工程—电力电子与电力传动] TG174.4[金属学及工艺—金属表面处理]