Yan Yu, Shu Chaozhu, Zeng Ting, Wen Xiaojuan, Liu Sheng, Deng Dehui, Zeng Ying
College of Materials and Chemistry and Chemical Engineering, Chengdu University of Technology, 1# Dongsanlu, Erxianqiao, Chengdu 610059, Sichuan, People's Republic of China.
State Key Laboratory of Catalysis, iChEM, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, People's Republic of China.
ACS Nano. 2022 Jun 28;16(6):9150-9162. doi: 10.1021/acsnano.2c01380. Epub 2022 Jun 13.
Aqueous Zn batteries with ideal energy density and absolute safety are deemed the most promising candidates for next-generation energy storage systems. Nevertheless, stubborn dendrite formation and notorious parasitic reactions on the Zn metal anode have significantly compromised the Coulombic efficiency (CE) and cycling stability, severely impeding the Zn metal batteries from being deployed in the proposed applications. Herein, instead of random growth of Zn dendrites, a guided preferential growth of planar Zn layers is accomplished via atomic-scale matching of the surface lattice between the hexagonal close-packed (hcp) Zn(002) and face-centered cubic (fcc) Cu(100) crystal planes, as well as underpotential deposition (UPD)-enabled zincophilicity. The underlying mechanism of uniform Zn plating/stripping on the Cu(100) surface is demonstrated by ab initio molecular dynamics simulations and density functional theory calculations. The results show that each Zn atom layer is driven to grow along the exposed closest packed plane (002) in hcp Zn metal with a low lattice mismatch with Cu(100), leading to compact and planar Zn deposition. In situ optical visualization inspection is adopted to monitor the dynamic morphology evolution of such planar Zn layers. With this surface texture, the Zn anode exhibits exceptional reversibility with an ultrahigh Coulombic efficiency (CE) of 99.9%. The MnO//Zn@Cu(100) full battery delivers long cycling stability over 548 cycles and outstanding specific energy and power density (112.5 Wh kg even at 9897.1 W kg). This work is expected to address the issues associated with Zn metal anodes and promote the development of high-energy rechargeable Zn metal batteries.
具有理想能量密度和绝对安全性的水系锌电池被认为是下一代储能系统最有前景的候选者。然而，锌金属阳极上顽固的枝晶形成和臭名昭著的寄生反应严重损害了库仑效率（CE）和循环稳定性，严重阻碍了锌金属电池在拟议应用中的部署。在此，通过六方密堆积（hcp）Zn(002)和面心立方（fcc）Cu(100)晶面之间的表面晶格原子尺度匹配以及欠电位沉积（UPD）实现的亲锌性，实现了平面锌层的引导优先生长，而不是锌枝晶的随机生长。从头算分子动力学模拟和密度泛函理论计算证明了在Cu(100)表面均匀镀/剥锌的潜在机制。结果表明，每个锌原子层被驱动沿着hcp锌金属中暴露的最密堆积面（002）生长，与Cu(100)的晶格失配较低，导致致密且平面的锌沉积。采用原位光学可视化检查来监测这种平面锌层的动态形态演变。凭借这种表面纹理，锌阳极表现出卓越的可逆性，库仑效率高达99.9%。MnO//Zn@Cu(100)全电池在548次循环中具有长循环稳定性，以及出色的比能量和功率密度（即使在9897.1 W kg时也达到112.5 Wh kg）。这项工作有望解决与锌金属阳极相关的问题，并促进高能可充电锌金属电池地发展。
