Sun, Yuanhe; Yao, Zeying; Lei, Qi; Zhao, Yuanxin; Ren, Zhiguo; Zhang, Wei; Si, Jingying; Zhang, Lei; Wen, Wen; Zhu, Daming; Li, Xiaolong; Tai, Renzhong

ADVANCED MATERIALS

2023, 35, 1521-4095

Sun, Yuanhe; Yao, Zeying; Lei, Qi; Zhao, Yuanxin; Ren, Zhiguo; Zhang, Wei; Si, Jingying; Zhang, Lei; Wen, Wen; Zhu, Daming; Li, Xiaolong; Tai, Renzhong

High-energy metal anodes for large-scale reversible batteries with inexpensive and nonflammable aqueous electrolytes promise the capability of supporting higher current density, satisfactory lifetime, nontoxicity, and low-cost commercial manufacturing, yet remain out of reach due to the lack of reliable electrode-electrolyte interphase engineering. Herein, in situ formed robust interphase on copper metal electrodes (CMEs) induced by a trace amount of potassium dihydrogen phosphate (0.05 m in 1 m CuSO4-H2O electrolyte) to fulfill all aforementioned requirements is demonstrated. Impressively, an unprecedented ultrahigh-speed copper plating/stripping capability is achieved at 100 mA cm-2 for over 12 000 cycles, corresponding to an accumulative areal capacity up to tens of times higher than previously reported CMEs. The use of solid-electrolyte interface-protection strategy brings at least an order of magnitude improvement in cycling stability for symmetric cells (Cu||Cu, 2800 h) and full batteries with CMEs using either sulfur cathodes (S||Cu, 1000 cycles without capacity decay) or zinc anodes (Cu||Zn with all-metal electrodes, discharge voltage approximate to 1.02 V). The comprehensive analysis reveals that the hydrophilic phosphate-rich interphase nanostructures homogenize copper-ion deposition and suppress nucleation overpotential, enabling dendrite-free CMEs with sustainability and ability to tolerate unusual-high power densities. The findings represent an elegant forerunner toward the promising goal of metal electrode applications. Low-cost and reliable in situ phosphate interphase engineering implements on aqueous copper metal electrodes. Robust interphase enables ultrahigh current shocks up to 100 mA cm-2, and brings at least an order of magnitude improvement in cycling stability for symmetric cells and full batteries, representing exciting possibilities for realizing practically aqueous metal electrodes.image