期刊
ACS APPLIED ENERGY MATERIALS
卷 4, 期 7, 页码 7073-7082出版社
AMER CHEMICAL SOC
DOI: 10.1021/acsaem.1c01133
关键词
alkaline battery; zinc; copper; bismuth; Zn/CuO cell; battery additive; EDXRD
资金
- U.S. Department of Energy's National Nuclear Security Administration [DE-NA-0003525]
- U.S. Department of Energy, Office of Electricity, and the Laboratory Directed Research and Development program at Sandia National Laboratories
In this study, a rechargeable alkaline zinc/copper oxide battery was successfully demonstrated, with the incorporation of Bi2O3 additive to enhance the battery performance. The role of Bi2O3 in stabilizing the copper oxide-based conversion cathode and promoting the reduction of copper species was highlighted as crucial for the improved electrochemical reversibility and cycling stability.
Resurrecting a battery chemistry thought to be only primary, we demonstrate the first example of a rechargeable alkaline zinc/copper oxide battery. With the incorporation of a Bi2O3 additive to stabilize the copper oxide-based conversion cathode, Zn/(CuO-Bi2O3) cells are capable of cycling over 100 times at >124 W h/L, with capacities from 674 mA h/g (cycle 1) to 362 mA h/g (cycle 150). The crucial role of Bi2O3 in facilitating the electrochemical reversibility of Cu2O, Cu(OH)(2), and Cu-o was supported by scanning and transmission electrochemical microscopy, cyclic voltammetry, and rotating ring-disc electrode voltammetry and monitored via operando energy-dispersive X-ray diffraction measurements. Bismuth was identified as serving two roles, decreasing the cell resistance and promoting Cu(I) and Cu(II) reduction. To mitigate the capacity losses of long-term cycling CuO cells, we demonstrate two limited depth of discharge (DOD) strategies. First, a 30% DOD (202 mA h/g) retains 99.9% capacity over 250 cycles. Second, the modification of the CuO cathode by the inclusion of additional Cu metal enables performance at very high areal capacities of similar to 40 mA h/cm(2) and unprecedented energy densities of similar to 260 W h/L, with near 100% Coulombic efficiency. This work revitalizes a historically primary battery chemistry and opens opportunity to future works in developing copper-based conversion cathode chemistries for the realization of low-cost, safe, and energy-dense secondary batteries.
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