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摘要:
随着临近空间飞行器的战略地位日渐增长，其对大功率、高比能、长循环储能电池体系的需求也不断提高，锂金属电池具有超高的理论容量，有望成为新一代临近空间飞行器储能电池的有力候选者。锂金属电极具有极低的氧化还原电位、较高的理论容量，但锂枝晶生长带来的各种问题一直制约着锂金属负极的应用。基于氧化刻蚀和离子交换原理，在泡沫铜(CF)上制备CuO纳米线阵列并引入Au作为亲锂位点，成功构建了Au-CuO/CF纳米阵列三维（3D）集流体并应用于锂金属电池负极，其库伦效率、循环寿命及循环稳定性均明显优于未经修饰的CuO/CF纳米阵列三维集流体，与磷酸铁锂正极(LFP)组成全电池后放电比容量高于CuO/CF纳米阵列三维集流体并在700圈循环后仍有高达97.7%的容量保持率。Au-CuO/CF纳米阵列三维集流体制备工艺简单，电化学性能优异，全电池更表现出稳定的循环性能和极高的容量保持能力，具有成为下一代高比能量锂金属电池负极集流体的应用潜力。
Abstract:With the growing strategic position of near-space vehicles, the demand for energy storage batteries with high power, high specific energy, and long cycle life has also increased. Lithium metal battery with ultra-high theoretical specific energy is a promising candidate for the next-generation energy storage system of near-space vehicles. Lithium metal exhibits extremely low reduction potential and high theoretical capacity, but its application is limited by issues associated with dendrite growth. In this paper, based on oxidation etching and ion exchange mechanism, a three-dimensional (3D) Au-CuO nanowire array current collector on copper foam (CF) (Au-CuO/CF nanoarray 3D current collector) was successfully prepared via the preparation of CuO nanowire array on CF and the introduction of Au as lithophilic sites. This current collector was then applied as a lithium metal battery anode. Compared to the CuO/CF nanoarray 3D current collector, the Au-CuO/CF nanoarray 3D current collector demonstrated significantly improved Coulombic efficiency, cycle life, and cycling stability. When paired with a lithium iron phosphate (LFP) cathode, the full cell achieved a capacity retention of 97.7% after 700 cycles. The Au-CuO/CF nanoarray 3D current collector features simple preparation and excellent electrochemical performance, with the full cell demonstrating outstanding cycling stability and exceptional capacity retention, showing great potential as a next-generation high-energy-density lithium metal battery anode current collector.
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图 1 Au-CuO/CF及CuO/CF纳米阵列三维集流体的XRD图谱
Figure 1. XRD patterns of Au-CuO/CF and CuO/CF nanoarray 3D current collectors
图 3 Au-CuO/CF纳米阵列三维集流体的XPS分析
Figure 3. XPS image of Au-CuO/CF nanoarray 3D current collector
图 4 Au-CuO/CF纳米阵列三维集流体的SEM表征
Figure 4. SEM image of Au-CuO/CF nanoarray 3D current collector
图 5 Au-CuO/CF纳米阵列三维集流体的TEM表征
Figure 5. TEM characterization of Au-CuO/CF nanoarray 3D current collector
图 6 Au-CuO/CF纳米阵列三维集流体沉积/剥离Li的SEM表征
Figure 6. SEM characterization of Au-CuO/CF nanoarray 3D current collector after Li deposition/stripping
图 7 Au-CuO/CF和CuO/CF纳米阵列三维集流体在不同测试条件下的库伦效率
Figure 7. Coulombic efficiencies of Au-CuO/CF and CuO/CF nanoarray 3D current collector under different test conditions
图 8 Au-CuO/CF纳米阵列三维集流体循环100圈后的SEM表征
Figure 8. SEM characterization of Au-CuO/CF nanoarray 3D current collector after 100 cycles
图 9 Au-CuO/CF及CuO/CF纳米阵列三维集流体的充放电曲线及过电位曲线
Figure 9. Charging–discharging curve and overpotential curve of Au-CuO/CF and CuO/CF nanoarray 3D current collector
图 10 Li|Au-CuO@Li/CF和Li|CuO@Li/CF对称电池在1 mA/cm2-1 mAh/cm2条件下的电压-时间曲线
Figure 10. Voltage–time curve of Li|Au-CuO@Li/CF and Li|CuO@Li/CF symmetrical battery under condition of1 mA/cm2-1 mAh/cm2
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