Rechargeable Li-CO2 batteries are well-regarded for their high-energy, environmental friendliness, and resourceful use of CO2, but suffer from poor cycle reversibility. Herein, Al-doped Co3O4 nanoflakes featuring abundant metal vacancies (V-ACO/CC) were synthesized via a facile approach employing Al ions as both a dopant and sacrificial agents, which serve as high-efficient cathode catalyst for Li-CO2 batteries. Experiment results demonstrate that the incorporation of Al doping and metal vacancies modulates the electronic structure of Co-center and optimizes the growth path of discharge product. The cation vacancies generated by the sacrificed part of the Al atoms change the local charge distribution, strengthen the affinity of CO2 and reaction intermediates and facilitate the reversible decomposition of discharge products. Concurrently, the formation of covalent Al-O bonds by the remaining Al species reinforces the stability of nanostructures. Notably, the V-ACO/CC-based LCBs exhibit enhanced CO2 conversion kinetics, as evidenced by a high specific capacity (12.06 mAh cm−2 at 0.05 mA cm−2), fast rate capability and impressive stability (over 420 cycles under 0.1 mA cm−2).

中文翻译：

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通过集成铝掺杂和金属空位工程增强大容量锂二氧化碳电池的 Co3O4 纳米片反应性


可充电锂二氧化碳电池因其高能量、环境友好和充分利用二氧化碳而受到好评，但其循环可逆性较差。在此，采用Al离子作为掺杂剂和牺牲剂，通过简单的方法合成了具有丰富金属空位的Al掺杂Co3O4纳米片（V-ACO/CC），作为Li-CO2电池的高效阴极催化剂。实验结果表明，Al掺杂和金属空位的结合调节了Co中心的电子结构并优化了放电产物的生长路径。牺牲部分Al原子产生的阳离子空位改变了局部电荷分布，增强了CO2和反应中间体的亲和力，有利于放电产物的可逆分解。同时，剩余的 Al 物质形成共价 Al-O 键，增强了纳米结构的稳定性。值得注意的是，基于 V-ACO/CC 的 LCB 表现出增强的 CO2 转化动力学，高比容量（0.05 mA cm−2 时为 12.06 mAh cm−2）、快速倍率能力和令人印象深刻的稳定性（0.1 下超过 420 个循环）证明了这一点。 mA cm−2)。