Abstract
Uncontrolled growth of lithium dendrite will lead to low Coulombic efficiency and poor cycle stability, which hinders the commercialization of lithium metal batteries. Herein, a novel modified lithium anode with reduced graphene oxide conductive network containing trace lithiophilic phosphorus (P-rGO/Cu) is prepared by electrospraying technique combined with heat treatment process. The rGO layer has a concave and undulating conductive structure, which can significantly improve the effective electrical contact between lithium metal and the current collector, speed up the kinetics of interfacial electron transport and reaction, and improve the resistance of the negative electrode to the internal stress caused by volume change of the lithium, which is advantageous for the stability of the SEI film. The extremely small and uniformly distributed red phosphorus element avoids the volume change caused by lithiation to the maximum extent. Lithiophilic two-phase compound Li3P obtained by alloying P with Li can directionally induce the homogeneous nucleation and dense deposition of lithium metal, address the issue of lithium dendrites and extend the cycle life of the batteries. The obtained P-rGO/Cu exhibits excellent electrochemical performance with an average Coulombic efficiency (CE) of 98% at a current density of 1 mA·cm−2 for 400 cycles, and the capacity retention rate of the full cell matched with lithium iron phosphate (LFP) is 83% after 400 cycles at 1C.
Graphical abstract
摘要
锂枝晶的不受控生长会导致电池的库仑效率降低, 循环稳定性变差, 从而阻碍锂金属电池的商业化进程。本文采用电喷与热处理制得了亲锂微量磷元素夹杂分布的还原氧化石墨烯导电网络改性锂负极 (P-rGO/Cu) 。研究表明rGO层凹凸起伏的导电结构显著增强金属锂与集流体间有效电接触, 加速界面电子传输与反应动力学; 以及增强负极承受锂体积变化产生内应力的能力, 有利于SEI膜的稳定; 微量P元素引入rGO层避免了锂化带来的体积变化; 利用P与Li合金化得到的亲锂两相化合物Li3P对锂金属的均匀形核与致密沉积进行定向诱导, 解决了锂枝晶问题, 提升了锂电池循环寿命。得到的P-rGO/Cu锂负极表现出优异的电化学性能, 在1 mA·cm−2电流密度下循环400圈的平均库伦效率(CE) 高达98%, 匹配磷酸铁锂 (LFP) 的全电池1C(170 mA·g−1) 循环400圈后容量保持率为83%。
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Acknowledgements
This study was financially supported by the Key-Area Research and Development Program of Guangdong Province (No. 2020B090919003), the National Natural Science Foundation of China (Nos. 52261160384, 51872157 and 52072208), the Fundamental Research Project of Shenzhen (No. JCYJ20190808153609561), the Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program (No. 2017BT01N111) and the Support Plan for Shenzhen Manufacturing Innovation Center (No. 20200627215553988). Authors thank the Materials and Devices Testing Center of Tsinghua University Shenzhen International Graduate School (Tsinghua SIGS).
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Chen, JX., Zhang, GQ., Qin, XY. et al. Lithium-induced graphene layer containing Li3P alloy phase to achieve ultra-stable electrode interface for lithium metal anode. Rare Met. 43, 562–574 (2024). https://doi.org/10.1007/s12598-023-02433-7
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DOI: https://doi.org/10.1007/s12598-023-02433-7