Key Laboratory of Mesoscopic Chemistry of MOE and Collaborative Innovation Center of Chemistry for Life Sciences, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China.
Key Laboratory of MEMS of the Ministry of Education, Department of Physics, Southeast University, Nanjing 210096, China.
Nanoscale. 2016 Apr 14;8(14):7408-15. doi: 10.1039/c5nr08832a.
Lithiated transition metal phosphates with large theoretical capacities have emerged as promising cathode materials for rechargeable lithium-ion batteries. However, the poor kinetic properties caused by their low intrinsic electronic and ionic conductivity greatly hinder their practical applications. In this work, we demonstrate a novel strategy to prepare monoclinic lithium vanadium phosphate nanoparticles implanted in carbon nanofibers as the cathodes of Li-ion cells with high capacity, flexibility, long cycle stability and significantly improved high-rate performance. The composite nanofibers were obtained by electrospinning using polyacrylonitrile and Li3V2(PO4)3 nanoparticles, followed by annealing and coating with a thin layer of carbon by plasma enhanced chemical vapor deposition. The Li3V2(PO4)3 nanocrystals with the monoclinic phase were uniformly distributed in the composite nanofibers. The electrochemical performances of the as-prepared binder-free fibrous cathodes were characterized by potentiostatic and galvanostatic tests. At the rate of 0.5 C in the range of 3.0-4.3 V, the composite displayed an initial discharge capacity of 128 mA h g(-1) (96.2% of the theoretical capacity). A discharge capacity of 120 mA h g(-1) was observed even at a high rate of 10 C, and a capacity retention of 98.9% was maintained after 500 cycles at 5 C, indicating excellent high-rate capability and capacity retention. Compared to the control samples without a carbon outer-layer, the composite nanofibers with carbon coating demonstrated much better electrochemical performances. It indicates that the carbon coating can further protect the structural integrity of nanofabric electrodes during the charge/discharge processes without hindering the Li-ion mobility and also can prevent undesired side reactions with an electrolyte, thus greatly improving the rate performance and cyclic stability of the cathode.
具有大理论容量的层状过渡金属磷酸盐作为可充电锂离子电池的阴极材料具有广阔的应用前景。然而,其低本征电子和离子电导率导致较差的动力学性能,严重阻碍了它们的实际应用。在这项工作中,我们展示了一种新的策略,即用聚丙烯腈和 Li3V2(PO4)3 纳米粒子通过静电纺丝制备出具有高容量、柔韧性、长循环稳定性和显著改善的高倍率性能的锂离子电池用层状磷酸钒锂单晶纳米颗粒嵌入碳纤维的阴极。通过在氩气气氛中对聚丙烯腈和 Li3V2(PO4)3 纳米粒子的混合物进行静电纺丝,然后进行退火和等离子体增强化学气相沉积(PECVD)在纤维表面包覆一层很薄的碳,得到复合纳米纤维。具有单斜相的 Li3V2(PO4)3 纳米晶均匀分布在复合纳米纤维中。通过恒电位和恒电流测试对制备的无粘结剂纤维状阴极的电化学性能进行了表征。在 3.0-4.3 V 的电压范围内,以 0.5 C 的速率进行测试时,复合阴极的初始放电容量为 128 mA h g(-1)(理论容量的 96.2%)。在 10 C 的高倍率下,仍可观察到 120 mA h g(-1)的放电容量,在 5 C 下 500 次循环后保持 98.9%的容量保持率,表明具有优异的高倍率性能和容量保持率。与没有碳外层的对照样品相比,具有碳涂层的复合纳米纤维表现出更好的电化学性能。这表明碳涂层可以在充放电过程中进一步保护纳米纤维电极的结构完整性,而不会阻碍锂离子的迁移,还可以防止与电解质发生不必要的副反应,从而显著提高阴极的倍率性能和循环稳定性。