Liu Weili, Du Lingyu, Ju Shunlong, Cheng Xueyi, Wu Qiang, Hu Zheng, Yu Xuebin
Department of Materials Science, Fudan University, Shanghai 200433, People's Republic of China.
Department of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, People's Republic of China.
ACS Nano. 2021 Mar 23;15(3):5679-5688. doi: 10.1021/acsnano.1c00924. Epub 2021 Mar 15.
Red phosphorus (RP) has attracted great attention as a potential candidate for anode materials of high-energy density sodium-ion batteries (NIBs) due to its high theoretical capacity, appropriate working voltage, and natural abundance. However, the low electrical conductance and huge volumetric variation during the sodiation-desodiation process, causing poor rate performance and cyclability, have limited the practical application of RP in NIBs. Herein, we report a rational strategy to resolve these issues by encapsulating nanoscaled RP into conductive and networked carbon nanocages (denoted as RP@CNCs) using a combination of a phosphorus-amine based method and evacuation-filling process. The large interior cavities volume of CNCs and controllable solution-based method enable the ultrahigh RP loading amount (85.3 wt %) in the RP@CNC composite. Benefiting from the synergic effects of the interior cavities and conductive network, which afford high structure stability and rapid electron transport, the RP@CNC composite presents a high systematic capacity of 1363 mA h g at a current density of 100 mA g after 150 cycles, favorable high-rate capability, and splendid long-cycling performance with capacity retention over 80% after 1300 cycles at 5000 mA g. This prototypical design promises an efficient solution to maximize RP loading as well as to boost the electrochemical performance of RP-based anodes.
红磷(RP)因其高理论容量、合适的工作电压和天然丰度,作为高能量密度钠离子电池(NIBs)负极材料的潜在候选者而备受关注。然而,其低电导率以及在脱钠-钠化过程中巨大的体积变化,导致倍率性能和循环稳定性较差,限制了红磷在钠离子电池中的实际应用。在此,我们报道了一种合理的策略来解决这些问题,即通过基于磷-胺的方法和抽空-填充过程相结合,将纳米级红磷封装到导电的网络状碳纳米笼(记为RP@CNCs)中。碳纳米笼大的内腔体积和基于溶液的可控方法使得RP@CNC复合材料中红磷的负载量超高(85.3 wt%)。得益于内腔和导电网络的协同效应,它们提供了高结构稳定性和快速电子传输,RP@CNC复合材料在150次循环后,在100 mA g的电流密度下呈现出1363 mA h g的高比容量,具有良好的高倍率性能,并且在5000 mA g下经过1300次循环后具有出色的长循环性能,容量保持率超过80%。这种典型设计有望为最大化红磷负载量以及提升基于红磷的负极的电化学性能提供一种有效的解决方案。