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表面转化反应实现了用于高性能锂离子电池的先进红磷/碳阳极。

On-surface conversion reaction realizes advanced red phosphorus/carbon anode for high-performance lithium-ion batteries.

作者信息

Huang Yujie, Li Hao, Wu Mengjun, Tian Tian, Wang Rui, Zeng Sixiu, Song Jiangping, Tang Haolin

机构信息

State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China.

State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China; Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory, Xianhu Hydrogen Valley, Foshan 528200, China.

出版信息

J Colloid Interface Sci. 2024 Oct 15;672:117-125. doi: 10.1016/j.jcis.2024.05.235. Epub 2024 Jun 1.

Abstract

Red phosphorus (RP), the one of the most prospective anodes in lithium-ion batteries (LIBs), has been severely limited due to the intrinsic defects of massive volume expansion and low electronic conductivity. The vaporization-condensation-conversion (VCC), which confines RP nanoparticles into carbon host, is the most widely used method to address the above drawbacks and prepare RP/C nanostructured composites. However, the volume effect-dominated RP caused by the inevitably deposition of RP vapor on the surface of carbon material suffers from the massive volume change and unstable solid electrolyte interface (SEI) film. Herein, we propose a simple interfacial modification method to eliminate the superficial RP and yield stable surface composed of ion-conducting Li3PS4 solid electrolyte, endowing RP/AC composites excellent cycling performance and ultrafast reaction kinetics. Therefore, the RP/AC@S composites exhibit 926 mAh/g after 320 cycles at 0.2 A/g (running over 181 days), with 81.6 % capacity retention and a corresponding capacity decay rate of as low as 0.059 %. When coupled with LiFePO4 cathode, the full cells present superior cycling performance (62.1 mAh/g after 500 cycles at 1 A/g) and excellent rate capability (81.1 mAh/g at 1.0 A/g).

摘要

红磷(RP)是锂离子电池(LIBs)中最具前景的负极材料之一,但由于其存在大量体积膨胀和低电子电导率等固有缺陷,其应用受到严重限制。蒸发 - 冷凝 - 转化(VCC)法将RP纳米颗粒限制在碳基体中,是解决上述缺点并制备RP/C纳米结构复合材料最广泛使用的方法。然而,由于RP蒸汽不可避免地沉积在碳材料表面而导致的以体积效应为主的RP,会经历大量的体积变化和不稳定的固体电解质界面(SEI)膜。在此,我们提出一种简单的界面改性方法,以消除表面的RP,并产生由离子导电的Li3PS4固体电解质组成的稳定表面,赋予RP/AC复合材料优异的循环性能和超快的反应动力学。因此,RP/AC@S复合材料在0.2 A/g下循环320次(运行超过181天)后,容量为926 mAh/g,容量保持率为81.6%,相应的容量衰减率低至0.059%。当与LiFePO4正极耦合时,全电池表现出优异的循环性能(在1 A/g下循环500次后为62.1 mAh/g)和出色的倍率性能(在1.0 A/g下为81.1 mAh/g)。

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