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一种共价P-C键在工程化碳载体中稳定红磷用于高性能锂离子电池阳极。

A Covalent P-C Bond Stabilizes Red Phosphorus in an Engineered Carbon Host for High-Performance Lithium-Ion Battery Anodes.

作者信息

Zhang Shaojie, Liu Cheng, Wang Huili, Wang Haipeng, Sun Jiantong, Zhang Yiming, Han Xinpeng, Cao Yu, Liu Shuo, Sun Jie

机构信息

Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China.

出版信息

ACS Nano. 2021 Feb 23;15(2):3365-3375. doi: 10.1021/acsnano.0c10370. Epub 2021 Jan 20.

Abstract

The red phosphorus (RP) anode has attracted great attention due to its high theoretical specific capacity (2596 mAh/g) and suitable lithiation potential. To solve the inherent poor electrical conductivity and the large volume expansion due to the lithiation process, a vaporization-condensation strategy is considered as a promising method. However, there are two important issues that deserve attention in the vaporization-condensation process. First, the low P mass loading in the carbon-based frameworks (∼30 wt %) limits the energy density. Second, a residual white phosphorus (WP) leads to the safety problems of flammability and high toxicity. Herein, we found that the edge structure of carbon framework can offer the strong adsorption for P and form a P-C bond, which accelerate the adsorption and polymerization of P leading to high P mass loading and safety. When the porous carbon (PC) with plenty of edge carbons was used as the matrix to load P by vaporization-condensation, the RP loading is close to the highest theoretical mass loading of ∼50 wt % calculated based on the feeding ratio of RP/PC = 1/1. Therefore, the RP-PC anode provides a high specific capacity of 965.2 mAh/g even after 1100 cycles at 1000 mA/g (equivalent to 1 C) and a high-rate capacity of 496.8 mAh/g at 8320 mA/g (equivalent to 16.7 C) after 1000 cycles (the specific capacity and current density are calculated based on the total weight of RP and PC).

摘要

红磷(RP)阳极因其高理论比容量(2596 mAh/g)和合适的锂化电位而备受关注。为了解决其固有的导电性差以及锂化过程中体积大幅膨胀的问题,汽化-冷凝策略被认为是一种很有前景的方法。然而,在汽化-冷凝过程中有两个重要问题值得关注。首先,碳基框架中磷的低质量负载(约30 wt%)限制了能量密度。其次,残留的白磷(WP)会导致易燃性和高毒性等安全问题。在此,我们发现碳框架的边缘结构能够对磷提供强吸附作用并形成P-C键,这加速了磷的吸附和聚合,从而实现高磷质量负载并保障安全。当使用具有大量边缘碳的多孔碳(PC)作为基质通过汽化-冷凝来负载磷时,基于RP/PC = 1/1的进料比计算,RP负载接近约50 wt%的最高理论质量负载。因此,即使在1000 mA/g(相当于1 C)下循环1100次后,RP-PC阳极仍具有965.2 mAh/g的高比容量,在1000次循环后,在8320 mA/g(相当于16.7 C)下具有496.8 mAh/g的高倍率容量(比容量和电流密度是基于RP和PC的总重量计算的)。

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