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量身定制带来最佳贴合度:在完全受限的红磷体系中具有卓越的钠/钾离子存储性能。

Tailor-Made Gives the Best Fits: Superior Na/K-Ion Storage Performance in Exclusively Confined Red Phosphorus System.

作者信息

Ruan Jiafeng, Mo Fangjie, Long Ziyao, Song Yun, Fang Fang, Sun Dalin, Zheng Shiyou

机构信息

Department of Materials Science, Fudan University, Shanghai 200433, China.

School of Materials Science and Engineering, University of Shanghai for Science and Technology, Shanghai 200093, China.

出版信息

ACS Nano. 2020 Sep 22;14(9):12222-12233. doi: 10.1021/acsnano.0c05951. Epub 2020 Aug 20.

Abstract

As the most promising anodic candidate for alkali ion batteries, red phosphorus (P) still faces big challenges, such as the poor rate and cycling performance, which are caused by the insulative nature and the large volume change throughout the alloy/dealloy process. To ameliorate above issues, the traditional way is confining P into the carbon host. However, investigations on maximizing P utilization are inadequate; in other words, how to achieve entire confinement with a high loading amount is still a problem. Additionally, the application of P in potassium-ion batteries (PIBs) is in its infant stage, and the corresponding potassiation product is controversial. Herein, a nitrogen-doped stripped-graphene CNT (N-SGCNT) as carbon framework is prepared to exclusively confine ultrafine P to construct P@N-SGCNT composites. Benefitting from the cross-linked structure, N-SGCNT loaded with 41.2 wt % P (P@N-SGCNT) shows outstanding Na/K storage performance. For instance, P@N-SGCNT exhibits high reversible capacities of 2480 mAh g for sodium-ion batteries (SIBs) and 762 mAh g for PIBs, excellent rate capabilities of 1770 mAh g for SIBs and 354 mAh g for PIBs at 2.0 A g, and long cycling stability (a capacity of 1936 mAh g after 2000 cycles for SIBs and 319 mAh g after 1000 cycles for PIBs). Furthermore, due to this exclusively confined P structure, the K storage mechanism with the end product of KP has been identified by experimental and theoretical results.

摘要

作为碱金属离子电池最具潜力的阳极候选材料,红磷(P)仍面临着巨大挑战,如倍率性能和循环性能较差,这是由其绝缘性质以及在合金化/脱合金化过程中的大体积变化所导致的。为改善上述问题,传统方法是将P限制在碳主体中。然而,关于最大化P利用率的研究并不充分;换句话说,如何在高负载量下实现完全限制仍是一个问题。此外,P在钾离子电池(PIB)中的应用尚处于起步阶段,且相应的钾化产物存在争议。在此,制备了一种氮掺杂的剥离石墨烯碳纳米管(N-SGCNT)作为碳骨架,专门用于限制超细P以构建P@N-SGCNT复合材料。受益于交联结构,负载41.2 wt% P的N-SGCNT(P@N-SGCNT)表现出出色的钠/钾存储性能。例如,P@N-SGCNT对钠离子电池(SIB)展现出2480 mAh g的高可逆容量,对PIB展现出762 mAh g的高可逆容量;在2.0 A g下,对SIB具有1770 mAh g的优异倍率性能,对PIB具有354 mAh g的优异倍率性能,以及长循环稳定性(SIB在2000次循环后容量为1936 mAh g,PIB在1000次循环后容量为319 mAh g)。此外,由于这种专门限制的P结构,通过实验和理论结果确定了以KP为最终产物的钾存储机制。

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