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用于锂硫电池的钙钛矿双金属氢氧化物纳米笼实现多硫化物的协同吸附与催化转化

Coordinated Adsorption and Catalytic Conversion of Polysulfides Enabled by Perovskite Bimetallic Hydroxide Nanocages for Lithium-Sulfur Batteries.

作者信息

Wang Xinliang, Han Junwei, Luo Chong, Zhang Bin, Ma Jiabin, Li Zejian, He Yan-Bing, Yang Quan-Hong, Kang Feiyu, Lv Wei

机构信息

Shenzhen Geim Graphene Center, Engineering Laboratory for Functionalized Carbon Materials, Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen, 518055, China.

Nanoyang Group, State Key Laboratory of Chemical Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072, China.

出版信息

Small. 2021 Aug;17(31):e2101538. doi: 10.1002/smll.202101538. Epub 2021 Jun 23.

Abstract

Catalysis is an effective remedy for the fast capacity decay of lithium-sulfur batteries induced by the shuttling of lithium polysulfides (LiPSs), but too strong adsorption ability of many catalysts toward LiPSs increases the risk of catalyst passivation and restricts the diffusion of LiPSs for conversion. Herein, perovskite bimetallic hydroxide (CoSn(OH) ) nanocages are prepared, which are further wrapped by reduced graphene oxide (rGO) as the catalytic host for sulfur. Because of the coordinated valence state of Co and Sn and the intrinsic defect of the perovskite structure, such bimetallic hydroxide delivers moderate adsorption ability and enhanced catalytic activity toward LiPS conversion. Coupled with the hollow structure and the wrapped rGO as double physical barriers, the redox reaction kinetics, and sulfur utilization are effectively improved with such a host. The assembled battery delivers a good rate performance with a high capacity of 644 mAh g at 2 C and long stability with a capacity decay of 0.068% per cycle over 600 cycles at 1 C. Even with a higher sulfur loading of 3.2 mg cm and a low electrolyte/sulfur ratio of 5 µL mg , the battery still shows high sulfur utilization and good cycling stability.

摘要

催化作用是解决多硫化锂(LiPSs)穿梭导致锂硫电池快速容量衰减的有效方法,但许多催化剂对LiPSs的吸附能力过强,增加了催化剂钝化的风险,并限制了LiPSs转化的扩散。在此,制备了钙钛矿型双金属氢氧化物(CoSn(OH) )纳米笼,并进一步用还原氧化石墨烯(rGO)包裹作为硫的催化主体。由于Co和Sn的配位价态以及钙钛矿结构的固有缺陷,这种双金属氢氧化物对LiPS转化具有适度的吸附能力和增强的催化活性。再加上空心结构和包裹的rGO作为双重物理屏障,这种主体有效地改善了氧化还原反应动力学和硫利用率。组装的电池在2 C时具有644 mAh g的高容量,表现出良好的倍率性能,在1 C下600次循环中容量衰减率为0.068%,具有长循环稳定性。即使硫负载量高达3.2 mg cm 且电解质/硫比低至5 µL mg ,该电池仍表现出高硫利用率和良好的循环稳定性。

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