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氰桥杂金属气凝胶的热解:一种将 Sn-M(M=Fe、Ni)合金固定在碳基质内以实现稳定快速锂存储的通用方法。

Pyrolysis of cyano-bridged hetero-metallic aerogels: a general route to immobilize Sn-M (M = Fe, Ni) alloys within a carbon matrix for stable and fast lithium storage.

机构信息

Jiangsu Key Laboratory of New Power Batteries, Jiangsu Collaborative Innovation Center of Biomedical Functional Materials, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, PR China.

出版信息

Nanoscale. 2018 Mar 8;10(10):4962-4968. doi: 10.1039/c7nr06768b.

Abstract

The practical application of Sn-M (M = Fe, Ni, Co, and Cu) alloys, a promising anodic category for lithium-ion batteries, is hindered primarily by their huge volume change upon cycling. Immobilization of Sn-M alloys within carbon matrices has proven to be effective to improve their cycling stability, but the traditional pyrolysis of separate Sn, M, and C precursors often leads to uneven distribution of the three components in Sn-M-C ternary anodes. Herein, we report a facile and general aerogel-derived pyrolysis route to realize homogeneous embedding of uniformly-sized Sn-M alloy nanocrystals, within a nanoporous carbon matrix, using cyano-bridged hetero-metallic (Sn-M) aerogels hybridized with carbon sources as precursors. Using the optimized citric acid (CA) as a carbon source, the formations of nanoporous Sn-Fe@C and Sn-Ni@C networks have been illustrated as examples through pyrolyzing CA/Sn-Fe and CA/Sn-Ni aerogels, respectively. By virtue of their compositional/structural superiorities toward lithium storage, the as-prepared Sn-Fe@C and Sn-Ni@C networks manifest higher capacities, enhanced cycling stability, and improved rate capability compared to the Sn-M-C composites and carbon samples derived from bare aerogels and CA precursors, respectively. Specifically, the Sn-Fe@C network manifests a high reversible capacity of 441.6 mA h g after 100 cycles at 100 mA g and an average capacity of 438.6 mA h g at 1 A g. This work shows a new guideline for designing highly-uniform Sn-M-C, Sb-M-C, and Bi-M-C ternary anodes for boosting energy storage.

摘要

Sn-M(M = Fe、Ni、Co 和 Cu)合金作为锂离子电池有前途的阳极类别,其实际应用主要受到其循环过程中巨大体积变化的阻碍。将 Sn-M 合金固定在碳基质内已被证明可以有效提高其循环稳定性,但传统的 Sn、M 和 C 前体的热解通常会导致 Sn-M-C 三元阳极中三种成分的不均匀分布。在此,我们报告了一种简便通用的气凝胶衍生热解方法,使用氰桥杂化(Sn-M)气凝胶与碳源作为前体制备均匀尺寸的 Sn-M 合金纳米晶均匀嵌入纳米多孔碳基质中。使用优化的柠檬酸(CA)作为碳源,通过分别热解 CA/Sn-Fe 和 CA/Sn-Ni 气凝胶,说明了形成纳米多孔 Sn-Fe@C 和 Sn-Ni@C 网络的过程。由于它们在储锂方面的组成/结构优势,与 Sn-M-C 复合材料和分别源自裸气凝胶和 CA 前体的碳样品相比,所制备的 Sn-Fe@C 和 Sn-Ni@C 网络表现出更高的容量、增强的循环稳定性和改善的倍率性能。具体而言,Sn-Fe@C 网络在 100 mA g 下循环 100 次后表现出 441.6 mA h g 的高可逆容量,在 1 A g 下的平均容量为 438.6 mA h g。这项工作为设计用于提高储能的高度均匀的 Sn-M-C、Sb-M-C 和 Bi-M-C 三元阳极提供了新的指导方针。

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