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化学进展 2022, Vol. 34 Issue (6): 1369-1383 DOI: 10.7536/PC210733 前一篇   后一篇

• 综述与评论 •

“蛋黄蛋壳”结构纳米电极材料设计及在锂/钠离子/锂硫电池中的应用

李芳远1, 李俊豪1, 吴钰洁1, 石凯祥1, 刘全兵1,*(), 彭翃杰2,*()   

  1. 1 广东工业大学轻工化工学院 广州 510006
    2 电子科技大学 成都 611731
  • 收稿日期:2021-07-26 修回日期:2021-09-23 出版日期:2021-12-02 发布日期:2021-12-02
  • 通讯作者: 刘全兵, 彭翃杰
  • 基金资助:
    国家自然科学基金项目(21975056); 国家自然科学基金项目(U1801257); 国家自然科学基金项目(52002079)
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Design and Preparation of Electrode Nanomaterials with “Yolk-Shell”Structure for Lithium/Sodium-Ion/Lithium-Sulfur Batteries

Fangyuan Li1, Junhao Li1, Yujie Wu1, Kaixiang Shi1, Quanbing Liu1(), Hongjie Peng2()   

  1. 1 School of Chemical Engineering and Light Industry, Guangdong University of Technology,Guangzhou 510006, China
    2 University of Electronic Science and Technology of China, Chengdu 611731, China
  • Received:2021-07-26 Revised:2021-09-23 Online:2021-12-02 Published:2021-12-02
  • Contact: Quanbing Liu, Hongjie Peng
  • Supported by:
    National Natural Science Foundation of China(21975056); National Natural Science Foundation of China(U1801257); National Natural Science Foundation of China(52002079)

“蛋黄蛋壳”结构纳米材料,具有易于调控的“蛋黄”、“蛋壳”和“空腔”结构,可视作“纳米反应器”,在催化、储能等领域表现出显著的应用潜力。尤其在电化学能源存储和转换方面,该结构纳米电极具有大的比表面积和独特的核壳结构,在充放电过程中可缓解电极的体积变化,提供快速的离子/电子输运通道,强化中间产物的吸附和提升转换反应效率等,能显著提高电极稳定性、倍率性能和循环性能,是一类较为理想的电极材料。本文针对“蛋黄蛋壳”结构纳米电极在锂/钠离子电池、锂硫电池等新兴二次电池领域的实际应用,总结了具有该结构纳米电极的设计与合成策略,包括:模板法、奥斯特瓦尔德熟化、电化学置换、克肯达尔效应等,评述了各种策略的优缺点以及电极材料的应用进展,最后对该类材料在锂/钠体系及锂硫电池二次电池方面的研究与应用前景进行了展望。

关键词： 锂离子电池, 钠离子电池, 锂硫电池, 蛋黄蛋壳结构制备, 纳米电极

“Yolk-shell” nanomaterials with adjustable “yolk”, "shell" and "cavity" structures are regarded as "nanoreactors" and have outstanding performance in the application fields of catalysis and energy storage. Especially for electrochemical energy storage and conversion, this type of material has a considerable specific surface area and a special core-shell structure, which could alleviate the volume change of the electrode, provide fast ions/electron transport channels, enhance the adsorption of intermediates, and strengthen the conversion reactions during the charge/discharge process. It can significantly improve electrode stability, rate and cycling performance, which is a relatively ideal electrode material. This article focuses on the application of “yolk-shell” nanostructured electrodes in the field of secondary batteries including lithium-ion batteries, sodium-ion batteries, and lithium-sulfur batteries and summarizes the design and synthesis strategies of this type of nanostructured electrodes, including template method, Ostwald ripening, Galvanic replacement, and Kirkendall effect, presents the advantages and disadvantages of various methods for electrochemical applications, and finally discusses prospects of yolk-shell structure in research and applications of lithium/sodium-based and lithium-sulfur secondary batteries.

Contents

1 Introduction

2 Template methods

2.1 SiO2 as a hard template

2.2 Metal oxide as a hard template

2.3 Carbon as a hard template

2.4 Soft templates

3 Self-assemble methods

3.1 Ostwald ripening to synthesis of yolk-shell structure

3.2 Galvanic replacement to the synthesis of yolk-shell structure

3.3 Kirkendall effect on synthesis of yolk-shell structure

4 The applications of yolk-shell structure in batteries

4.1 Yolk-shell in lithium-ion batteries

4.2 Yolk-shell in sodium-ion batteries

4.3 Yolk-shell in lithium-sulfur batteries

5 Conclusion and outlook

Key words: Li-ion battery, sodium-ion battery, Li-S battery, synthesis yolk-shell structure, nano-electrode
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图1 SiO2作硬模板YS结构制备流程图[21]
Fig. 1 Schematic of the preparation of yolk-shell structure using SiO2 as the hard template[21]. Copyright 2017, Elsevier
图2 部分刻蚀SiO2 YS结构制备流程图[34]
Fig. 2 Schematic of the preparation of yolk-shell structure via partially etched SiO2 template[34]. Copyright 2020, RSC
图3 聚苯乙烯作热解模板制备YS结构纳米电极流程图[18]
Fig. 3 Schematic of the preparation of yolk-shell structure using polystyrene as pyrolysis template[18]. Copyright 2018, RSC
图4 蛋黄壳锡@空腔@碳微球形成机理示意图[42]
Fig. 4 Schematic diagram of the formation mechanism of yolk-shell Sn@Void@C microspheres[42]. Copyright 2015, Wiley
图5 奥斯特瓦尔德熟化合成YS结构[43]
Fig. 5 Schematic of the preparation of yolk-shell structure via Ostwald ripening[43]. Copyright 2015, ACS
图6 电化学置换合成YS结构[49]
Fig. 6 Schematic of the preparation of yolk-shell structure via galvanic replacement[49]. Copyright 2017, ACS
图7 克肯达尔效应在纳米纤维中形成中空SnO2纳米球的机理及其在球体表面区域的化学转化过程[52]
Fig. 7 Formation mechanism of a hollow SnO2 nanosphere in the nanofiber by the nanoscale Kirkendall effect and its chemical conversion process in the surface region of a sphere[52]. Copyright 2015, Wiley
表1 模板法及自模板法的合成优势及缺点
Table 1 Synthesis advantages and disadvantages of template method and self-template method
方法 优点 缺点
硬模板法 层层组装, 方便调控合成精度 需要模板, 步骤冗杂, 环境不友好, 难以放大
软模板法 不需要模板 需要模板, 形貌均一性难控制, 步骤冗杂, 难以放大
奥斯特瓦尔德熟化 合成方法简单, 容易按比例放大, 不需要模板, 重复率高, 对壳厚度和颗粒均匀性的控制极好, 生成成本低 难以精确合成, 难以精确单独合成
电化学置换 难以精准把控反应条件, 难以精确单独合成“核心”和“外壳”, 限制金属材料前驱体
克肯达尔效应 难以精确合成,需要两种不同扩散速率的金属材料
图8 可控的YS结构作为锂离子电池负极材料的应用及电化学性能[74]。(A)为材料合成图;(B)为CV图;(C)为充放电性能图;(D)为循环性能图;(E)为倍率性能图
Fig. 8 Highly monodisperse dumbbell-like yolk-shell MnO/carbon microspheres for lithium storage and their lithiation evolution[74]. (A) schematic of the fabrication procedure; (B) the cyclic voltammetry curve; (C) the charge discharge voltage profiles at 0.26 C; (D) the cycling performance at 1.32 C and (E) the rate performance. Copyright 2020, Elsevier
图9 可控的YS结构作为钠离子电池负极材料的应用及电化学性能[82]:(a)为材料合成图;(b)为CV图;(c)为充放电性能图;(d)为循环性能图;(e)为倍率性能图
Fig. 9 Optimizing the void size of yolk-shell Bi@void@C nanospheres for high-power-density sodium-ion Batterie[82]. (a) Schematic illustration of the synthesis process; (b) cyclic voltammetry curves; (c) charge/discharge curves; (d) cycling stability at 1 A·g-1; (e) rate performance. Copyright 2020, ACS
图10 具有可控的蛋黄和空隙体积以及壳厚度的YS碳微球及其在锂硫电池正极材料和电化学性能中的应用及电化学性能[7]:(a)为材料合成图;(b)为充放电性能图;(c)为循环性能图;(d)为倍率性能图
Fig. 10 Yolk-shell carbon microspheres with controlled yolk and void volumes and shell thickness and their application as a cathode material for Li-S batteries and electrochemical performance[7]. (a) Schematic illustration of the synthesis process; (b) charge/discharge curves, (c) cycling stability, (d) rate performance. Copyright 2017, RSC
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