Anode Current Collector for Aqueous Zinc-ion Batteries: Issues and Design Strategies

doi:10.6023/A22100413

Acta Chimica Sinica ›› 2023, Vol. 81 ›› Issue (1): 29-41.DOI: 10.6023/A22100413 Previous Articles Next Articles

Review

水系锌离子电池负极集流体关键问题及设计策略

姬慧敏^a, 谢春霖^a, 张旗^a, 李熠鑫^a, 李欢欢^b, 王海燕^a^,^*()

a 中南大学化学化工学院长沙 410083
b 河南师范大学化学化工学院新乡 453007

投稿日期:2022-10-08 发布日期:2022-12-01

作者简介:

姬慧敏, 中南大学化学化工学院在读博士生, 师从王海燕教授. 2021年本科毕业于中南大学, 同年直接攻读博士学位. 主要从事金属能源研究.

谢春霖, 中南大学化学化工学院在读博士生, 师从王海燕教授. 2019年本科毕业于湖南科技大学, 2022年硕士毕业于中南大学. 目前主要研究方向为金属能源界面化学调控, 以第一作者身份在Adv. Energy Mater., Carbon Energy, Chin. Chem. Lett., Research等期刊上发表多篇论文.

张旗, 博士, 硕士生导师, 研究方向为金属负极界面电化学, 目前以通讯作者或第一作者身份在Nat. Commun., Angew. Chem. Int. Ed.等国际著名刊物上发表多篇论文, 获得中国化学会菁青化学星火奖、京博科技奖-化学化工与材料京博优秀博士论文奖优秀奖, 承担国家自然科学基金青年基金项目、湖南省自然科学基金青年基金项目、中南大学科研启动基金.

李熠鑫, 中南大学讲师, 本科就读于南开大学化学学院化学专业, 随后被保送至南开大学化学学院直接攻读南开大学无机化学专业博士, 师从无机化学家陈军院士. 研究方向主要是水系二次电池和金属燃料电池, 目前发表SCI论文10余篇, 其中以第一作者和通讯作者在国际顶尖期刊J. Am. Chem. Soc., Chem, Adv. Funct. Mater., Chem. Commun., J. Mater. Chem. A上发文5篇, 承担湖南省自然科学基金青年项目, 南开大学教育部重点实验室开放基金和中南大学科研启动基金.

李欢欢, 河南师范大学化学化工学院副教授. 博士毕业于东北师范大学高分子化学与物理专业, 师从张景萍教授; 2017年7月入职河南师范大学, 研究方向为能源材料与能源化学. 至今共发表SCI论文52篇(H指数23), 其中以第一作者/通讯作者在Adv. Energy Mater., ACS Energy Lett., Chem. Commun.等期刊发表论文20余篇.

王海燕, 中南大学化学化工学院教授, 博士生导师, 青年长江学者, 国际先进材料协会会士, 香江学者, 湖南省科技创新领军人才, 湖南省杰出青年基金获得者. 曾获国家公派留学University of St. Andrews, 曾于香港科技大学从事研究工作. 近年来一直从事新能源材料、电池器件及资源绿色循环研究, 目前以通讯作者在Nat. Commun., Angew. Chem. Int. Ed等国际知名期刊发表论文150余篇, SCI他引8000余次, H指数55. 获授权国家发明专利14项. 获湖南省自然科学二等奖, 重庆市科技进步一等奖等.

基金资助:
湖南省科技计划项目(2022RC3050); 湖南省科技计划项目(2017TP1001); 湖南省研究生科研创新项目(CX20220159); 中南大学中央高校基本科研业务费专项资金(2022ZZTS0071); 河南师范大学化学化工学院开放科研基金资助

Anode Current Collector for Aqueous Zinc-ion Batteries: Issues and Design Strategies

Huimin Ji^a, Chunlin Xie^a, Qi Zhang^a, Yixin Li^a, Huanhuan Li^b, Haiyan Wang^a()

a College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China
b School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, China

Received:2022-10-08 Published:2022-12-01
Contact: ^*E-mail: wanghy419@csu.edu.cn
Supported by:
Science and technology innovation Program of Hunan Province(2022RC3050); Science and technology innovation Program of Hunan Province(2017TP1001); Hunan Provincial Innovation Foundation For Postgraduate(CX20220159); Fundamental Research Funds for the Central Universities of Central South University(2022ZZTS0071); Open Research Fund of School of Chemistry and Chemical Engineering, Henan Normal University

Aqueous zinc ion batteries possess the characteristics of cost-effectiveness, environmental benignancy, intrinsic safety, and relatively high energy density, and are promising to be used in large-scale electrochemical energy storage devices. However, the current commercial zinc foil anode is considerably excessive compared with cathode active materials, which significantly decreases the energy density of the battery. And there are serious problems of anode perforation, tab falling off and so on. Loading zinc on current collector as anode is effective to improve depth of discharge and avoid the electrode perforation. Nevertheless, the zinc dendrites and side reactions are prone to generate at the current collector interface, and they seriously affect the cycle life of the battery. In this review, the causes of zinc dendrites and side reactions and their influence on the electrochemical performance of zinc anode are analyzed, and the design ideas of the zinc anode current collectors are summarized from two aspects of composition selection and structure construction, including the selection of zincophilic materials, the design of preferred-orientation substrates and the construction of three-dimensional current collector structures. Designing an appropriate current collector can effectively regulate the plating and stripping behavior of zinc metal and promote the practical application of aqueous zinc ion batteries.

Key words: zinc anode, current collector, zinc dendrite, zincophilicity, preferred-orientation, three-dimensional structure

Cite this article

Huimin Ji, Chunlin Xie, Qi Zhang, Yixin Li, Huanhuan Li, Haiyan Wang. Anode Current Collector for Aqueous Zinc-ion Batteries: Issues and Design Strategies[J]. Acta Chimica Sinica, 2023, 81(1): 29-41.

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Fig. & Tab. 11

Figure 1. (a) Schematic of the formation of zinc dendrites[36]. (b) Schematic and (c) equivalent circuit of the galvanic corrosion between substrate and zinc[20] (a) Reprinted with permission from Ref. 36. Copyright 2021 American Chemical Society. (b), (c) Reprinted with permission from Ref. 20. Copyright 2021 Wiley

Figure 2. Schematic diagrams of (a) dense nucleation and subsequent formation of Zn-dendrite on zincophobic surface and (b) spacious Zn nucleation and homogeneous Zn deposition on surface with zincophilic sites[37] (a), (b) Reprinted with permission from Ref. 37. Copyright 2021 Wiley

Figure 3. (a) The in situ SDM images of the morphology of zinc deposition on carbon felt host and tin (Sn)-modified carbon felt host[40]. (b) LSV curves of carbon felt host and tin (Sn)-modified carbon felt host in 3 mol?L-1 KCl electrolyte at 10 mV?s-1 [40]. (c) Voltage profiles of galvanostatic Zn deposition on various substrates. (d) Schematic of the seeded Zn plating on the Ag islands patterned on carbon. (e) Scanning electron microscopy (SEM) images and elemental mapping images of the carbon paper coated with patterned Ag islands before and after Zn plating[49] (a), (b) Reprinted with permission from Ref. 40. Copyright 2020 Wiley. (c~e) Reprinted with permission from Ref. 49. Copyright 2021 American Chemical Society

Figure 4. (a) Contour mapping of Bader charge of graphene (Left) and N-doped graphene (Right). (b) Charge transfer from graphene/N-doped graphene to zinc. (c) 3D charge difference between graphene (red)/N-doped graphene (blue) and zinc of different adsorption sites. (d) Binding energies between graphene/N-doped graphene and zinc[37] Reprinted with permission from Ref. 37. Copyright 2021 Wiley

Figure 5. (a) Schematic illustration of preferred orientations of Zn crystal plane[59]. (b) The free-energy diagram for the HER[62]. (c) Atomic arrangements of Zn(002) and graphene(002)[64]. (d) Scheme illustrating the design principle of epitaxial metal electrodeposition[64]. (e) SEM of Zn deposits on graphene-coated stainless steel[64]. (f) Cycling performance of Zn||α-MnO2 full cells with and without graphene, with controlled N:P electrode capacity ratios[64]. (g) Atomic illustration of the heterointerface between Ti3C2Tx MXene and zinc and uniform Zn depositions[21] (a) Open access. (b) Reprinted with permission from Ref. 59. Copyright 2021 Wiley. (c~e) Reproduced with permission from Ref. 64. Copyright 2019 American Association for the Advancement of Science. (g) Reprinted with permission from Ref. 21. Copyright 2021 American Chemical Society

Figure 6. (a) SEM image and the corresponding inverse pole figure (IPF) map of the polycrystalline copper with large grain size. (b) (001) pole figure of the polycrystalline copper with large grain size. Optical patterns of the polycrystalline copper with large grain size (c) before and (d) after zinc deposition. The regions cycled by red and yellow refer to high-activity facet and inert facet, respectively. Finite element simulations of electric field on the surface with (e) random and (f) uniform orientation. SEM images of (g) R-Cu and (h) F-Sn@Cu after zinc plating for 2 mAh?cm-2 at the current density of 5 mA?cm-2 [70]. Electron backscattered diffraction (EBSD) analysis of (i) routine Cu foil and (j) Cu(100) foil. (k) Schematic illustration of crystallographic orientation of the Zn UPD and OPD layers on Cu(100)[71] (a~h) Reprinted with permission from Ref. 70. Copyright 2022 Chunlin Xie et al. (i~k) Reprinted with permission from Ref. 71. Copyright 2022 American Chemical Society

Figure 7. (a~d) Top-view SEM images of Zn electrodes cycled at 1, 2, 7.5, 10 mA?cm-2. (e~h) Cross-section SEM observation of Zn electrodes at various current densities. (i) Illustration of the proposed electrochemical deposition processes on planar current collector and 3D current collector (a~h) Reprinted with permission from Ref. 72. Copyright 2019 Wiley. (i) Open access

Figure 8. Scanning electron microscopy images of (a) copper mesh[18] and (b) carbon-based fiber[78]. (c) Schematic illustrations of zinc deposition on zinc plate and Zn@CF [73]. SEM images of zinc electrode of (d) zinc plate and (e) Zn@CF during the cycling of Zn||Co3O4 batteries [73]. (f) Schematic illustration of the formation of zinc dendrite on fiber current collector [78]. (g) Schematic illustrations of Zn deposition on CM@CuO and copper mesh[79] (a) Reprinted with permission from Ref. 18. Copyright 2019 Wiley. (b) Reprinted with permission from Ref. 78. Copyright 2021 Wiley. (c~e) Reprinted with permission from Ref. 73. Copyright 2016 Wiley. (f) Reprinted with permission from Ref. 78. Copyright 2021 Wiley. (g) Reprinted with permission from Ref. 79. Copyright 2020 Wiley

Figure 9. (a) 3D NP Zn-Cu alloy electrode fabrication process. (b) Top-view and (c) cross-sectional SEM images of 3D NP Zn-Cu alloy electrode. (d) Schematic of ion and electron transport in 3D NP Zn-Cu alloy electrode [86] Reprinted with permission of Ref. 86. Copyright 2020 Wiley

Figure 10. (a) Structure of ZIF-8 (blue: Zn; green: N; black: C; and white, H). The yellow sphere shows the inner pore of the sodalite cage, and the orange sphere visualizes the pore aperture window of the six-membered hexagonal rings. (b) TEM images and elemental mappings of the samples prepared at different temperatures. (c) SEM images of Zn deposits at a current density of 1.0 mA?cm-2 for different capacities. (d) Schematic illustration of the Zn plating with ZIF-8 substrate [87]. SEM images of (e) Cflower, (f) Cdisk and (g) Csphere[16] (a~d) Reprinted with permission of Ref. 87. Copyright 2019 Elsevier Inc. (e~g) Reprinted with permission of Ref. 16. Copyright 2022 American Chemical Society

集流体材料	设计策略	锌负载量	循环寿命	参考文献
镀锡碳毡	亲锌性金属与三维结构	40 mAh•cm^-2	290 h (40 mA•cm^-2, 20 mAh•cm^-2)	[80]
纳米多孔锡网	亲锌性金属与三维结构	4 mAh•cm^-2	350 h (1 mA•cm^-2, 1 mAh•cm^-2)	[9]
CuO@Cu网	亲锌性材料与三维结构	5 mAh•cm^-2	350 h (1 mA•cm^-2, 1 mAh•cm^-2)	[79]
(100)面择优铜	择优取向	10 mAh•cm^-2	550 h (1 mA•cm^-2, 1 mAh•cm^-2)	[71]
泡沫铜	三维结构	3.39 mAh•cm^-2	300 h (2 mA•cm^-2, 1 mAh•cm^-2)	[27]
三维中空SiO₂/TiO₂/碳纤维	梯度亲锌性材料与三维结构	10 mAh•cm^-2	600 h (10 mA•cm^-2, 1 mAh•cm^-2) 200 h (20 mA•cm^-2, 1 mAh•cm^-2)	[78]
C_flower@Cu	纳米材料三维结构	1~2 mg•cm^-2	1000 h (2 mA•cm^-2, 1 mAh•cm^-2) 150 h (5 mA•cm^-2, 2.5 mAh•cm^-2)	[16]

Table 1. Summary of recently reported design strategies for the zinc anode current collectors

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水系锌离子电池负极集流体关键问题及设计策略

Anode Current Collector for Aqueous Zinc-ion Batteries: Issues and Design Strategies

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