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Progress in Chemistry 2021, Vol. 33 Issue (11): 1983-2001 DOI: 10.7536/PC210453 Previous Articles   Next Articles

Special Issue: 锂离子电池

• Review •

Research Progress of Anode Materials for Zinc-Based Aqueous Battery in a Neutral or Weak Acid System

Xianwen Wu1, Fengni Long1, Yanhong Xiang1, Jianbo Jiang1, Jianhua Wu1, Lizhi Xiong1, Qiaobao Zhang2()   

  1. 1 School of Chemistry and Chemical Engineering, Jishou University,Jishou 416000, China
    2 College of Materials, Xiamen University,Xiamen 361005, China
  • Received: Revised: Online: Published:
  • Contact: Qiaobao Zhang
  • Supported by:
    National Natural Science Foundation of China(52064013); National Natural Science Foundation of China(52072323); National Natural Science Foundation of China(51762017); National Natural Science Foundation of China(52064014); National Natural Science Foundation of China(51862008); Key Program of Hunan Provincial Education Department(18A285)
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Zinc is an ideal electrode material for green rechargeable batteries because of its abundant raw materials, light weights, excellent electrical conductivity and ductility, as well as high theoretical specific capacity. The zinc-based aqueous battery with the neutral or weak acidic aqueous solution as electrolyte and zinc as the anode has the characteristics of high security, low cost and non-toxic battery materials, simple preparation process, and environmentally friendly. It has abroad application prospects in the field of storage devices for energy and power-driven battery. However, the problems such as zinc dendrite, hydrogen evolution, corrosion, and passivation during the process of charging and discharging limit its practical application. In this paper, the existing problems and current solutions of zinc anode for zinc-based aqueous batteries were reviewed, and the developmental trend of the anode has prospected.

Contents

1 Introduction

2 The challenges of zinc anode

2.1 Zinc dendrite

2.2 Corrosion and passivation

2.3 Hydrogen evolution

3 Optimizing strategy for zinc anode

3.1 Additives

3.2 Zinc alloy

3.3 Surface modification

3.4 Structural design

3.5 Intercalation-type anode

3.6 Electrolyte optimization

4 Summary and outlook

Key words: aqueous zinc ion battery, electrode material, zinc anode, dendrite, structure design
Fig. 1 Vicious cycle of adverse reaction of zinc anode
Fig. 2 (a) Cycling performance of unmodified ZnAB and modified ZnAB + AC reversible Zn-ion batteries at current density of 200 mA·g-1;(b) reaction principle of anode ZnAB + AC[69];(c) SEM images of Zn-Al-LDH sample[71];(d) SEM images of Zn-Al-Cu LDH sample[72]
Table 1 Electrochemical performance of ZnAB + AC anode battery with different mass ratio[69]
Serial number Capacity retentions(%) Current density(mAh·g-1)
(After 80 cycles)
ZnAB 56.7 97.2
ZnAB+5 wt% AC 62.5 107.2
ZnAB+8 wt% AC 77.9 133.3
ZnAB+12 wt% AC 85.6 146.1
ZnAB+15 wt% AC 82.3 138.1
Fig. 3 (a) Comparison of electrochemical performance between the Zn-Al eutectic alloy anode and pure zinc anode battery at 0.5 A·g-1;(b) the principle of Zn88Al12 anode[73];(c) Coulombic efficiency of the Cu-Zn/Zn electrode comparing with those of the bare Zn electrode;(d) schematic illustration of the function of the Cu-Zn alloy on the Cu-Zn/Zn electrode[74]
Table 2 The electrochemical performance of two batteries using Zn@ZrO2 and Zn as anode
Battery Capacity(mAh·g-1)
(1 A·g-1 after 1 cycle)		 Capacity retention(%)
(after 1145 cycle)
V2O5//Zn 192.3 15.8
V2O5//Zn@ZrO2 204.2 100
Table 3 The electrochemical performance of two batteries using Zn@KL-Zn and Zn as anode
Battery Capacity(mAh·g-1)
0.5 A·g-1(after 600 cycles)
MnO2//Zn 56.8
MnO2//Zn @KL-Zn 190
Fig. 4 (a) Reaction process of deposition/dissolution reaction between the pure zinc anode and the ZrO2-coated zinc anode[83];(b) reaction process of the deposition/dissolution of pure zinc anode with TiO2 coating zinc anode[85];(c) schematic illustrations of the morphology of Zn and KL-Zn anodes during the Zn2+ deposition process[84];(d) photos of zinc electrode before and after surface coating of MOF layer;(e) Schematic diagram of surface structure and reaction of zinc anode coated with MOF[86];(f) dendrite-free Ga-In@Zn anode by alloying-diffusion synergistic strategy[82]
Fig. 5 (a) Rate capability of Zn@GF//HQ-NaFe[90];(b) cycling performances of Zn@CFs//α-MnO2 full cell at 1 C rate[91];(c) charge-discharge curve of Zn@Copper foam//β-MnO2 full battery[97];(d) cycling performances of the MOF based ZIBs[98]
Table 4 Long cycle performance of β-MnO2//Zn、、Zn@Cu foil、Zn@Cu foam batteries at 1 A·g-1
Battery Current density(mAh·g-1)
1 A·g-1(after 600 cycles)
β-MnO2//Zn 55.8
β-MnO2//Zn@Cu foil 91.1
β-MnO2//Zn@Cu foam 173.8
Fig. 6 (a) The work mechanism of 9,10-anthraquinone//ZnMn2O4;(b) the cycle performance of 9,10-anthraquinone//ZnMn2O4[99];(c) the cycle performance of h-MoO3//Zn0.2MnO2 battery[103];(d) cycling performance of Na0.14TiS2/ZnMn2O4 full battery at a current density of 0.2 A·g-1[102]
Fig. 7 (a) Electrochemical performance of the Zn//LiMn2O4 full cell[116];(b) cyclic performance of Zn//MnO2 full cell under 100 mA·g-1 current density[117]
Fig. 8 (a) Cyclability of the batteries with zinc anode with organic additives and commercialized zinc foil;(b) XRD results of the zinc anode electroplated with different organic additives and commercial zinc[124];(c) cyclability of Zinc-based Aqueous Battery with zinc anode with inorganic additives and commercial zinc foil;(d) XRD patterns of zinc anode and commercial zinc foil prepared by electrodeposition with different inorganic additives[125]
Fig. 9 (a) Scheme of the Mg2+ functional mechanism for hybrid electrolyte;(b) discharge-charge profiles for MgVO cathode at current density of 100 mA·g-1 in different electrolytes[130]
Fig. 10 (a) The chemical structure of TpPa-SO3Zn0.5;(b) the structural model of TpPa-SO3Zn0.5 ;(c) Coulomb efficiency and cycle performance diagram of a Zn|TpPa-SO3Zn0.5|MnO2 cell[136];(d) the design of ultrathin all-in-one ZIBs schematic process[137]
Fig. 11 (a,b) SEM images of the morphologies grown at the Zn anode after plating/stripping for more than 5000 h in Zn(OTf)2-(TMP-DMC) electrolyte at a current density of 1.0 mA cm-2[142];(c) schematic illustration of the environments of solvated TMP and free TMP in concentrated(i.e., 1.0 mol·L-1 Na++0.5 mol·L-1 Zn2+) and dilute(i.e., 0.5 mol·L-1 Zn2+) electrolytes[143]
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