Yao Xiong,Qingning Li,Ketong Luo,Lu Zhong,Guangfeng Li,Shengkui Zhong,Dongliang Yan
Aqueous zinc ion batteries (AZIBs) have got increasingly worldwide attention in virtue of the excellent advantages of cheap price, safety and high specific capacity. Nevertheless, the formation of dendrites and the hydrogen evolution reaction on the Zn anode leads to low cycle life and restrict their commercial application. In this paper, an inexpensive, safe, eco-friendly and effective electrolyte additive , carboxymethyl cellulose (CMC), which can guide a uniform Zn deposition during the plating and stripping process and further inhibit the growth of dendrite, has been proposed. The experimental results indicate that the Zn//Zn symmetric cells show remarkable cycling performance for >600 h at a current density of 5 mA cm −2 with 1 mAh cm −2 and 1000 h at a current density of 1 mA cm −2 with 1 mAh cm −2 , respectively. In addition, the Zn//V 2 O 5 full cells with addition of CMC can obtain a desirable specific capacity for 173 mAh g −1 and keep a high-capacity retention of 54.2 % (19.5 % for without CMC additive) after 1000 cycles at 2A g −1 . A reasonable improved mechanism of electrochemical performance by addition of CMC electrolyte additive has been proposed. This work demonstrates that addition of CMC in electrolyte is a promising strategy for inhibiting Zn dendrite and corrosion in AZIBs.
Xingyun Zhang,Kailimai Su,Yue Hu,Kaiyuan Xue,Yan Wang,Minmin Han,Junwei Lang
The zinc anode mainly faces technical problems such as short circuits caused by the growth of dendrite, low coulomb efficiency, and a short cycle life caused by side reactions, which impedes the rapid development of aqueous zinc-ion batteries (AZIBs). Herein, a common ionic liquid, 1,1-Spirobipyrrolidinium tetrafluoroborate ([SBP]BF4), is selected as a new additive for pure ZnSO4electrolyte. It is found that this additive could regulate the solvation sheath of hydrated Zn2+ions, promote the ionic mobility of Zn2+, homogenize the flux of Zn2+, avoid side reactions between the electrolyte and electrode, and inhibit the production of zinc dendrites by facilitating the establishment of an inorganic solid electrolyte interphase layer. With the 1% [SBP]BF4-modified electrolyte, the Zn||Zn symmetric cell delivers an extended plating/stripping cycling life of 2000 h at 1 mA cm−2, which is much higher than that of the cell without additives (330 h). As a proof of concept, the Zn‖V2O5battery using the [SBP]BF4additive shows excellent cycling stability, maintaining its specific capacity at 97 mAh g−1after 2000 cycles at 5 A g−1, which is much greater than the 46 mAh g−1capacity of the non-additive battery. This study offers zinc anode stabilization through high-efficiency electrolyte engineering.
Aqueous Zn metal batteries suffer from rapid cycling deterioration due to the severe water corrosion and dendrite growth on Zn anodes. Herein, a highly antiwater Znx-diethylenetriaminepenta(methylene-phosphonic acid) interface layer with good zinc affinity and special nanoscaled 3D granular structure is designed on Zn metal to address these problems. Experimental results combined with theoretical analysis and COMSOL simulations reveal that the hydrophobic groups in such Zn-based organic complex are the decisive factor in preventing H2O from damaging Zn anode surface. The massive Zn2+ attractive sites formed by interaction of methylene-phosphonic acid groups and Zn cause ion channel for fast zinc-ion adsorption and migration. And the developed nano granular architecture on the surface induces redistributed Zn2+ ion flux to realize homogenization with smooth and compact surface deposition. Under the synergism, such modified anodes exhibit long cycling lifespan over 1300 h with a relatively low polarization voltage at 5 mA cm–2. Also, the assembled full cells (including Zn//V2O5 and Zn//MnO2 cell) based on this anode are also demonstrated. The work provides a simple, low cost, and efficient pathway by combining the two concepts of structural design and constructing protective layers on the surface to prepare high-performance Zn anodes toward prospering aqueous zinc–metal batteries.
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