Abstract:Metal anodes represent as a prime choice for the coming generation rechargeable batteries with high energy density. However, daunting challenges including electrode volume variation and inevitable side reactions preclude them from becoming a viable technology. Here, a facile replacement reaction was employed to fabricate a three-dimensional (3D) interdigitated metal/solid electrolyte composite electrode, which not only provides a stable host structure for buffering the volume change within the composite but al… Show more
“…Remarkably, Figure 3d indicates that the cumulative capacity of 0.3 m additive modified Zn anodes can be greatly improved up to 990, 1330, 3872, 5000, and even 5600 mAh cm −2 under different working conditions, which are much higher than that of pure Zn anode. Compared with previous reports, such achieving ultrahigh cycling stability and ultrahigh cumulative capacity (Table S1, Supporting Information) in this work is superior not only to other types of metal or alloy‐based interface strategies (Figure S9, Supporting Information), [ 29,32–38 ] but also to the inorganic compound (such as ZnF 2 , ZnO, TiO 2 , and ZrO 2 )‐based interface modifications as well as the electrolyte additive methods (Figure 3e). [ 13,15,39–49 ] Again, all the electrochemical performance tests based on Zn|Zn symmetric cells demonstrate the deposition kinetics and reversibility of Zn plating/stripping behavior can be significantly boosted by in situ built In metal interphase via a facile electrolyte additive modification.…”
Dendrite growth and parasitic side reactions are thorny issues that seriously damage the anode-electrolyte interface during Zn plating/stripping process, leading to uncontrollable Zn deposition and restraining application of aqueous Zn-ion batteries (AZIBs). Here, a unique facile strategy to in situ build indium (In) metal interphase on the Zn anode is first proposed. The combination of experimental and theoretical investigations demonstrate that such metallic interphase prevents the hydrogen evolution reaction (HER) and Zn corrosion, and guides preferential growth along the Zn(002) plane to achieve smooth Zn deposition. As a result, the modified Zn anodes achieve the ultrahigh cumulative capacities of 5600 and 5000 mAh cm −2 at the high current densities of 2 and 5 mA cm −2 , respectively, demonstrating an ultrastable plating/stripping behavior. More encouragingly, the rate performance and cyclic stability of the Zn-V 2 O 5 battery with the electrolyte additive can still deliver a specific capacity of 383.6 mAh g −1 after 5000 cycles at the high current density of 5 A g −1 . The strategy presented here as well as the in-depth understanding of modified mechanism can not only provide an effective solution to address the Zn anode concerns, but also deepen the understanding of AZIBs.
“…Remarkably, Figure 3d indicates that the cumulative capacity of 0.3 m additive modified Zn anodes can be greatly improved up to 990, 1330, 3872, 5000, and even 5600 mAh cm −2 under different working conditions, which are much higher than that of pure Zn anode. Compared with previous reports, such achieving ultrahigh cycling stability and ultrahigh cumulative capacity (Table S1, Supporting Information) in this work is superior not only to other types of metal or alloy‐based interface strategies (Figure S9, Supporting Information), [ 29,32–38 ] but also to the inorganic compound (such as ZnF 2 , ZnO, TiO 2 , and ZrO 2 )‐based interface modifications as well as the electrolyte additive methods (Figure 3e). [ 13,15,39–49 ] Again, all the electrochemical performance tests based on Zn|Zn symmetric cells demonstrate the deposition kinetics and reversibility of Zn plating/stripping behavior can be significantly boosted by in situ built In metal interphase via a facile electrolyte additive modification.…”
Dendrite growth and parasitic side reactions are thorny issues that seriously damage the anode-electrolyte interface during Zn plating/stripping process, leading to uncontrollable Zn deposition and restraining application of aqueous Zn-ion batteries (AZIBs). Here, a unique facile strategy to in situ build indium (In) metal interphase on the Zn anode is first proposed. The combination of experimental and theoretical investigations demonstrate that such metallic interphase prevents the hydrogen evolution reaction (HER) and Zn corrosion, and guides preferential growth along the Zn(002) plane to achieve smooth Zn deposition. As a result, the modified Zn anodes achieve the ultrahigh cumulative capacities of 5600 and 5000 mAh cm −2 at the high current densities of 2 and 5 mA cm −2 , respectively, demonstrating an ultrastable plating/stripping behavior. More encouragingly, the rate performance and cyclic stability of the Zn-V 2 O 5 battery with the electrolyte additive can still deliver a specific capacity of 383.6 mAh g −1 after 5000 cycles at the high current density of 5 A g −1 . The strategy presented here as well as the in-depth understanding of modified mechanism can not only provide an effective solution to address the Zn anode concerns, but also deepen the understanding of AZIBs.
“…1a ). A consequence is that operation of metal anode batteries is generally limited to the regime i << i L 4 , 16 – 22 , which is a barrier to their use in electric grid and fast-charging electrified transportation applications where long-term stability at high current densities is demanded. Fig.…”
Aqueous zinc batteries are attracting interest because of their potential for cost-effective and safe electricity storage. However, metallic zinc exhibits only moderate reversibility in aqueous electrolytes. To circumvent this issue, we study aqueous Zn batteries able to form nanometric interphases at the Zn metal/liquid electrolyte interface, composed of an ion-oligomer complex. In Zn||Zn symmetric cell studies, we report highly reversible cycling at high current densities and capacities (e.g., 160 mA cm−2; 2.6 mAh cm−2). By means of quartz-crystal microbalance, nuclear magnetic resonance, and voltammetry measurements we show that the interphase film exists in a dynamic equilibrium with oligomers dissolved in the electrolyte. The interphase strategy is applied to aqueous Zn||I2 and Zn||MnO2 cells that are charged/discharged for 12,000 cycles and 1000 cycles, respectively, at a current density of 160 mA cm−2 and capacity of approximately 0.85 mAh cm−2. Finally, we demonstrate that Zn||I2-carbon pouch cells (9 cm2 area) cycle stably and deliver a specific energy of 151 Wh/kg (based on the total mass of active materials in the electrode) at a charge current density of 56 mA cm−2.
“…Compared to the ex situ formed protective layers, the in situ formed layers do not require additional binders and often possess stronger adhesion. To date, several kinds of in situ formed protective layers, such as ZIF‐8, [ 114 ] carbon, [ 115 ] zinc phosphate, [ 116 ] ZF 2 , [ 117–119 ] ZnP, [ 120 ] ZnSe, [ 121–123 ] Zn/indium hydroxide sulfate, [ 124 ] AgZn 3 [ 125 ] and polydopamine, [ 126 ] have been reported. These layers are generally in situ formed by electrochemical synthesis, thermal calcination, chemical treatment and other strategies.…”
Section: Protective Layers For Zn Anodesmentioning
Rechargeable zinc-ion batteries (ZIBs) have shown great potential as an alternative to lithium-ion batteries. The ZIBs utilize Zn metal as the anode, which possesses many advantages such as low cost, high safety, eco-friendliness, and high capacity. However, on the other hand, the Zn anode also suffers from many issues, including dendritic growth, corrosion, and passivation. These issues are largely related to the surface and interface properties of the Zn anode. Many efforts have therefore been devoted to the modification of the Zn anode, aiming to eliminate the above-mentioned problems. This review gives a comprehensive summary on the mechanism behind these issues as well as the recent progress on Zn anode modification with focus on the strategies of surface and interface engineering, covering the design and application of both the Zn anode supports and surface protective layers, along with abundant examples. In addition, the promising research directions and perspective on these strategies are also presented.
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