Multi‐Scale Structure Engineering of ZnSnO₃ for Ultra‐Long‐Life Aqueous Zinc‐Metal Batteries

Abstract

Suppressing the severe water‐induced side reactions and uncontrolled dendrite growth of zinc (Zn) metal anodes is crucial for aqueous Zn‐metal batteries to achieve ultra‐long cyclic lifespans and promote their practical applications. Herein, a concept of multi‐scale (electronic‐crystal‐geometric) structure design is proposed to precisely construct the hollow amorphous ZnSnO3 cubes (HZTO) for optimizing Zn metal anodes. In situ gas chromatography demonstrates that Zn anodes modified by HZTO (HZTO@Zn) can effectively inhibit the undesired hydrogen evolution. The pH stabilization and corrosion suppression mechanisms are revealed via operando pH detection and in situ Raman analysis. Moreover, comprehensive experimental and theoretical results prove that the amorphous structure and hollow architecture endow the protective HZTO layer with strong Zn affinity and rapid Zn2+ diffusion, which are beneficial for achieving the ideal dendrite‐free Zn anode. Accordingly, excellent electrochemical performances for the HZTO@Zn symmetric battery (6900 h at 2 mA cm−2, 100 times longer than that of bare Zn), HZTO@Zn||V2O5 full battery (99.3% capacity retention after 1100 cycles), and HZTO@Zn||V2O5 pouch cell (120.6 Wh kg−1 at 1 A g−1) are achieved. This work with multi‐scale structure design provides significant guidance to rationally develop advanced protective layers for other ultra‐long‐life metal batteries.

Ultralong Cycle Life and High Rate of Zn‖I2 Battery Enabled by MBene‐Hosted I2 Cathode

“…The charge/discharge plateaus turn slightly inclined (Figure S16a, Supporting Information), which is a common phenomenon due to polarization. [ 48–50 ] The discharge capacity can be well maintained to be 127.5 mAh g −1 after 75 000 cycles with the coulombic efficiency approaching to 100% (Figure S16b, Supporting Information). Besides, 120.7 mAh g −1 of discharge capacity was delivered at 10 A g −1 when using stainless steel foil as current collector, consolidating that the capacity contribution from the hydrophobic carbon cloth current collector is negligible (Figure S17, Supporting Information).…”

Double-sided engineering for space-confined reversible Zn anodes

“…41 With such functional surface modification, side reactions are prohibited and Zn deposition uniformity is effectively improved. 42–48 However, during long-term cycling at high DOD, Zn anodes experience large volume fluctuations, and an uneven stripping process leads to stress concentration and structural damage. In such cases, the surface coating layer easily loses its protection on Zn anodes, and the detachment of the protective materials deteriorates Zn plating/stripping reversibility.…”

Stabilizing layered superlattice MoSe2 anodes by the rational solvation structure design for low‐temperature aqueous zinc‐ion batteries

“…The emerging environment‐friendly, low‐cost, and high‐safety Zn‐ion batteries (ZIBs) based on high‐ion‐conductivity aqueous electrolytes receive great research enthusiasm due to high theoretical capacity (820 mAh g −1 ) and relatively low redox potential (−0.763 V vs. standard hydrogen electrode) of Zn 2+ /Zn 1 . Although the Mn‐O, V‐O, organic materials, and Prussian blue analogs are demonstrated as available cathodes for accommodating Zn 2+ ions in ZIBs, 2–4 the thermodynamically unstable Zn metal anode in an aqueous electrolyte faces severe problems of Zn dendrite growth and interfacial hydrogen evolution reaction (HER), which push researchers to develop advanced strategies to prevent these side reactions 5–11 . However, the inherent competitive reaction between Zn 2+ deposition and HER causes the inevitable interface parasitic side reactions and irreversible loss of a certain amount of Zn 2+ ions.…”

“…cathodes for accommodating Zn 2+ ions in ZIBs, [2][3][4] the thermodynamically unstable Zn metal anode in an aqueous electrolyte faces severe problems of Zn dendrite growth and interfacial hydrogen evolution reaction (HER), which push researchers to develop advanced strategies to prevent these side reactions. [5][6][7][8][9][10][11] However, the inherent competitive reaction between Zn 2+ deposition and HER causes the inevitable interface parasitic side reactions and irreversible loss of a certain amount of Zn 2+ ions.…”