Regulating Zn Ion Desolvation and Deposition Chemistry Toward Durable and Fast Rechargeable Zn Metal Batteries

Abstract

The high Zn ion desolvation energy, sluggish Zn deposition kinetics, and top Zn plating pattern are the key challenges toward practical Zn anodes. Herein, these key issues are addressed by introducing zinc pyrovanadate (ZVO) as a solid zinc-ion conductor interface to induce smooth and fast Zn deposition underneath the layer. Electrochemical studies, computational analysis, and in situ observations reveal the boosted desolvation and deposition kinetics, and uniformity by ZVO interface. In addition, the anti-corrosion ability of Zn anodes is improved, resulting in high Zn stripping/plating reversibility. Consequently, the ZVO layer renders fast rechargeability and durable life in both Zn symmetric cells (1050 h at 10 mA cm −2 , 1 mAh cm −2 ) and Zn/V 2 O 5 batteries (79.1% capacity retention after 1000 cycles at 2 A g −1 ) with low electrode polarization. This work provides insights into the design of solid zinc-ion conductor interface to enhance the interface stability and kinetics of Zn metal anodes.

Adaptive Ionization-Induced Tunable Electric Double Layer for Practical Zn Metal Batteries over Wide pH and Temperature Ranges

“…As portrayed in Figures S15 and S16, the nucleation overpotential (NOP) of Zn reduction increased from 54 mV to 86 mV after introducing the 80 mM Gly additive, and the higher NOP contributed to the formation of finer Zn crystal particles, yielding a compact deposition layer on the anode surface . Thereafter, chronoamperometry (CA) curves (Figure S17) illustrated that the Gly ± adsorbed on the Zn anode’s surface is competent to restrict the Zn 2+ ions’ two-dimensional (2D) diffusion, as shown in Figure f. , Meanwhile, the Gly ± -containing EDL provides a transfer number ( t Zn 2+ ) of 0.59 (Figure S18), much higher than that of the conventional EDL ( t Zn 2+ = 0.23), thus leading to the reasonable conclusion that Gly ± is ideal for reducing the concentration gradient of Zn 2+ at the electrode/electrolyte interface to inhibit uneven deposition caused by locally high Zn 2+ -concentrations. ,, …”

“…63,64 Meanwhile, the Gly ± -containing EDL provides a transfer number (t Zn 2+ ) of 0.59 (Figure S18), much higher than that of the conventional EDL (t Zn 2+ = 0.23), thus leading to the reasonable conclusion that Gly ± is ideal for reducing the concentration gradient of Zn 2+ at the electrode/electrolyte interface to inhibit uneven deposition caused by locally high Zn 2+ -concentrations. 53,65,66 Molecular dynamics (MD) simulations and experimental tests were exploited to investigate the alteration of Zn 2+ solvation structures in Gly-containing electrolytes in this work. The results of MD simulations showed (Figures 4a−b and S19) that Gly ± appeared around the Zn 2+ solvation structure due to coordination between -COO − and Zn 2+ .…”

Stabilizing a zinc anode via a tunable covalent organic framework-based solid electrolyte interphase

“…By performing EIS, fitted with an equivalent circuit (Fig. S10†) with ZSimpWin software, R ct at different temperatures (Table S5†) can calculate E a , which represents the de-solvation energy barrier, according to the equation: 34–36 where R ct , A , E a , R , and T represent the charge transfer resistance, pre-exponential factor, activation energy, molar gas constant, and absolute temperature. In Fig.…”

“…By performing EIS, fitted with an equivalent circuit (Fig. S10 †) with ZSimpWin software, R ct at different temperatures (Table S5 †) can calculate E a , which represents the de-solvation energy barrier, according to the equation: [34][35][36] ln R ct…”

Low‐Cost Multi‐Function Electrolyte Additive Enabling Highly Stable Interfacial Chemical Environment for Highly Reversible Aqueous Zinc Ion Batteries

“…After cycling, a significant amount of the Zn 4 SO 4 (OH) 6 •xH 2 O by-products with a hexagonal plate structure was observed on the Zn surface in the BE electrolyte. [42][43][44][45] This indicates that CTAB effectively inhibits the formation of by-products, leading to a more stable electrolyte system. Furthermore, the ratio of I (002) to I (101) increases from 0.80 to 1.66 with the addition of 0.2 m CTAB, indicating a preference for Zn 2+ deposition on the (002) plane in the 0.2 m CTAB-ZS electrolyte (Figure 2c).…”