Stacked Lamellar Matrix Enabling Regulated Deposition and Superior Thermo‐Kinetics for Advanced Aqueous Zn‐Ion System under Practical Conditions

Abstract

Zinc anodes have attracted widespread attention for their intrinsic safety, low cost, and abundant resources, but still suffer from severe irreversibility due to spontaneous corrosion and nonplanar dendrite formation in aqueous electrolytes. In this work, a 3D stacked lamellar matrix (SLM) composed of ZnF 2 /Zn 3 (PO 4 ) 2 /CF X is elaborately designed on a Zn substrate via simple chemical/electrochemical reactions, delivering enhanced thermodynamic stability and rapid zinc ions transport kinetics. The abundant ion conduction channels in SLM could also redistribute Zn 2+ ions flux and further suppress the dendrite growth. With these synergetic effects, the SLM-Zn anodes enable exceptional performance, including a high depth of discharge (90%) in a Zn|Zn symmetrical cell for 187 h, steady charge/discharge process (94.1% retention of SLM-Zn|MnO 2 full cell for 1000 cycles at a harsh rate of 15 C), and low negative/positive capacity ratio (≈3.3) in SLM-Zn|AC hybrid supercapacitor with limited Zn anode (10 µm) and high-load cathode (≈1.77 mA h cm −2 ), which greatly promotes the application of aqueous Zn-ion energy system under practical conditions.

High‐Rate, Large Capacity, and Long Life Dendrite‐Free Zn Metal Anode Enabled by Trifunctional Electrolyte Additive with a Wide Temperature Range

“…In addition, the average CE of the Zn||Cu cell with the ZnSO 4 : CH 3 COONH 4 electrolyte was up to 99.23% even after 3000 cycles (Figure 2d–g ), revealing the fascinating reversibility of Zn plating/stripping. Compared to recent reports, [ 26 , 42 , 44 , 45 , 47 , 48 , 49 , 50 , 52 , 53 , 54 , 55 , 56 , 57 , 58 ] the cumulative capacity of the zinc anode was as high as 6880 mAh cm –2 with the modification of CH 3 COONH 4 additive, and the product of the maximum current density and areal capacity could reach to 200 (Figure 2h ), proving that our work fulfills the requirements of high capacity, large current, and long cycle life, which is hopeful for application in practical production.…”

Stimulating Cu–Zn alloying for compact Zn metal growth towards high energy aqueous batteries and hybrid supercapacitors

“…5d and e exhibited outstanding cycling stability with 70.9% capacity retention over 7000 cycles at a current density of 4 A g −1 , of which cumulative capacity corresponds to 3171 mA h cm −2 . When compared with previous AZIB demonstrations, 12–14,25,28,32,60,64,65,69–76 the result stands out as being the most reversible among the cells operating at DOD Zn higher than 20% (Fig. S22 and Table S3, ESI†).…”

“…5c, we visually compare the cycling stability of the DES-Zn electrode with those of Zn electrodes reported in previous studies based on symmetric cell performances. 13,14,[57][58][59][60][61][62][63][64][65] We collected the demonstrations based on planar geometries for representing equivalent surface areas that operated over 100 cycles while excluding the results obtained at ultrahigh current densities (48 mA cm À2 ), which can often be negated by the limited rate capability of separators and cathodes. 66 The areal capacity per cycle, DOD Zn , cumulative capacity, and applied current density are denoted by the radii of the circles, x-and yaxes, and color scale, respectively.…”

Surface and Interface Engineering of Zn Anodes in Aqueous Rechargeable Zn‐Ion Batteries

“…For instance, a 3D stacked lamellar matrix composed of ZnF 2 /Zn 3 (PO 4 ) 2 /CF X was deposited onto Zn anode surface via thermal calcination and electrodeposition, delivering enhanced thermodynamic stability and rapid Zn 2+ ion transport kinetics. [129] The channels and functional sites can not only effectively uniform the Zn 2+ ion flux to inhibit the Zn dendrite growth, but also eliminate the side reactions on the Zn anode surface to enhance the utilization of metallic Zn (Figure 14C). The reported in situ formed coating materials and their corresponding electrochemical performance are summarized in Table 3.…”

“…C) The formation of hybrid ZnF 2 /Zn 3 (PO 4 ) 2 /CFx layer on Zn electrode and the surface chemistry on Zn electrodes. Reproduced with permission [129]. Copyright 2021, Wiley-VCH.…”