Stable Zinc Anodes through Synergistic Copper Etching and Zincophilic Polyanionic Crosslinking Membrane

doi:10.6023/A24010006

Abstract

Rechargeable aqueous zinc-based batteries offer several advantages, including high capacity, high energy density, low redox potential, low cost-effectiveness, and good safety, making them a viable option for energy storage alternatives. However, the dendrite growth and side reactions on the zinc metal anode during the galvanization/stripping process significantly decrease the Coulombic Efficiency (CE), reversibility and hinder their practical application. Therefore, we have developed a simple, and effective method to solve this problem. Firstly, a polyanionic crosslinked polymer film (referred to as PZ, where P represents PSS and Z represents ZnCl₂) was deposited on zinc foil using an electrochemical deposition method, resulting from the reaction of sodium polystyrene sulfonate (PSS) and zinc chloride. Secondly, a displacement reaction is employed to introduce the chemically inert copper metal that is zinophilic, resulting in a cross-linked polymer with zinophilic polyanion and a copper etching protective layer (denoted as PZC, where C represents Cu). The rich sulfonate acid groups can promote the exsolution of [Zn(H₂O)₆]²⁺, improve the interface transfer of Zn²⁺, and repel the contact between SO₄^2- and the zinc anode. Through reconstructing the copper etching protective layer, the high zinc affinity of copper promotes deposition kinetics, while the chemical inertness of copper suppresses the occurrence of side reactions. The results indicate that at a high current density of 5 mA•cm^-2, PZC@Zn//PZC@Zn symmetric cells have a lifespan of up to 4055 h (31-fold enhancement over the performance of the bare zinc symmetric cells), and a cumulative electroplating capacity of 10.14 Ah•cm^-2. In addition, Ti//PZC@Zn half-cell demonstrates a CE of 98.28%, showcasing stable and reversible galvanization/stripping process. Furthermore, the YP-50F//PZC@Zn zinc-ion hybrid supercapacitor display stable cycling performance with 15000 cycles at 2 A•g^-1 and deliver a discharge specific capacity of up to 82.35 mAh•g^-1. The α-MnO₂//PZC@Zn aqueous zinc-ion batteries exhibit a discharge-specific capacity of 103.57 mAh•g^-1 after 2000 cycles at 1 A•g^-1 with a CE of 99.58%. This study gives a novel approach to design advanced dendrite-free zinc metal anodes and presents promising implications for future development.

Key words: electrochemical deposition, membrane, copper etching, exsolution, dendrite-free Zn anode

Cite this article

Zaitao Hao, Jianfei Zhao, Huitong Li, Zhan Li, Lang Pan, Jiang Li. Stable Zinc Anodes through Synergistic Copper Etching and Zincophilic Polyanionic Crosslinking Membrane[J]. Acta Chimica Sinica, 2024, 82(4): 416-425.

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Fig. & Tab. 8

Figure 1. Synthetic scheme of PZC@Zn electrodes

Figure 2. SEM images and corresponding contact angle measurements images of (a) Bare Zn, (b) PZ@Zn and (c) PZC@Zn; (d) SEM images of PZC@Zn and (e~g) corresponding element mappings; cross-sectional SEM of (h) PZ@Zn and (i) PZC@Zn; (j) XRD patterns of Bare Zn, PZ@Zn and PZC@Zn

Figure 3. (a) XPS survey scan spectra and high-resolution XPS spectra for (b) C 1s, (c) S 2p, and (d) Zn 2p of PZ@Zn; (e) XPS survey scan spectra and high-resolution XPS spectra for (f) Cu 2p of PZC@Zn

Figure 4. Cycling performance and voltage profiles at selected cycles of the Bare Zn, PZ@Zn and PZC@Zn symmetric cells: (a) 0.5 mA?cm-2, 0.25 mAh?cm-2; (b) 5 mA?cm-2, 1 mAh?cm-2. (c) Rate performance at a fixed capacity of 1 mAh?cm-2; (d) comparison of cycle performance and current densitiy of the PZC@Zn anodes with some previously reported anodes

Figure 5. (a) EIS curves, (b) Tafel polarization curves, (c) chronoamperometry curves, (d) exsolution energy calculated by Arrhenius equation, (e) voltage-capacity curves for Zn deposition at 5 mA?cm-2 and (f) Zn nucleation overpotentials at different current densities of the Bare Zn, PZ@Zn and PZC@Zn symmetric cells

Figure 6. (a, c, e) SEM images and (b, d, f) corresponding XRD results of the Bare Zn, PZ@Zn and PZC@Zn anodes with different numbers of cycle at 3 mA?cm-2 with 1 mAh?cm-2

Figure 7. (a) CEs of Zn plating/stripping for Ti//Bare Zn, Ti//PZ@Zn and Ti//PZC@Zn half-cells at 1 mA?cm-2 with 0.5 mAh?cm-2; (b) voltage profiles of Ti//PZC@Zn half-cells; (c) voltage-time curves at 1 mA?cm-2; (d) CV curves at 1 mV?s-1; (e) SEM images after 40 cycles test and (f) corresponding XRD images

Figure 8. (a) CV curves at 80 mV?s-1 and (b) EIS curves of YP-50F//Bare Zn, YP-50F//PZ@Zn and YP-50F//PZC@Zn ZHSCs; (c) voltage-capacity curves of YP-50F//PZC@Zn ZHSCs; (d) rate performance, (e) long-term cycling performance and (f) SEM images after 4000 cycles test of YP-50F//Bare Zn, YP-50F//PZ@Zn and YP-50F//PZC@Zn ZHSCs; (g) “CHD” LED lit by the YP-50F//PZC@Zn ZHSCs

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