Uniform Zinc Plating Enabled By Polyimide Nanofiber Network for Long-Life Aqueous Zinc Metal Batteries
Authors: Lai Chi-Yu , Liao Yin-Song , Chou Jyh-Pin , Hu Chi-Chang 
Published: February 2024

The rapid development of portable electronics and emerging electric vehicles has created a pressing need for electrical energy storage systems. Among these systems, zinc metal batteries (ZMBs) have shown great potential due to their high theoretical capacity density, low reduction potential, and low-cost anodes. However, the large-scale application of rechargeable ZMBs has been limited by the well-known issues of dendrite growth and adverse side reactions in zinc metal electrodes[1].

Various strategies have been proposed to overcome the challenges associated with zinc dendrite growth, including substrate structure optimization, surface modification of zinc metal, and design of novel electrolytes. Among these approaches, constructing a protective layer on the zinc anode surface is a promising strategy due to its simplicity and cost-effectiveness. A dense polyamide coating layer, prepared by the doctor blading method, has been developed to regulate the aqueous Zn deposition behavior by elevating the nucleation barrier and restricting the 2D diffusion of Zn2+ ions [2]. Additionally, an Al2O3 coating layer has been developed using atomic layer deposition to improve the rechargeability of Zn anodes for zinc-ion batteries (ZIBs)[3]. However, these dense layers face a significant challenge to ionic conductivity due to the high energy barrier that hinders the diffusion of Zn2+ ions, leading to poor battery performance, especially under high current densities.

Herein, we report utilizing an electrospun polyimide network (noted as PI-Zn hereafter) to resolve this dilemma. The polyimide (PI) chain has numerous carbonyl oxygen atoms that function as electron donors, supported by theoretical calculations (Fig.1). These atoms can establish stable bonds with Zn ions, thereby reducing the activation energy for de-solvation and enhancing the kinetics of Zn ion deposition. Unlike traditional coating methods, our electrospinning polymers form a fiber-like network structure that provides ion channels, thereby enhancing ion transportation. From the Nyquist plots of symmetrical batteries (Fig. 2), the PI-Zn electrode exhibits smaller charge transfer resistance and lower activation energy compared to the bare Zn electrode. The Transmission X-Ray Microscope results (Fig.3) reveal that the deposition on the bare Zn is heterogeneous and dendritic. In contrast, the PI-Zn electrode presented a smooth surface and dendrite-free morphology. The result demonstrates that the charge transfer ability, de-solvation, and deposition kinetics have been improved by PI-Zn, which further increases the plating uniformity.

The stability of the Zn anode was evaluated by long-term galvanostatic cycling of a symmetrical Zn cell (Fig. 4). The cell with bare Zn failed after cycling for 100 h at a current density of 1 mA cm-2 resulting from the short circuit. In comparison, the cell with PI-Zn exhibits a stable polarization voltage and an ultralong cycling life of over 1200 hours, indicating the extremely reversible plating/stripping enabled by the PI network. Further interrogation of the PI-Zn was carried out by stringent deep-discharge tests in symmetrical Zn cells under extremely high current density and capacity of 20 mA cm-2 and 10 mA h cm-2. The result shows that the cell with PI-Zn can cycle for more than 200 hours, two times longer than that with bare Zn, proving the advantages of the unique fiber-like network structure, which provides fast and homogeneous Zn ion transportation. Moreover, the fiber network effectively suppresses the hydrogen evolution reaction, verified by the corrosion test, despite the existence of numerous ion channels.

Full prototype cells were assembled to prove the practical applications of our strategy. Two promising cathodes for aqueous ZIBs, MnVOH and MnO2, in two different electrolyte systems (Zn(OTf)2 and ZnSO4) were coupled with bare Zn or PI-Zn. For both systems, the capacity retention and Coulombic efficiency are both significantly improved with the help of PI network. The results are consistent with the lifespan difference of symmetrical Zn cells, as expected due to the same plating and stripping processes on Zn. These findings demonstrate that the strategy presented here stands to both dramatically extend battery cycle life and boost battery performance, a promising approach to solve the anode issues in advanced Zn batteries.

Cao, Z., et al., Advanced Energy Materials, 2020. 10(30): p. 2001599.

Zhao, Z., et al., Energy & Environmental Science, 2019. 12(6): p. 1938-1949.

He, H., et al., Journal of materials chemistry A, 2020. 8(16): p. 7836-7846.

Figure 1