• Accepted manuscript •

### Ultra-High Proton/Vanadium Selectivity of Polybenzimidazole Membrane by Incorporating Phosphotungstic Acid Functionalized Nanofibers for Vanadium Redox Flow Battery

Xiaobing Yang, Lei Zhao, Xulei Sui, Linghui Meng, Zhenbo Wang

1. MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, P. R. China
• Received:2019-05-02 Revised:2019-06-02 Accepted:2019-06-05 Published:2019-06-13
• Contact: Zhenbo Wang, Linghui Meng E-mail:wangzhb@hit.edu.cn;menglinh@hit.edu.cn
• Supported by:
The project was supported by the National Natural Science Foundation of China (21273058, 21673064, 51802059 and 21503059), China Postdoctoral Science Foundation (2018M631938, 2018T110307 and 2017M621284), Heilongjiang Postdoctoral Fund, China (LBH-Z17074) and Fundamental Research Funds for the Central Universities, China (HIT. NSRIF. 2019040 and HIT. NSRIF. 2019041).

Abstract: Proton exchange membrane (PEM) is a key component of vanadium redox flow battery (VRB), and its proton/vanadium selectivity plays an important role in the performance of a VRB single cell. Commercially available perfluorosulfonic acid (Nafion) membranes have been widely used due to their excellent proton conductivity and favorable chemical resistance. However, the large pore size micelle channels formed by the pendant sulfonic acid groups lead to the excessive penetration of vanadium ions, which seriously affects the coulombic efficiency (CE) of the single cell and accelerates the self-discharge rate of the battery. Additionally, the expensive cost of Nafion is also an important reason to limit its large-scale application. In this paper, the dense and low-cost hydrocarbon polymer polybenzimidazole (PBI) is used as the matrix material of the PEM, which is doped with phosphotungstic acid (PWA) to acquire excellent proton conductivity, and the intrinsic high resistance of PBI for vanadium ions is helpful to obtain high proton/vanadium selectivity. Considering the enormous water solubility of PWA and its easy leaching from membrane, organic polymer nano-Kevlar fibers (NKFs) are utilized as the anchoring agent of PWA, which achieves good anchoring effect and solves the problem of the poor compatibility between inorganic anchoring agent and the polymer matrix. The formation of PWA functionalized NKFs was characterized by scanning electron microscope (SEM) and Fourier transform infrared (FT-IR) spectroscopy. The anchoring stability of NKFs for PWA was evaluated by UV-Vis spectroscopy. The characterizations including water uptake, swelling ratio, ion exchange capacity, proton conductivity, vanadium ion permeability and ion selectivity were performed to evaluate the basic properties of the membranes. At the same time, the charge-discharge, self-discharge and cycle performance of single cell assembled with the composite membrane and recast Nafion were tested at various current densities from 40 to 100 mA·cm-2. Simple tuning for the filling amount of NKFs@PWA gives the composite membrane superior ion selectivity including an optimal value of 3.26×105 S·min·cm-3, which is 8.5 times higher than that of recast Nafion (0.34×105 S·min·cm-3). As a result, the VRB single cell assembled with the composite membrane exhibits higher CE and significantly lower self-discharge rate compared with recast Nafion. Typically, the CE of the VRB based on PBI-(NKFs@PWA)-22.5% membrane is 97.31% at 100 mA·cm-2 while the value of recast Nafion is only 90.28%. The open circuit voltage (VOC) holding time above 0.8 V of the single cell assembled with the composite membrane is 95 h, which is about 2.4 times as long as that of recast Nafion-based VRB. The utilization of PBI as a separator for VRB can effectively suppress the penetration of vanadium ions, achieve higher proton/vanadium selectivity and superior battery performance as well as reduce the cost of the PEM, which will play an active role in the promotion of VRB applications.

MSC2000:

• O646