A High-Performance Polyimide Composite Membrane with Flexible Polyphosphazene Derivatives for Vanadium Redox Flow Battery

A sulfonated polyimide, S-F-abSPI, with alkyl sulfonic acid side chains, and a polyphosphonitrile derivative, poly[4-methoxyphenoxy (4-fluorophenoxy) phosphazene] (PFMPP), were designed and synthesized. Composite modification of the S-F-abSPI membrane was carried out using PFMPP, resulting in the preparation of composite membranes with different composite ratios, which were then subjected to performance testing and characterization. Experimental results revealed a significant enhancement in the proton conductivity of the S-F-abSPI membrane, reaching 0.116 S cm^-1, slightly higher than that of the N212 membrane. The S-F-abSPI/1% PFMPP composite membrane exhibited the optimal comprehensive performance, with a surface resistance as low as 0.54 Ω cm², comparable to that of the N212 membrane. At a high current density of 200 mA cm^-2 during charge-discharge, the composite membrane achieved a voltage efficiency (VE) of 83.12% and an energy efficiency (EE) of 81.95%. Cycling tests over 200 cycles demonstrated the composite membrane's excellent long-term cycling stability. The alkyl sulfonic acid side chains enhanced the proton conductivity of the membrane, while electrostatic potential distribution calculations indicated strong interactions between PFMPP and the base membrane, enhancing the membrane's mechanical strength, reducing vanadium ion permeability, and improving chemical stability and vanadium ion selectivity. This composite membrane holds promise for high-performance VRFB applications.