Abstract
The trade-off between the ionic conductivity and the stability of the proton exchange membrane (PEM) is a major concern in the development of PEM water electrolysis (PEMWE). This review focuses on the design and fabrication of homogeneous and composite PEMs for water electrolysis and establishes the structure-performance relationships between the membrane chemical/physical structures and their efficiency metrics-specifically, proton conductivity, hydrogen permeability, and chemical and mechanical stability. A special focus is placed on the fundamental connection between the microstructure and performance of membrane materials. At the molecular level, we systematically illustrate the design principles for main chains, side chains, and sulfonate groups, covering both fluorinated PEMs (encompassing perfluorinated and partially fluorinated membranes) and non-fluorinated PEMs (including aromatic polymers with heteroatom backbones and all-carbon backbones). At the macroscopic level, the review provides an in-depth exploration of two primary modification strategies: creating composites with organic polymers and with inorganic nanofillers. In summary, this review elucidates how these composite approaches leverage material synergies to improve the membrane's mechanical integrity, proton conduction efficiency, and chemical resistance and offers a theoretical framework for the rational design of next-generation, high-performance PEMs to advance the commercialization of PEMWE technology.