Research Progress of Rare-Earth-Functionalized Carbon Electrodes for Vanadium Redox Flow Batteries

Commercial carbon-based electrodes such as graphite felt and carbon felt in all-vanadium redox flow batteries suffer from inherent drawbacks, including slow vanadium ion redox kinetics, insufficient intrinsic catalytic activity, fiber corrosion, and functional group loss under strong acidic oxidative conditions, significantly limiting battery energy efficiency and long-term operational reliability. Rare-earth elements, with their unique 4f electron shell structure, tunable electronic levels, abundant surface oxygen vacancy defects, and strong coordination ability, offer a dual pathway—electronic and microstructural modulation—to optimize the interfacial electrocatalytic behavior of carbon electrodes, providing a novel materials system to overcome electrode performance bottlenecks in vanadium batteries. This review systematically summarizes recent advances in rare-earth-functionalized carbon electrodes and electrocatalysts for vanadium redox flow batteries, elaborating on core modification strategies, performance enhancement trends, and synergistic catalytic mechanisms. It also presents quantitative experimental results from the literature to clearly demonstrate the benefits: CeO2-modified graphite felt at 0.2 wt% shows a 10.8% increase in energy efficiency compared to pristine graphite felt at a current density of 200 mA·cm−2, while multi-rare-earth co-doped carbon electrodes achieve a 65% reduction in charge transfer resistance relative to unmodified electrodes. The review systematically categorizes two dominant modification routes—surface nano-decoration with rare-earth oxides and lattice bulk doping with rare-earth elements—and summarizes design principles and enhancement mechanisms of diverse composite catalytic systems, including rare-earth–carbon nanocomposites, rare-earth-based heterojunctions, and porous rare-earth catalysts. It further analyzes critical challenges in current research, such as unclear long-term stability mechanisms, high costs of high-purity rare-earth raw materials, immature large-scale fabrication processes, and limited in situ dynamic characterization techniques. Compared with existing reviews, this work clearly distinguishes between surface loading and lattice doping as two distinct rare-earth modification approaches, clarifying their differences in active site formation, electronic regulation logic, and cycling stability. It establishes a comprehensive theoretical framework for the coupled electronic–geometric effects in rare-earth-modified carbon electrodes, linking the intrinsic physicochemical properties of rare earths, material microstructure design, and battery electrochemical performance. Moreover, it innovatively proposes a pathway toward full-lifecycle recycling and reuse of rare-earth-based catalytic electrodes for industrial implementation. This review provides a complete theoretical foundation for developing high-performance, long-cycle, low-cost vanadium redox flow battery electrode materials and supports their engineering scale-up, contributing to the development of large-scale, long-duration energy storage technologies.