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June 3, 2026Advanced Science2 citationsOpen Access

Beyond d‐Band Catalysis: A Critical Review and Descriptor Framework for Rare‐Earth Engineering in Lithium–Sulfur Batteries

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FWFan WangSSShihzad ShakilGWGuozhi Wu

Key Points

  • This review evaluates the multifunctional roles of rare earth elements in lithium-sulfur batteries and establishes a framework for their effective application.
  • Comprehensive analysis of REE-based materials in various battery components including cathodes and electrolytes.
  • Benchmarking against practical metrics such as sulfur loading, areal capacity, and rate capability.
  • Outlining a descriptor-guided framework centered on 4f chemistry to improve catalytic behavior.
  • Identified promising architectures using rare earth elements, enhancing polysulfide management and stability.
  • Showcased persistent limitations in mechanistic validation and the need for consistent reporting practices.
  • Emphasized the importance of a tailored framework to unlock the full potential of 4f chemistry.

Abstract

Rare earth elements (REEs) have emerged as a distinctive class of functional materials for lithium-sulfur (Li-S) batteries, offering catalytic behavior that extends beyond the conventional d-band paradigm of transition-metal systems. Their localized 4f orbitals, variable oxidation states, strong Lewis acidity, and defect chemistry enable multifunctional regulation of polysulfide adsorption and redox conversion. They also enhance interfacial stability. This review evaluates REE-based materials across cathodes, separators, electrolyte/additive systems, and integrated cell architectures, with emphasis on how REEs function as redox mediators, polar anchors, and electronic/ionic interface modulators. Some credible advances arise not from isolated material effects, but from conductive integration, balanced adsorption-conversion, and coordinated deployment across multiple cell components. By benchmarking reported systems against practical metrics, including high sulfur loading, areal capacity, rate capability, and pouch-cell relevance, we identify promising REE-enabled architectures while also highlighting persistent limitations in mechanistic validation and reporting consistency. We further argue that rational progress in this field requires a descriptor-guided framework tailored to 4f chemistry, in which crystal-field splitting, electronegativity, f-d hybridization, oxygen vacancy concentration, and Lewis acidity collectively govern catalytic behavior. Finally, we outline future directions centered on underexplored lanthanides, operando and multiscale characterization, hybrid REE/transition-metal designs, and circular-economy strategies for sustainable deployment.

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Cite This Study

Wang et al. (2026) studied this question.

synapsesocial.com/papers/6a1fc616dee9eb8c0dce74cahttps://doi.org/10.1002/advs.75890
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