High-entropy materials (HEMs) have emerged as a novel concept in the field of materials science and have garnered significant attention in cutting-edge domains such as catalysis, thermoelectric conversion, and electrochemical energy storage. Distinct from traditional materials, HEMs are based on the design concept of "multi-element solid solution", where the entropy-increasing dominant distribution of more than five elements at lattice sites enables the simultaneous regulation of the capacity decay of electrode materials, the interface compatibility of electrolytes, and the cycle durability of full batteries. The successful applications of high-entropy materials in lithium-sulfur batteries, solid-state electrolytes, and other frontier fields in recent years have affirmed their unique values in achieving the synergistic optimization of "high energy density - high safety - low cost", providing a new material design dimension for the next-generation energy storage technology.
HEMs with their distinctive performance regulation ability and multi-element synergy effect, exhibit significant application prospects in the field of energy storage. Although existing reviews have explored the universal laws of high-entropy materials in battery systems (cathode/anode/electrolyte) from the core effect perspective, there remain notable research gaps: in terms of material systems, existing studies are overly concentrated on traditional cathode materials such as rock salt and layered oxides, while the NASICON-type high-entropy materials with the advantage of three-dimensional ion channels have not been deeply analyzed; at the mechanism research level, the focus on electrolytes is mostly on the high-entropy solvation behaviors in liquid systems, neglecting the regularity summary of the correlation mechanism between component disorder and electrochemical performances in inorganic solid-state oxide electrolytes (especially NASICON-type).
Recently, a team of material scientists led by Mengqiang Wu from University of Electronic Science and Technology of China transcended the existing review framework and first established a systematic analysis system for NASICON-type high-entropy materials: (1) Elucidate the regulation mechanism of component disorder on material lattice distortion, interface reconstruction, and ion transport kinetics at the atomic scale, revealing the essential laws of the high-entropy strategy in enhancing electrochemical performance; (2) Integrate the latest research progress of NASICON-type high-entropy materials in cathodes, electrolytes, and anodes across dimensions, and verify their unique advantages in synergistically optimizing the stability of the electrode-electrolyte interface and ion conductivity through typical cases; (3) Provide a feasible approach to address the inherent issues of NASICON systems such as lattice stress accumulation and cycle attenuation. This review will lay a theoretical foundation for the development of the next generation of high-stability and high-energy-density high-entropy energy storage devices.
The team published their work in Journal of Advanced Ceramics on April 15, 2025.
"In this review, we systematically analyzed the fundamental principles underpinning the entropy-driven optimization of electrochemical performance in battery materials, with a focus on the interplay between compositional disorder and functional enhancements. For the first time, we comprehensively review recent advances in NASICON-type HEMs spanning cathodes, solid-state electrolytes, and anodes. Through investigations, the profound impact of high-entropy strategies on critical material parameters was elucidated, including lattice strain modulation, interfacial stability reinforcement, charge-transfer kinetics optimization, and ion transport pathway regulation. Furthermore, we evaluate the current challenges in high-entropy NASICON-type battery design and propose actionable strategies for advancing next-generation high-entropy battery systems, emphasizing rational compositional screening, entropy-stabilized interface design, and machine learning-assisted property prediction." said Youmei Li, a research assistant at the School of Materials and Energy, University of Electronic Science and Technology of China, whose research interests focus on NASICON-type solid electrolyte materials.
"For NASICON cathode materials, the high-entropy strategy exerts the following functions:
(1) Elevating energy density: The high-entropy strategy can activate high-potential and multi-electron couples, facilitate favorable conversions (such as certain difficult-to-attain intermediate phase equilibrium states), and inhibit adverse phase transitions. It can also narrow the band gap to enhance electronic conductivity, thereby raising the output voltage and significantly increasing the energy density. The introduction of strongly electronegative F⁻ or N³⁻ into the polyanion and the utilization of their inductive effects further augment the working voltage and enhance the overall performance of the material.
(2) Enhancing structural stability: Under the synergy of various effects (such as vacancies, pinning effect, entropy stabilization effect, cocktail effect, etc.), the high-entropy strategy reinforces the crystal structure stability of the cathode material. The lattice/volume strain induced by multi-electron reactions is reduced, and the cycling stability is enhanced; the ion transport channels are broadened, the transport path is shortened, the electronic conductivity and ion diffusion kinetics are improved, and simultaneously, the voltage hysteresis and energy loss are effectively mitigated.
(3) Among them, metal ions with larger ionic radii exert a pinning effect on Na⁺/Li⁺ vacancies, suppressing the gliding of transition metals (Transition metal, TM) and unfavorable phase transitions. By moderately increasing the configurational entropy, the structural collapse of the electrode material within the high-voltage region is effectively alleviated." said Youmei Li.
"For NASICON electrolyte materials, the high-entropy strategy exerts the following functions:
(1) Promoting interface stability: The high-entropy effect is capable of suppressing phase expansion/contraction and transition metal migration within the grain structure, delaying crack propagation in high-stress regions, facilitating the attainment of crack-free solid electrolytes, and effectively impeding dendrite growth. The high-entropy effect can reduce the porosity of grain boundaries and increase the density of grain boundaries at lower sintering temperatures, thereby reducing grain boundary resistance. The high-entropy effect gives rise to disordered crystal structures, which can prevent adverse side reactions with reactive metals (Li/Na) and enhance the chemical stability of the material.
(2) Facilitating ion transport: The high-entropy effect promotes the generation of more available vacancies to achieve charge balance. The disordered arrangement within the lattice enables ions to migrate through different channels and paths in multiple dimensions and at multiple sites, reducing mutual hindrance among ions and effectively impeding electron transfer, thereby increasing ion mobility. In long-range ordered crystal structures, ions tend to form stable arrangements with higher binding energy; however, local short-range disorder in high-entropy materials leads to potential energy overlap, forming a percolation network with smaller potential energy differences, reducing ion binding energy, accelerating ion dissociation and migration, and thereby enhancing ionic conductivity. Due to the presence of abundant atomic/ion substitution sites, the system presents higher configurational entropy and more complex microscopic states, promoting the disordered movement and transfer of ions and enhancing ion diffusion kinetics." said Youmei Li.
However, current research on HEMs in battery design remains exploratory, with multi-element synergies governing electrochemical performance through valence states, atomic radii, and electronegativity variations. While HEMs enhance stability and ionic transport via configurational entropy and defect tolerance, challenges persist in thermal/chemical metastability (phase separation, grain boundary segregation) and functional trade-offs (capacity/mechanical compromises). Advanced synthesis techniques (ultra-fast heating, nano-structuring) and element-specific doping strategies aim to mitigate these limitations. Design principles across NASICON-type cathodes, anodes, and electrolytes share entropy-driven stabilization logic, leveraging core effects: (1) multi-element "cocktail effects" for capacity/conductivity optimization, (2) entropy-maximized interfaces to suppress degradation, and (3) lattice distortion-mediated stress buffering. Future efforts require systematic mapping of composition-property relationships to establish predictive models, while cross-domain insights (e.g., machine learning-guided element selection, defect engineering) could unify the "entropy-functionality-stability" paradigm across battery components. While envisioning future technological breakthroughs, Li also presented objective and impartial evaluations as well as pragmatic and feasible evolutionary proposals.
Other contributors include Ming Zhang, Zixuan Fang, Mengqiang Wu from the School of Materials and Energy at University of Electronic Science and Technology of China in Chengdu, China; Jintian Wu from the School of Chemistry and Engineering at University of Science and Engineering in Zigong, China; Ziqiang Xu from the Yangtze Delta Region Institute at University of Electronic Science and Technology of China in Huzhou, China.
This work was supported by Sichuan Science and Technology Department Program (Grant No. 2025ZNSFSC0100, 2023YFG0082, 2023ZHJY0019) and Chengdu Science and Technology Project (Grant No. 2024-YF08-00031- GX, YF0800062-GX).
About Author
Youmei Li is a research assistant at the School of Materials and Energy, University of Electronic Science and Technology of China (UESTC). Her research focuses on NASICON-type solid electrolyte materials.
About Journal of Advanced Ceramics
Journal of Advanced Ceramics (JAC) is an international academic journal that presents the state-of-the-art results of theoretical and experimental studies on the processing, structure, and properties of advanced ceramics and ceramic-based composites. JAC is Fully Open Access, monthly published by Tsinghua University Press, and exclusively available via SciOpen . JAC's 2023 IF is 18.6, ranking in Top 1 (1/31, Q1) among all journals in "Materials Science, Ceramics" category, and its 2023 CiteScore is 21.0 (top 5%) in Scopus database. ResearchGate homepage: https://www.researchgate.net/journal/Journal-of-Advanced-Ceramics-2227-8508
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