高熵碳化物的制备与应用研究进展
Research Progress on the Preparation and Applications of High-Entropy Carbides
DOI: 10.12677/ms.2025.158178, PDF,    科研立项经费支持
作者: 董傲怡, 王贯西, 申少毅, 余志刚, 陈炳全, 刘世凯*：河南工业大学材料科学与工程学院，河南 郑州；刘鑫鑫：深圳市吉嘉新材料科技有限公司，广东 深圳；王基峰：郑州嵩山硼业科技有限公司，河南 郑州
关键词: 高熵碳化物；高熵效应；制备工艺；应用进展；性能优化；High-Entropy Carbides； High-Entropy Effect； Preparation Techniques； Application Advances； Performance Optimization
摘要: 高熵碳化物(High-Entropy Carbides, HECs)作为新兴多主元陶瓷材料，凭借其独特的高熵效应、晶格畸变效应、迟滞扩散效应及“鸡尾酒”效应，在高温稳定性、力学性能及功能特性方面展现出显著优势。本文基于热力学稳定性判据与固溶体形成机制，系统综述了高熵碳化物的研究进展：首先阐释其热力学基础与四大核心效应，分析岩盐型等晶体结构特征及按金属元素组合的分类体系；重点评述六类制备工艺的原理、优势与局限性，指出纳米化、低能耗及成分均匀性为优化方向；进而探讨其在热障涂层、超级电容器及航天高温部件等领域的应用成效；最后还展望其在锌离子电池正极材料中的潜力，并指出当前面临制备工艺复杂、稳定性不足等挑战，为未来高熵碳化物的设计与应用提供理论参考。
Abstract: High-entropy carbides (HECs), as an emerging class of multi-principal-element ceramic materials, exhibit remarkable advantages in high-temperature stability, mechanical properties, and functional characteristics due to their unique high-entropy effect, lattice distortion effect, sluggish diffusion effect, and “cocktail” effect. Based on thermodynamic stability criteria and solid-solution formation mechanisms, this paper systematically reviews recent advances in HECs: 1) The thermodynamic fundamentals and four core effects are elucidated, with an analysis of rock-salt-type crystal structures and classification systems based on transition-metal combinations. 2) Six major preparation methods are critically evaluated in terms of their principles, advantages, and limitations, highlighting optimization strategies such as nano crystallization, low-energy synthesis, and compositional homogeneity. 3) Their application performance is discussed in thermal barrier coatings, supercapacitors, and high-temperature aerospace components. 4) Finally, their potential as cathode materials for zinc-ion batteries is prospected, while current challenges—including complex synthesis routes and insufficient stability—are identified, providing theoretical insights for the future design and application of HECs.
文章引用：董傲怡, 王贯西, 刘鑫鑫, 王基峰, 申少毅, 余志刚, 陈炳全, 刘世凯. 高熵碳化物的制备与应用研究进展[J]. 材料科学, 2025, 15(8): 1667-1678. https://doi.org/10.12677/ms.2025.158178

参考文献

[1] 谢鸿翔, 项厚政, 马瑞奇, 等. 高熵陶瓷材料的研究进展[J]. 材料导报, 2022, 36(6): 61-68.
[2] 郑博远, 吴一栋, 惠希东. 高熵碳化物陶瓷第一性原理计算研究进展与展望[J]. 智能安全, 2024, 3(2): 87-95.
[3] 顾俊峰, 邹冀, 张帆, 等. 高熵陶瓷材料研究进展[J]. 中国材料进展, 2019, 38(9): 855-865+886.
[4] 梅雨, 陈军, 邓文韬, 等. 高熵电化学储能材料的研究进展与新机遇[J]. 硅酸盐学报, 2022, 50(1): 174-184.
[5] Yeh, J. (2006) Recent Progress in High-Entropy Alloys. Annales de Chimie Science des Matériaux, 31, 633-648. [Google Scholar] [CrossRef] 
[6] Rost, C.M., Sachet, E., Borman, T., Moballegh, A., Dickey, E.C., Hou, D., et al. (2015) Entropy-Stabilized Oxides. Nature Communications, 6, Article No. 8485. [Google Scholar] [CrossRef] [PubMed]
[7] Miracle, D.B. and Senkov, O.N. (2017) A Critical Review of High Entropy Alloys and Related Concepts. Acta Materialia, 122, 448-511. [Google Scholar] [CrossRef] 
[8] Ranganathan, S. (2003) Alloyed Pleasures: Multimetallic Cocktails. Current Science, 85, 1404-1406.
[9] 林颖, 胡雅楠, 吴圣川, 等. 基于成分与力学性能调控的NbTiMoVHf(Zr)Si系难熔高熵合金优化[J]. 材料热处理学报, 2023, 44(4): 121-128.
[10] 雷志立, 鲁世强, 邓莉萍. Si对NbCr2/Cr合金组织及性能的影响[J]. 特种铸造及有色合金, 2018, 38(2): 128-131.
[11] 孙涛. (TiZrHfNbTaMe)C(Me=V,Cr,Mo,W)高熵陶瓷的显微组织与性能[D]: [硕士学位论文]. 哈尔滨: 哈尔滨工业大学, 2019.
[12] 王云平, 刘世民, 董闯. 高熵陶瓷材料研究进展及挑战[J]. 材料工程, 2024, 52(1): 83-100
[13] 陈克丕, 李泽民, 马金旭, 等. 高熵陶瓷材料研究进展与展望[J]. 陶瓷学报, 2020, 41(2): 157-163.
[14] 何忠书, 丁方政, 玄伟东, 等. 高熵碳化物材料研究进展[J]. 材料导报, 2024, 38(S1): 95-107.
[15] Zhang, G., Zheng, Y., Zhou, W., Zhao, Y., Zhang, J., Ke, Z., et al. (2018) Microstructure and Mechanical Properties of Ti(C,N)-Based Cermets Fabricated by in Situ Carbothermal Reduction of TiO2 and Subsequent Liquid Phase Sintering. Ceramics International, 44, 3092-3098. [Google Scholar] [CrossRef] 
[16] Li, B., Liu, C., Fang, Z., Yang, Z., Ding, F., Bai, L., et al. (2022) Synthesis of Single-Phase (ZrTiTaNbMo)C High-Entropy Carbide Powders via Magnesiothermic Reduction Process. Journal of the European Ceramic Society, 42, 6767-6773. [Google Scholar] [CrossRef] 
[17] 褚衍辉, 余仁旺, 贺刚, 等. 燃烧合成高熵碳化物纳米颗粒活化过硫酸盐降解四环素污染物(英文) [J]. Science China(Materials), 2022, 65(11): 3144-3149.
[18] 刘倩, 刘含莲, 黄传真, 等. 高熵碳氮化物陶瓷的研究现状及应用展望[J]. 工具技术, 2023, 57(9): 16-23.
[19] Liu, Q., Liu, H., Huang, C., et al. (2023) Effects of Deposition Temperature on the Microstructure, Mechanical Properties, High Temperature Corrosion and Oxidation Properties of AlCrNbTiZr High Entropy Alloy Coatings. International Journal of Refractory Metals and Hard Materials, 61, 1344-1347.
[20] Li, N., Wu, L.H., Li, Z.K., Fu, H.M., Zhu, Z.W., Xue, P., et al. (2023) Achieving Superior Superplasticity in CoCrFeNiCu High Entropy Alloy via Friction Stir Processing with an Improved Convex Tool. Materials Science and Engineering: A, 873, Article 145034. [Google Scholar] [CrossRef] 
[21] Sedegov, A., Vorotilo, S. and Tsybulin, V. (2019) Synthesis and Study of High-Entropy Ceramics Based on the Carbides of Refractory Metals. International Conference on Synthesis and Consolidation of Powder Materials: SCPM-2018, Chenogolovka, 23-26 October 2018, 220-226.
[22] Yang, Y., Bi, J., Sun, K., Qiao, L., Liang, G., Wang, H., et al. (2023) The Effect of Chemical Element on Hardness in High-Entropy Transition Metal Diboride Ceramics. Journal of the European Ceramic Society, 43, 5774-5781. [Google Scholar] [CrossRef] 
[23] Zhang, Z., He, Q., Wu, H., li, T., Zhang, Y., Lu, H., et al. (2023) Balancing Thermal Conductivity and Strength of Hot-Pressed ALN Ceramics via Pre-Sintering and Annealing Process. Ceramics International, 49, 32628-32634. [Google Scholar] [CrossRef] 
[24] Tagir, M., Nikolay, R., Anatoliy, P., et al. (2019) Synthesis of Titanium Orthorhombic Alloy Spherical Powders by Mechanical Alloying and Plasma Spheroidization Processes. Materials Letters, 256, Article 126615. [Google Scholar] [CrossRef] 
[25] Razumov, N., Makhmutov, T., Kim, A., et al. (2024) Preparation and Thermophysical Properties of Medium-Entropy Fluorite-Structured Oxide of (Y0·25Zr0.25Hf0.25Ce0.25)O2-δ. Ceramics International, 50, 17302-17310. [Google Scholar] [CrossRef] 
[26] Ma, Y., Pan, A., Yang, X., et al. (2024) Preparation, Characterization and Performance of High-Entropy Carbonitride Ceramics. Ceramics International, 50, 3034-3040. [Google Scholar] [CrossRef] 
[27] Ning, S., Wen, T., Ye, B., et al. (2019) Low Temperature Synthesis of an Equiatomic (TiZrHfVNb)C5 High Entropy Carbide by a Mechanically-Induced Carbon Diffusion Route. Ceramics International, 45, 21858-21863. [Google Scholar] [CrossRef] 
[28] Wang, H., Han, X., Liu, W. and Wang, Y. (2021) Oxidation Behavior of High-Entropy Carbide (Hf0.2Ta0.2Zr0.2Ti0.2Nb0.2)C at 1400-1600˚C. Ceramics International, 47, 10848-10854. [Google Scholar] [CrossRef] 
[29] Wang, H., Wang, S., Cao, Y., Liu, W. and Wang, Y. (2021) Oxidation Behaviors of (Hf0.25Zr0.25Ta0.25Nb0.25)C and (Hf0.25Zr0.25Ta0.25Nb0.25)C-Sic at 1300-1500˚C. Journal of Materials Science & Technology, 60, 147-155. [Google Scholar] [CrossRef] 
[30] Jun, H.K., Lee, S.J., Han, D., et al. (2020) Au-Incorporated NiO Nanocomposite Thin Films as Electrochromic Electrodes for Superca-Pacitors. Electrochimica Acta, 33, 10745-10752.
[31] Yu, M.L., Zhao, S., Wang, Y., Wu, Q., Zheng, M.X., Wei, G., et al. (2019) Free‐Standing Reduced Graphene Oxide/moO3‐x Composite Film with High Performance for Flexible Supercapacitors. ChemistrySelect, 4, 9165-9173. [Google Scholar] [CrossRef] 
[32] Zhang, X., Fu, Q., Huang, H., Wei, L. and Guo, X. (2019) Silver‐Quantum‐Dot‐Modified Moo3 and MnO2 Paper‐Like Freestanding Films for Flexible Solid‐State Asymmetric Supercapacitors. Small, 15, Article 1805235. [Google Scholar] [CrossRef] [PubMed]
[33] Sathiya, M., Jacquet, Q., Doublet, M., Karakulina, O.M., Hadermann, J. and Tarascon, J. (2018) A Chemical Approach to Raise Cell Voltage and Suppress Phase Transition in O3 Sodium Layered Oxide Electrodes. Advanced Energy Materials, 8, Article 1702599. [Google Scholar] [CrossRef] 
[34] Chen, X., Wang, S., Shi, J., Du, X., Cheng, Q., Xue, R., et al. (2019) Direct Laser Etching Free‐standing Mxene‐MoS2 Film for Highly Flexible Micro‐Supercapacitor. Advanced Materials Interfaces, 6, Article 1901160. [Google Scholar] [CrossRef] 
[35] Parveen, S., Kavyashree, and Pandey, S.N. (2019) Electrochemical Study of 3D Hierarchical Dandelion-Fiber Flake-Like Structure of Al(OH)3/MnO2 Nanocomposite Thin Film for Future Supercapacitor Applications. Electrochimica Acta, 319, 832-842. [Google Scholar] [CrossRef] 
[36] Robert, K., Douard, C., Demortière, A., Blanchard, F., Roussel, P., Brousse, T., et al. (2018) On Chip Interdigitated Micro‐Supercapacitors Based on Sputtered Bifunctional Vanadium Nitride Thin Films with Finely Tuned Inter‐ and Intracolumnar Porosities. Advanced Materials Technologies, 3, Article 1800036. [Google Scholar] [CrossRef] 
[37] 张先丽. 低维高熵碳化物(FeCoCrMnNi)C的电化学赝电容[D]: [硕士学位论文]. 成都: 成都理工大学, 2023.
[38] 张亚宁, 汪凯伦, 朱锦鹏, 等. 高熵稀土铝酸盐双陶瓷涂层的制备及热防护性能研究[J]. 热喷涂技术, 2022, 14(3): 13-22.
[39] 徐世南, 赵善举, 徐立友. 高熵陶瓷材料研究进展与应用现状[J]. 空天技术, 2024(6): 9-26.
[40] 赵子樊. 抗损伤、低热导率的隔热/热密封材料的制备与性能研究[D]: [博士学位论文]. 北京: 中国地质大学, 2020.
[41] Meng, P., Wang, W., Shang, J., Liu, P., Xu, H., Wang, Q., et al. (2023) 2D Vs2@mxene Based Zinc Ion Batteries with Spani‐Contained Electrolyte Enables Dendrite‐Free Anode for Stable Cycling. Small Methods, 7, Article 2201471. [Google Scholar] [CrossRef] [PubMed]
[42] Ma, T., Chen, X. and Li, Q. (2025) Electrochemically Directed Synthesis of Tic Nanotube Arrays for Aqueous Zinc-Ion Batteries. Journal of Materials Chemistry A, 13, 5898-5908. [Google Scholar] [CrossRef] 
[43] Liu, W., Yu, K. and Zhu, Z. (2024) Hollow-Structured V2C Mxene Nanosheets/Carbon Nanocomposites for Aqueous Zinc Ion Batteries. ACS Applied Nano Materials, 7, 24958-24968. [Google Scholar] [CrossRef] 

为你推荐