Innovative High-Entropy Strategy Extending Traditional Metal Substitution for Optimizing Prussian Blue Analogues in Rechargeable Batteries

Abstract

High-entropy materials (HEMs) possess unique properties that can be tailored for specific performance characteristics, making them suitable for various battery applications. In particular, HEMs have shown significant promise in enhancing the electrochemical performance of Prussian blue analogues (PBAs) across various battery systems, including sodium-ion, potassium-ion, lithium-sulfur, aqueous zinc-ion, and aqueous ammonium-ion batteries. This article examines case studies to explore how the high-entropy strategy enhances PBA performance. It also provides an overview of traditional metal substitution methods in modifying the two main types of PBAs, that is, Fe-based and Mn-based PBA electrode materials. Additionally, other optimization methods, such as defect modulation, surface modification, composite structures, and electrolyte modulation, are also discussed. Finally, the article delves deeply into the relationship between high-entropy techniques and traditional metal substitution in modifying PBA electrode materials from the perspectives of element design and performance enhancement, aiming to provide comprehensive theoretical guidance for readers.

Keywords

batteries / high-entropy / metal substitution / Prussian blue analogues

References

[1] J. Peng, W. Zhang, Q. Liu, et al., “Prussian Blue Analogues for Sodium-Ion Batteries: Past, Present, and Future,” Advanced Materials 34, no. 15 (2022): 2108384.

[2] W. Li, C. Han, G. Cheng, S. Chou, H. Liu, and S. Dou, “Chemical Properties, Structural Properties, and Energy Storage Applications of Prussian Blue Analogues,” Small 15, no. 32 (2019): 1900470.

[3] A. Zhou, W. Cheng, W. Wang, et al., “Hexacyanoferrate-Type Prussian Blue Analogs: Principles and Advances toward High-Performance Sodium and Potassium Ion Batteries,” Advanced Energy Materials 11, no. 2 (2021): 2000943.

[4] L. Li, Z. Hu, Y. Lu, et al., “A Low-Strain Potassium-Rich Prussian Blue Analogue Cathode for High Power Potassium-Ion Batteries,” Angewandte Chemie 133, no. 23 (2021): 13160-13166.

[5] S. Chong, Y. Wu, S. Guo, Y. Liu, and G. Cao, “Potassium Nickel Hexacyanoferrate as Cathode for High Voltage and Ultralong Life Potassium-ion Batteries,” Energy Storage Mater 22 (2019): 120-127.

[6] J. W. Heo, M. S. Chae, J. Hyoung, and S. T. Hong, “Rhombohedral Potassium-Zinc Hexacyanoferrate as a Cathode Material for Nonaqueous Potassium-Ion Batteries,” Inorganic Chemistry 58, no. 5 (2019): 3065-3072.

[7] B. Singh and A. Indra, “Prussian Blue- and Prussian Blue Analogue-derived Materials: Progress and Prospects for Electrochemical Energy Conversion,” Mater Today Energy 16 (2020): 100404.

[8] L. Deng, Z. Yang, L. Tan, L. Zeng, Y. Zhu, and L. Guo, “Investigation of the Prussian Blue Analog Co₃ [Co(CN)₆]₂ as an Anode Material for Nonaqueous Potassium-Ion Batteries,” Advanced Materials 30, no. 31 (2018): 1802510.

[9] C. Zhang, Y. Xu, M. Zhou, et al., “Potassium Prussian Blue Nanoparticles: A Low-Cost Cathode Material for Potassium-Ion Batteries,” Advanced Functional Materials 27, no. 4 (2017): 1604307.

[10] Y. Zhu, Y. Yin, X. Yang, et al., “Transformation of Rusty Stainless-Steel Meshes Into Stable, Low-Cost, and Binder-Free Cathodes for High-Performance Potassium-Ion Batteries,” Angewandte Chemie International Edition 56, no. 27 (2017): 7881-7885.

[11] Y. Lu, L. Wang, J. Cheng, and J. B. Goodenough, “Prussian Blue: A New Framework of Electrode Materials for Sodium Batteries,” Chemical Communications 48, no. 52 (2012): 6544.

[12] S. Chong, Y. Chen, Y. Zheng, et al., “Potassium Ferrous Ferricyanide Nanoparticles as a High Capacity and Ultralong Life Cathode Material for Nonaqueous Potassium-ion Batteries,” Journal of Materials Chemistry A 5, no. 43 (2017): 22465-22471.

[13] H. W. Lee, R. Y. Wang, M. Pasta, S. Woo Lee, N. Liu, and Y. Cui, “Manganese Hexacyanomanganate Open Framework as a High-Capacity Positive Electrode Material for Sodium-ion Batteries,” Nature Communications 5, no. 1 (2014): 5280.

[14] S. I. Tobishima and A. Yamaji, “Ethylene Carbonate—propylene Carbonate Mixed Electrolytes for Lithium Batteries,” Electrochimica Acta 29, no. 2 (1984): 267-271.

[15] J. Han, A. Varzi, and S. Passerini, “The Emergence of Aqueous Ammonium-Ion Batteries,” Angewandte Chemie 134, no. 14 (2022): e202115046.

[16] M. Salado, M. Amores, C. Pozo-Gonzalo, M. Forsyth, and S. Lanceros-Méndez, “Advanced and Sustainable Functional Materials for Potassium-ion Batteries,” Energy Mater 3, no. 5 (2023): 300037.

[17] M. Zarrabeitia, J. Carretero-González, M. Leskes, et al., “Could Potassium-ion Batteries Become a Competitive Technology?” Energy Mater 3, no. 6 (2023).

[18] S. Fan, Y. Liu, Y. Gao, et al., “The Design and Synthesis of Prussian Blue Analogs as a Sustainable Cathode for Sodium-ion Batteries,” SusMat 3, no. 6 (2023): 749-780.

[19] Z. Li, T. Liu, R. Meng, et al., “Insights Into the Structure Stability of Prussian Blue for Aqueous Zinc Ion Batteries,” Energy & Environmental Materials 4, no. 1 (2021): 111-116.

[20] M. S. Chae, J. W. Heo, H. H. Kwak, H. Lee, and S. T. Hong, “Organic Electrolyte-based Rechargeable Zinc-ion Batteries Using Potassium Nickel Hexacyanoferrate as a Cathode Material,” Journal of Power Sources 337 (2017): 204-211.

[21] X. Wang, B. Wang, Y. Tang, et al., “Manganese Hexacyanoferrate Reinforced by PEDOT Coating towards High-Rate and Long-Life Sodium-ion Battery Cathode,” Journal of Materials Chemistry A 8, no. 6 (2020): 3222-3227.

[22] W. Shu, C. Han, and X. Wang, “Prussian Blue Analogues Cathodes for Nonaqueous Potassium-Ion Batteries: Past, Present, and Future,” Advanced Functional Materials 34, no. 1 (2024): 2309636.

[23] M. Jiang, Z. Hou, L. Ren, Y. Zhang, and J. G. Wang, “Prussian blue and Its Analogues for Aqueous Energy Storage: From Fundamentals to Advanced Devices,” Energy Storage Materials 50 (2022): 618-640.

[24] L. Chen, W. Sun, K. Xu, et al., “How Prussian Blue Analogues Can Be Stable in Concentrated Aqueous Electrolytes,” ACS Energy Letters 7, no. 5 (2022): 1672-1678.

[25] K. Du, Y. Liu, Y. Zhao, et al., “High-Entropy Prussian Blue Analogues Enable Lattice Respiration for Ultrastable Aqueous Aluminum-Ion Batteries,” Advanced Materials 36, no. 30 (2024): 2404172.

[26] Z. Hu, B. Zhang, H. Zhang, and Y. Ma, “Optimizing Prussian Blue Analogues for Potassium-Ion Batteries: Advanced Strategies,” Batter Supercaps (2024): e202400448.

[27] B. Ouyang and Y. Zeng, “The Rise of High-Entropy Battery Materials,” Nature Communications 15, no. 1 (2024): 973.

[28] W. Zheng, G. Liang, Q. Liu, et al., “The Promise of High-Entropy Materials for High-Performance Rechargeable Li-ion and Na-ion Batteries,” Joule 7, no. 12 (2023): 2732-2748.

[29] F. Ding, Y. Lu, L. Chen, and Y. S. Hu, “High-Entropy Strategy for Electrochemical Energy Storage Materials,” Electrochemical Energy Reviews 7, no. 1 (2024): 16.

[30] K. Wang, W. Hua, X. Huang, et al., “Synergy of Cations in High Entropy Oxide Lithium Ion Battery Anode,” Nature Communications 14, no. 1 (2023): 1487.

[31] J. Wang, S. L. Dreyer, K. Wang, et al., “P2-Type Layered High-Entropy Oxides as Sodium-ion Cathode Materials,” Materials Futures 1, no. 3 (2022): 035104.

[32] Q. Wang, A. Sarkar, D. Wang, et al., “Multi-Anionic and -Cationic Compounds: New High Entropy Materials for Advanced Li-ion Batteries,” Energy & Environmental Science 12, no. 8 (2019): 2433-2442.

[33] Y. Dong, Z. Zhou, Y. Ma, et al., “Layered-Structured Sodium-Ion Cathode Materials: Advancements Through High-Entropy Approaches,” ACS Energy Letters 9, no. 10 (2024): 5096-5119.

[34] C. Zhao, F. Ding, Y. Lu, L. Chen, and Y. Hu, “High-Entropy Layered Oxide Cathodes for Sodium-Ion Batteries,” Angewandte Chemie International Edition 59, no. 1 (2020): 264-269.

[35] J. Qian, C. Wu, Y. Cao, et al., “Prussian Blue Cathode Materials for Sodium-Ion Batteries and Other Ion Batteries,” Advanced Energy Materials 8, no. 17 (2018): 1702619.

[36] Y. Ma, Y. Ma, S. L. Dreyer, et al., “High-Entropy Metal-Organic Frameworks for Highly Reversible Sodium Storage,” Advanced Materials 33, no. 34 (2021): 2101342.

[37] Y. Ma, Y. Hu, Y. Pramudya, et al., “Resolving the Role of Configurational Entropy in Improving Cycling Performance of Multicomponent Hexacyanoferrate Cathodes for Sodium-Ion Batteries,” Advanced Functional Materials 32, no. 34 (2022): 2202372.

[38] J. Dai, S. Tan, L. Wang, et al., “High-Voltage Potassium Hexacyanoferrate Cathode via High-Entropy and Potassium Incorporation for Stable Sodium-Ion Batteries,” ACS Nano 17, no. 21 (2023): 20949-20961.

[39] B. Xie, B. Sun, T. Gao, Y. Ma, G. Yin, and P. Zuo, “Recent Progress of Prussian Blue Analogues as Cathode Materials for Nonaqueous Sodium-ion Batteries,” Coordination Chemistry Reviews 460 (2022): 214478.

[40] X. Li, Y. Shang, D. Yan, L. Guo, S. Huang, and H. Y. Yang, “Topotactic Epitaxy Self-Assembly of Potassium Manganese Hexacyanoferrate Superstructures for Highly Reversible Sodium-Ion Batteries,” ACS Nano 16, no. 1 (2022): 453-461.

[41] Y. Wang, F. Zhang, Q. Long, et al., “Enhancing Cyclic Stability of Mn-Based Prussian Blue Cathode for Potassium Ion Storage by High-Spin Fe Substitution Strategy,” Energy Storage Materials 71 (2024): 103399.

[42] H. Fu, C. Liu, C. Zhang, et al., “Enhanced Storage of Sodium Ions in Prussian Blue Cathode Material Through Nickel Doping,” Journal of Materials Chemistry A 5, no. 20 (2017): 9604-9610.

[43] Y. Zhu, Z. Zhang, J. Bao, et al., “Multi-Metal Doped High Capacity and Stable Prussian Blue Analogue for Sodium Ion Batteries,” International Journal of Energy Research 44, no. 11 (2020): 9205-9212.

[44] Y. Ma, T. Brezesinski, B. Breitung, and Y. Ma, “High-Entropy Hexacyanoferrates as Robust Cathode Active Materials for Sodium Storage,” Matter 6, no. 2 (2023): 313-315.

[45] X. Zhang, K. Ren, Y. Liu, et al., “Progress on Entropy Production Engineering for Electrochemical Catalysis,” Acta Physico-Chimica Sinica 40, no. 7 (2023): 2307057.

[46] C. Oses, C. Toher, and S. Curtarolo, “High-Entropy Ceramics,” Nature Reviews Materials 5, no. 4 (2020): 295-309.

[47] R. Carroll, C. Lee, C. W. Tsai, et al., “Experiments and Model for Serration Statistics in Low-Entropy, Medium-Entropy and High-Entropy Alloys,” Scientific Reports 5, no. 1 (2015): 16997.

[48] Y. Ma, Y. Ma, Q. Wang, et al., “High-Entropy Energy Materials: Challenges and New Opportunities,” Energy & Environmental Science 14, no. 5 (2021): 2883-2905.

[49] D. B. Miracle and O. N. Senkov, “A Critical Review of High Entropy Alloys and Related Concepts,” Acta Materialia 122 (2017): 448-511.

[50] A. Sarkar, L. Velasco, D. Wang, et al., “High Entropy Oxides for Reversible Energy Storage,” Nature Communications 9, no. 1 (2018): 3400.

[51] A. Sarkar, Q. Wang, A. Schiele, et al., “High-Entropy Oxides: Fundamental Aspects and Electrochemical Properties,” Advanced Materials 31, no. 26 (2019): 1806236.

[52] A. Sarkar, B. Breitung, and H. Hahn, “High Entropy Oxides: The Role of Entropy, Enthalpy and Synergy,” Scripta Materialia 187 (2020): 43-48.

[53] Y. Chen, H. Fu, Y. Huang, et al., “Opportunities for High-Entropy Materials in Rechargeable Batteries,” ACS Materials Letters 3, no. 2 (2021): 160-170.

[54] S. Schweidler, M. Botros, F. Strauss, et al., “High-Entropy Materials for Energy and Electronic Applications,” Nature Reviews Materials 9, no. 4 (2024): 266-281.

[55] Y. Yao, Q. Dong, A. Brozena, et al., “High-Entropy Nanoparticles: Synthesis-Structure-Property Relationships and Data-Driven Discovery,” Science 376, no. 6589 (2022): eabn3103.

[56] C. M. Rost, E. Sachet, T. Borman, et al., “Entropy-Stabilized Oxides,” Nature Communications 6, no. 1 (2015): 8485.

[57] B. Jiang, Y. Yu, J. Cui, et al., “High-Entropy-Stabilized Chalcogenides With High Thermoelectric Performance,” Science 371, no. 6531 (2021): 830-834.

[58] W. L. Hsu, C. W. Tsai, A. C. Yeh, and J. W. Yeh, “Clarifying the Four Core Effects of High-Entropy Materials,” Nature Reviews Chemistry 8, no. 6 (2024): 471-485.

[59] A. Sarkar and Q. Wang, “High-Entropy Oxides: Fundamental Aspects and Electrochemical Properties,” Advanced Materials 31, no. 26 (2019): 1806236.

[60] A. Joshi, S. Chakraborty, S. H. Akella, et al., “High-Entropy Co-Free O3-type Layered Oxyfluoride: A Promising Air-Stable Cathode for Sodium-Ion Batteries,” Advanced Materials 35, no. 51 (2023): 2304440.

[61] H. Gao, J. Li, F. Zhang, et al., “Revealing the Potential and Challenges of High-Entropy Layered Cathodes for Sodium-Based Energy Storage,” Advanced Energy Materials 14, no. 20 (2024): 2304529.

[62] X. Z. Wang, Y. Zuo, Y. Qin, et al., “Fast Na⁺ Kinetics and Suppressed Voltage Hysteresis Enabled by a High-Entropy Strategy for Sodium Oxide Cathodes,” Advanced Materials 36, no. 24 (2024): 2312300.

[63] Y. Zeng, B. Ouyang, J. Liu, et al., “High-Entropy Mechanism to Boost Ionic Conductivity,” Science 378, no. 6626 (2022): 1320-1324.

[64] M. Botros and J. Janek, “Embracing Disorder in Solid-State Batteries,” Science 378, no. 6626 (2022): 1273-1274.

[65] Z. Gu, J. Guo, J. Cao, et al., “An Advanced High-Entropy Fluorophosphate Cathode for Sodium-Ion Batteries With Increased Working Voltage and Energy Density,” Advanced Materials 34, no. 14 (2022): 2110108.

[66] M. Li, C. Sun, Q. Ni, et al., “High Entropy Enabling the Reversible Redox Reaction of V⁴⁺ /V⁵⁺ Couple in NASICON-Type Sodium Ion Cathode,” Advanced Energy Materials 13, no. 12 (2023): 2203971.

[67] C. D. Wessells, R. A. Huggins, and Y. Cui, “Copper Hexacyanoferrate Battery Electrodes With Long Cycle Life and High Power,” Nature Communications 2, no. 1 (2011): 550.

[68] L. Wu, X. Hu, J. Qian, et al., “Sb-C Nanofibers With Long Cycle Life as an Anode Material for High-Performance Sodium-ion Batteries,” Energy and Environmental Science 7, no. 1 (2014): 323-328.

[69] C. Yang, S. Xin, L. Mai, and Y. You, “Materials Design for High-Safety Sodium-Ion Battery,” Advanced Energy Materials 11, no. 2 (2021): 2000974.

[70] S. Zhou, Z. Tang, Z. Pan, et al., “Regulating Closed Pore Structure Enables Significantly Improved Sodium Storage for Hard Carbon Pyrolyzing at Relatively Low Temperature,” SusMat 2, no. 3 (2022): 357-367.

[71] Y. Zhou, G. Xu, J. Lin, et al., “A Multicationic-Substituted Configurational Entropy-Enabled NASICON Cathode for High-Power Sodium-ion Batteries,” Nano Energy 128 (2024): 109812.

[72] X. Wu, C. Wu, C. Wei, et al., “Highly Crystallized Na₂CoFe(CN)₆ With Suppressed Lattice Defects as Superior Cathode Material for Sodium-Ion Batteries,” ACS Applied Materials & Interfaces 8, no. 8 (2016): 5393-5399.

[73] Y. Fang, L. Xiao, X. Ai, Y. Cao, and H. Yang, “Hierarchical Carbon Framework Wrapped Na₃V₂(PO₄)₃ as a Superior High-Rate and Extended Lifespan Cathode for Sodium-Ion Batteries,” Advanced Materials 27, no. 39 (2015): 5895-5900.

[74] Y. Huang, Y. Zhu, A. Nie, et al., “Enabling Anionic Redox Stability of P2-Na_5/6Li_1/4Mn_3/4O₂ by Mg Substitution,” Advanced Materials 34, no. 9 (2022): 2105404.

[75] M. D. Slater, D. Kim, E. Lee, and C. S. Johnson, “Sodium-Ion Batteries,” Advanced Functional Materials 23, no. 8 (2013): 947-958.

[76] G. Wan, B. Peng, L. Zhao, et al., “Dual-Strategy Modification on P2-Na_0.67Ni_0.33Mn_0.67O₂ Realizes Stable High-Voltage Cathode and High Energy Density Full Cell for Sodium-ion Batteries,” SusMat 3, no. 1 (2023): 58-71.

[77] W. Zuo, A. Innocenti, M. Zarrabeitia, D. Bresser, Y. Yang, and S. Passerini, “Layered Oxide Cathodes for Sodium-Ion Batteries: Storage Mechanism, Electrochemistry, and Techno-Economics,” Accounts of Chemical Research 56, no. 3 (2023): 284-296.

[78] Y. Xiao, N. M. Abbasi, Y. F. Zhu, et al., “Layered Oxide Cathodes Promoted by Structure Modulation Technology for Sodium-Ion Batteries,” Advanced Functional Materials 30, no. 30 (2020): 2001334.

[79] Y. Sun, S. Guo, and H. Zhou, “Adverse Effects of Interlayer-Gliding in Layered Transition-Metal Oxides on Electrochemical Sodium-ion Storage,” Energy & Environmental Science 12, no. 3 (2019): 825-840.

[80] T. Jin, H. Li, K. Zhu, P. F. Wang, P. Liu, and L. Jiao, “Polyanion-Type Cathode Materials for Sodium-ion Batteries,” Chemical Society Reviews 49, no. 8 (2020): 2342-2377.

[81] J. Zhou, B. Zheng, X. Huang, et al., “High Voltage, Long Cycling Organic Cathodes Rendered by in Situ Electrochemical Oxidation Polymerization,” Advanced Functional Materials 34, no. 52 (2024): 2411127.

[82] X. Wu, W. Zhou, C. Ye, et al., “Porphyrin-Thiophene Based Conjugated Polymer Cathode With High Capacity for Lithium-Organic Batteries,” Angewandte Chemie International Edition 63, no. 14 (2024): e202317135.

[83] X. Chen, X. Feng, B. Ren, et al., “High Rate and Long Lifespan Sodium-Organic Batteries Using Pseudocapacitive Porphyrin Complexes-Based Cathode,” Nano-Micro Letters 13, no. 1 (2021): 71.

[84] H. Yi, R. Qin, S. Ding, et al., “Structure and Properties of Prussian Blue Analogues in Energy Storage and Conversion Applications,” Advanced Functional Materials 31, no. 6 (2021): 2006970.

[85] D. Baster, Ł. Kondracki, E. Oveisi, S. Trabesinger, and H. H. Girault, “Prussian Blue Analogue—Sodium-Vanadium Hexacyanoferrate as a Cathode Material for Na-Ion Batteries,” ACS Applied Energy Materials 4, no. 9 (2021): 9758-9765.

[86] Y. Huang, X. Zhang, L. Ji, et al., “Boosting the Sodium Storage Performance of Prussian Blue Analogs by Single-crystal and High-Entropy Approach,” Energy Storage Materials 58 (2023): 1-8.

[87] J. Peng, B. Zhang, W. Hua, et al., “A Disordered Rubik's Cube-Inspired Framework for Sodium-Ion Batteries With Ultralong Cycle Lifespan,” Angewandte Chemie International Edition 62, no. 6 (2023): e202215865.

[88] Y. Zhang, J. Huang, L. Qiu, et al., “Hollow Stair-Stepping Spherical High-Entropy Prussian Blue Analogue for High-Rate Sodium Ion Batteries,” ACS Applied Materials & Interfaces 16, no. 21 (2024): 27684-27693.

[89] Y. Wang, N. Jiang, C. Yang, et al., “High-Entropy Prussian Blue Analogs With 3D Confinement Effect for Long-Life Sodium-ion Batteries,” Journal of Materials Chemistry A 12, no. 9 (2024): 5170-5180.

[90] Y. He, S. L. Dreyer, Y. Ting, et al., “Entropy-Mediated Stable Structural Evolution of Prussian White Cathodes for Long-Life Na-Ion Batteries,” Angewandte Chemie 136, no. 7 (2024): e202315371.

[91] Y. He, S. L. Dreyer, T. Akçay, et al., “Leveraging Entropy and Crystal Structure Engineering in Prussian Blue Analogue Cathodes for Advancing Sodium-Ion Batteries,” ACS Nano 18, no. 35 (2024): 24441-24457.

[92] C. Wei, X. Y. Fu, L. L. Zhang, et al., “Structural Regulated Nickel Hexacyanoferrate With Superior Sodium Storage Performance by K-Doping,” Chemical Engineering Journal 421 (2021): 127760.

[93] L. Shen, Y. Jiang, Y. Liu, J. Ma, T. Sun, and N. Zhu, “High-Stability Monoclinic Nickel Hexacyanoferrate Cathode Materials for Ultrafast Aqueous Sodium Ion Battery,” Chemical Engineering Journal 388 (2020): 124228.

[94] X. Zhao, Z. Xing, and C. Huang, “Investigation of High-Entropy Prussian Blue Analog as Cathode Material for Aqueous Sodium-ion Batteries,” Journal of Materials Chemistry A 11, no. 42 (2023): 22835-22844.

[95] B. Ran, R. Cheng, Y. Zhong, et al., “High Entropy Activated and Stabilized Nickel-Based Prussian Blue Analogue for High-Performance Aqueous Sodium-ion Batteries,” Energy Storage Materials 71 (2024): 103583.

[96] E. R. Nightingale, “Phenomenological Theory of Ion Solvation. Effective Radii of Hydrated Ions,” Journal of Physical Chemistry 63, no. 9 (1959): 1381-1387.

[97] X. Zhang, T. Xiong, B. He, et al., “Recent Advances and Perspectives in Aqueous Potassium-ion Batteries,” Energy & Environmental Science 15, no. 9 (2022): 3750-3774.

[98] C. Ma, C. Lin, N. Li, et al., “A High-Entropy Prussian Blue Analog for Aqueous Potassium-Ion Batteries,” Small 20, no. 23 (2024): 2310184.

[99] B. Liu, Q. Zhang, L. Zhang, X. Yong, L. Li, and C. Wang, “Manganese Charge Redistribution Induced by High-Entropy Charge Compensation Mechanism for Aqueous Potassium-ion Batteries,” Energy Storage Materials 66 (2024): 103221.

[100] J. Wang, Y. He, and J. Yang, “Sulfur-Based Composite Cathode Materials for High-Energy Rechargeable Lithium Batteries,” Advanced Materials 27, no. 3 (2015): 569-575.

[101] Y. Cao, M. Li, J. Lu, J. Liu, and K. Amine, “Bridging the Academic and Industrial Metrics for next-Generation Practical Batteries,” Nature Nanotechnology 14, no. 3 (2019): 200-207.

[102] L. Yin, J. Wang, F. Lin, J. Yang, and Y. Nuli, “Polyacrylonitrile/Graphene Composite as a Precursor to a Sulfur-Based Cathode Material for High-Rate Rechargeable Li-S Batteries,” Energy & Environmental Science 5, no. 5 (2012): 6966.

[103] M. Du, P. Geng, C. Pei, et al., “High-Entropy Prussian Blue Analogues and Their Oxide Family as Sulfur Hosts for Lithium-Sulfur Batteries,” Angewandte Chemie 134, no. 41 (2022): e202209350.

[104] N. Shen, T. Li, B. Li, et al., “Dual-Functional Mediators of High-Entropy Prussian Blue Analogues for Lithiophilicity and Sulfiphilicity in Li-S Batteries,” Nanoscale 16, no. 15 (2024): 7634-7644.

[105] Y. Zeng, X. Zhang, R. Qin, et al., “Dendrite-Free Zinc Deposition Induced by Multifunctional CNT Frameworks for Stable Flexible Zn-Ion Batteries,” Advanced Materials 31, no. 36 (2019): 1903675.

[106] L. Zhou, F. Yang, S. Zeng, et al., “Zincophilic Cu Sites Induce Dendrite-Free Zn Anodes for Robust Alkaline/Neutral Aqueous Batteries,” Advanced Functional Materials 32, no. 15 (2022): 2110829.

[107] X. He, H. Zhang, X. Zhao, et al., “Stabilized Molybdenum Trioxide Nanowires as Novel Ultrahigh-Capacity Cathode for Rechargeable Zinc Ion Battery,” Advancement of Science 6, no. 14 (2019): 1900151.

[108] H. Liu, J. G. Wang, Z. You, C. Wei, F. Kang, and B. Wei, “Rechargeable Aqueous Zinc-ion Batteries: Mechanism, Design Strategies and Future Perspectives,” Materials Today 42 (2021): 73-98.

[109] Y. Shi, Y. Chen, L. Shi, et al., “An Overview and Future Perspectives of Rechargeable Zinc Batteries,” Small 16, no. 23 (2020): 2000730.

[110] Y. Liao, H. C. Chen, C. Yang, et al., “Unveiling Performance Evolution Mechanisms of MnO₂ Polymorphs for Durable Aqueous Zinc-ion Batteries,” Energy Storage Materials 44 (2022): 508-516.

[111] Y. Jin, L. Zou, L. Liu, et al., “Joint Charge Storage for High-Rate Aqueous Zinc-Manganese Dioxide Batteries,” Advanced Materials 31, no. 29 (2019): 1900567.

[112] C. Zhong, B. Liu, J. Ding, et al., “Decoupling Electrolytes towards Stable and High-Energy Rechargeable Aqueous Zinc-Manganese Dioxide Batteries,” Nature Energy 5, no. 6 (2020): 440-449.

[113] J. Xing, Y. Zhang, Y. Jin, and Q. Jin, “Active Cation-Integration High-Entropy Prussian Blue Analogues Cathodes for Efficient Zn Storage,” Nano Research 16, no. 2 (2023): 2486-2494.

[114] H. Yu, L. Fan, H. Yan, et al., “Nickel Ferrocyanides for Aqueous Ammonium Ion Batteries,” Inorganic Chemistry Frontiers 9, no. 9 (2022): 2001-2010.

[115] X. Zhang, M. Xia, H. Yu, et al., “Hydrogen Bond-Assisted Ultra-Stable and Fast Aqueous NH⁴+ Storage,” Nano-Micro Letters 13, no. 1 (2021): 139.

[116] Y. Shen, J. Zou, H. Lan, et al., “Unlocking Prussian Blue Analogues Inert-Site to Achieve High-Capacity Ammonium Storage,” Advanced Functional Materials 34, no. 29 (2024): 2400598.

[117] M. Han, “A Rotatable Cathode With Tunable Steric Hindrance for High-Performance Aluminum Organic Batteries,” Journal of Materials Chemistry A 11, no. 25 (2023): 13527-13534.

[118] X. Zhao, L. Mao, Q. Cheng, et al., “Interlayer Engineering of Preintercalated Layered Oxides as Cathode for Emerging Multivalent Metal-ion Batteries: Zinc and beyond,” Energy Storage Materials 38 (2021): 397-437.

[119] K. Hurlbutt, S. Wheeler, I. Capone, and M. Pasta, “Prussian Blue Analogs as Battery Materials,” Joule 2, no. 10 (2018): 1950-1960.

[120] Y. Liu, J. Yang, Z. Gu, et al., “Entropy-Regulated Cathode With Low Strain and Constraint Phase-Change toward Ultralong-Life Aqueous Al-Ion Batteries,” Angewandte Chemie International Edition 63, no. 12 (2024): e202316925.

[121] Y. Gao, H. Yang, X. Wang, et al., “The Compensation Effect Mechanism of Fe-Ni Mixed Prussian Blue Analogues in Aqueous Rechargeable Aluminum-Ion Batteries,” Chemsuschem 13, no. 4 (2020): 732-740.

[122] D. Wang, H. Lv, T. Hussain, et al., “A Manganese Hexacyanoferrate Framework With Enlarged Ion Tunnels and Two-Species Redox Reaction for Aqueous Al-ion Batteries,” Nano Energy 84 (2021): 105945.

[123] S. Zhao, Z. Guo, K. Yan, et al., “The Rise of Prussian Blue Analogs: Challenges and Opportunities for High-Performance Cathode Materials in Potassium-Ion Batteries,” Small Structures 2, no. 1 (2021): 2000054.

[124] Z. Wang, L. Fang, X. Fu, et al., “A Ni/Co-Free High-Entropy Layered Cathode With Suppressed Phase Transition and Near-Zero Strain for High-Voltage Sodium-ion Batteries,” Chemical Engineering Journal 480 (2024): 148130.

[125] Y. Wang, R. Xiao, Y. S. Hu, M. Avdeev, and L. Chen, “P2-Na_0.6[Cr_0.6Ti_0.4]O₂ Cation-disordered Electrode for High-Rate Symmetric Rechargeable Sodium-ion Batteries,” Nature Communications 6, no. 1 (2015): 6954.

[126] L. Yang, C. Chen, S. Xiong, et al., “Multiprincipal Component P2-Na_0.6(Ti_0.2Mn_0.2Co_0.2Ni_0.2Ru_0.2)O₂ as a High-Rate Cathode for Sodium-Ion Batteries,” Journal of the American Chemical Society Au 1, no. 1 (2021): 98-107.

[127] Z. Lun, B. Ouyang, D. H. Kwon, et al., “Cation-disordered Rocksalt-Type High-Entropy Cathodes for Li-ion Batteries,” Nature Materials 20, no. 2 (2021): 214-221.

[128] B. Xie, P. Zuo, L. Wang, et al., “Achieving Long-Life Prussian Blue Analogue Cathode for Na-ion Batteries via Triple-cation Lattice Substitution and Coordinated Water Capture,” Nano Energy 61 (2019): 201-210.

[129] Y. Luo, J. Shen, Y. Yao, et al., “Inhibiting the Jahn-Teller Effect of Manganese Hexacyanoferrate via Ni and Cu Codoping for Advanced Sodium-Ion Batteries,” Advanced Materials 36, no. 32 (2024): 2405458.

[130] Y. Yang, J. Zhou, L. Wang, et al., “Prussian Blue and Its Analogues as Cathode Materials for Na-, K-, Mg-, Ca-, Zn- and Al-ion Batteries,” Nano Energy 99 (2022): 107424.

[131] J. Wang, C. Mi, P. Nie, S. Dong, S. Tang, and X. Zhang, “Sodium-Rich Iron Hexacyanoferrate With Nickel Doping as a High Performance Cathode for Aqueous Sodium Ion Batteries,” Journal of Electroanalytical Chemistry 818 (2018): 10-18.

[132] W. Li, C. Han, W. Wang, et al., “Stress Distortion Restraint to Boost the Sodium Ion Storage Performance of a Novel Binary Hexacyanoferrate,” Advanced Energy Materials 10, no. 4 (2020): 1903006.

[133] Z. Xu, Y. Sun, J. Xie, et al., “High-Performance Ni/Fe-Codoped Manganese Hexacyanoferrate by Scale-up Synthesis for Practical Na-ion Batteries,” Materials Today Sustainability 18 (2022): 100113.

[134] M. Wang, R. Ling, C. Yang, and W. Qi, “Structural Regulation of Mn-Based Prussian Blue Induced by Zinc-Substitution for Enhanced Sodium Storage Performance,” Electrochimica Acta 462 (2023): 142711.

[135] J. Wang, Z. Wang, H. Liu, et al., “Synthesis of Fe-Doped Mn-Based Prussian Blue Hierarchical Architecture for High-Performance Sodium Ion Batteries,” Electrochimica Acta 448 (2023): 142183.

[136] J. Peng, J. Wang, H. Yi, et al., “A Dual-Insertion Type Sodium-Ion Full Cell Based on High-Quality Ternary-Metal Prussian Blue Analogs,” Advanced Energy Materials 8, no. 11 (2018): 1702856.

[137] D. Yang, J. Xu, X. Z. Liao, Y. S. He, H. Liu, and Z. F. Ma, “Structure Optimization of Prussian Blue Analogue Cathode Materials for Advanced Sodium Ion Batteries,” Chemical Communications 50, no. 87 (2014): 13377-13380.

[138] M. Xie, M. Xu, Y. Huang, et al., “Na₂Ni_xCo_1−xFe(CN)₆: A Class of Prussian Blue Analogs With Transition Metal Elements as Cathode Materials for Sodium Ion Batteries,” Electrochemistry Communications 59 (2015): 91-94.

[139] Z. Wang, Y. Huang, R. Luo, et al., “Ion-exchange Synthesis of High-Energy-Density Prussian Blue Analogues for Sodium Ion Battery Cathodes With Fast Kinetics and Long Durability,” Journal of Power Sources 436 (2019): 226868.

[140] S. Yu, Y. Li, Y. Lu, et al., “A Promising Cathode Material of Sodium Iron-Nickel Hexacyanoferrate for Sodium Ion Batteries,” Journal of Power Sources 275 (2015): 45-49.

[141] T. Yimtrakarn, Y. A. Lo, J. Kongcharoenkitkul, J. C. Lee, and W. Kaveevivitchai, “High Capacity and Fast Kinetics Enabled by Metal-Doping in Prussian Blue Analogue Cathodes for Sodium-Ion Batteries,” Chemistry: An Asian Journal 19, no. 13 (2024): e202301145.

[142] Y. Chen, Y. Kang, H. Yang, et al., “Contribution of Different Metal Nodes on Stepwise Electrocatalysis in Lithium-Sulfur Batteries,” Energy Storage Materials 54 (2023): 488-497.

[143] M. Du, X. Wang, P. Geng, et al., “Polypyrrole-Enveloped Prussian Blue Nanocubes With Multi-Metal Synergistic Adsorption Toward Lithium Polysulfides: High-Performance Lithium-Sulfur Batteries,” Chemical Engineering Journal 420 (2021): 130518.

[144] H. Li, W. Zhang, K. Sun, et al., “Manganese-Based Materials for Rechargeable Batteries Beyond Lithium-Ion,” Advanced Energy Materials 11, no. 25 (2021): 2100867.

[145] W. Bao, H. Shen, Y. Zhang, et al., “Rejuvenating Manganese-Based Rechargeable Batteries: Fundamentals, Status and Promise,” Journal of Materials Chemistry A 12, no. 15 (2024): 8617-8639.

[146] M. Chen, Q. Liu, S. Wang, E. Wang, X. Guo, and S. Chou, “High-Abundance and Low-Cost Metal-Based Cathode Materials for Sodium-Ion Batteries: Problems, Progress, and Key Technologies,” Advanced Energy Materials 9, no. 14 (2019): 1803609.

[147] Y. Xu, S. Zheng, H. Tang, X. Guo, H. Xue, and H. Pang, “Prussian Blue and Its Derivatives as Electrode Materials for Electrochemical Energy Storage,” Energy Storage Materials 9 (2017): 11-30.

[148] S. Feng, J. Wang, N. Gao, J. Wen, X. Li, and J. Xiao, “Heterogeneous Interface of Ni-Mn Composite Prussian Blue Analog-Coated Structure Modulates the Adsorption and Conversion of Polysulfides in Lithium-Sulfur Batteries,” Electrochimica Acta 433 (2022): 141218.

[149] R. Chen, Y. Huang, M. Xie, et al., “Chemical Inhibition Method to Synthesize Highly Crystalline Prussian Blue Analogs for Sodium-Ion Battery Cathodes,” ACS Applied Materials & Interfaces 8, no. 46 (2016): 31669-31676.

[150] Y. Zeng, X. F. Lu, S. L. Zhang, D. Luan, S. Li, and X. W. (D.) Lou, “Construction of Co-Mn Prussian Blue Analog Hollow Spheres for Efficient Aqueous Zn-ion Batteries,” Angewandte Chemie International Edition 60, no. 41 (2021): 22189-22194.

[151] L. Du, S. Bi, M. Yang, Z. Tie, M. Zhang, and Z. Niu, “Coupling Dual Metal Active Sites and Low-Solvation Architecture Toward High-Performance Aqueous Ammonium-ion Batteries,” Pnas 119, no. 50 (2022): e2214545119.

[152] G. Du and H. Pang, “Recent Advancements in Prussian Blue Analogues: Preparation and Application in Batteries,” Energy Storage Materials 36 (2021): 387-408.

[153] J. Zhang, J. Wan, M. Ou, et al., “Enhanced all-Climate Sodium-ion Batteries Performance in a Low-Defect and Na-Enriched Prussian Blue Analogue Cathode by Nickel Substitution,” Energy Mater 3 (2023): 300008.

[154] Z. Su, J. Liu, M. Li, et al., “Defect Engineering in Titanium-Based Oxides for Electrochemical Energy Storage Devices,” Electrochemical Energy Reviews 3, no. 2 (2020): 286-343.

[155] W. Wang, Y. Gang, J. Peng, et al., “Effect of Eliminating Water in Prussian Blue Cathode for Sodium-Ion Batteries,” Advanced Functional Materials 32, no. 25 (2022): 2111727.

[156] A. Zhou, Z. Xu, H. Gao, L. Xue, J. Li, and J. B. Goodenough, “Size-, Water-, and Defect-Regulated Potassium Manganese Hexacyanoferrate With Superior Cycling Stability and Rate Capability for Low-Cost Sodium-Ion Batteries,” Small 15, no. 42 (2019): 1902420.

[157] L. Deng, J. Qu, X. Niu, et al., “Defect-Free Potassium Manganese Hexacyanoferrate Cathode Material for High-Performance Potassium-ion Batteries,” Nature Communications 12, no. 1 (2021): 2167.

[158] M. Jiang, Z. Hou, J. Wang, L. Ren, Y. Zhang, and J. G. Wang, “Balanced Coordination Enables Low-Defect Prussian Blue for Superfast and Ultrastable Sodium Energy Storage,” Nano Energy 102 (2022): 107708.

[159] X. Guo, Z. Wang, Z. Deng, et al., “Water Contributes to Higher Energy Density and Cycling Stability of Prussian Blue Analogue Cathodes for Aqueous Sodium-Ion Batteries,” Chemistry of Materials 31, no. 15 (2019): 5933-5942.

[160] J. Song, L. Wang, Y. Lu, et al., “Removal of Interstitial H₂O in Hexacyanometallates for a Superior Cathode of a Sodium-Ion Battery,” Journal of the American Chemical Society 137, no. 7 (2015): 2658-2664.

[161] J. Hu, H. Tao, M. Chen, et al., “Interstitial Water Improves Structural Stability of Iron Hexacyanoferrate for High-Performance Sodium-Ion Batteries,” ACS Applied Materials & Interfaces 14, no. 10 (2022): 12234-12242.

[162] X. Li and X. Sun, “Interface Design and Development of Coating Materials in Lithium-Sulfur Batteries,” Advanced Functional Materials 28, no. 30 (2018): 1801323.

[163] Q. Zhang, L. Fu, J. Luan, et al., “Surface Engineering Induced Core-Shell Prussian Blue@Polyaniline Nanocubes as a High-Rate and Long-Life Sodium-ion Battery Cathode,” Journal of Power Sources 395 (2018): 305-313.

[164] Y. Jiang, S. Yu, B. Wang, et al., “Prussian Blue@C Composite as an Ultrahigh-Rate and Long-Life Sodium-Ion Battery Cathode,” Advanced Functional Materials 26, no. 29 (2016): 5315-5321.

[165] H. Gao, B. Guo, J. Song, K. Park, and J. B. Goodenough, “A Composite Gel-Polymer/Glass-Fiber Electrolyte for Sodium-Ion Batteries,” Advanced Energy Materials 5, no. 9 (2015): 1402235.

[166] D. Su, M. Cortie, H. Fan, and G. Wang, “Prussian Blue Nanocubes With an Open Framework Structure Coated With PEDOT as High-Capacity Cathodes for Lithium-Sulfur Batteries,” Advanced Materials 29, no. 48 (2017): 1700587.

[167] Y. Liu, D. He, Y. Cheng, et al., “A Heterostructure Coupling of Bioinspired, Adhesive Polydopamine, and Porous Prussian Blue Nanocubics as Cathode for High-Performance Sodium-Ion Battery,” Small 16, no. 11 (2020): 1906946.

[168] H. B. Wu and X. W. (D.) Lou, “Metal-Organic Frameworks and Their Derived Materials for Electrochemical Energy Storage and Conversion: Promises and Challenges,” Science Advances 3, no. 12 (2017): eaap9252.

[169] Y. You, H. Yao, S. Xin, et al., “Subzero-Temperature Cathode for a Sodium-Ion Battery,” Advanced Materials 28, no. 33 (2016): 7243-7248.

[170] Y. Mao, Y. Chen, J. Qin, C. Shi, E. Liu, and N. Zhao, “Capacitance Controlled, Hierarchical Porous 3D Ultra-Thin Carbon Networks Reinforced Prussian Blue for High Performance Na-ion Battery Cathode,” Nano Energy 58 (2019): 192-201.

[171] J. Ge, L. Fan, A. M. Rao, J. Zhou, and B. Lu, “Surface-substituted Prussian Blue Analogue Cathode for Sustainable Potassium-ion Batteries,” Nature Sustainability 5, no. 3 (2021): 225-234.

[172] E. Trevisanello, R. Ruess, G. Conforto, F. H. Richter, and J. Janek, “Polycrystalline and Single Crystalline NCM Cathode Materials—Quantifying Particle Cracking, Active Surface Area, and Lithium Diffusion,” Advanced Energy Materials 11, no. 18 (2021): 2003400.

[173] S. Lou, Q. Liu, F. Zhang, et al., “Insights Into Interfacial Effect and Local Lithium-ion Transport in Polycrystalline Cathodes of Solid-State Batteries,” Nature Communications 11, no. 1 (2020): 5700.

[174] X. Liang, J. Hwang, and Y. Sun, “Practical Cathodes for Sodium-Ion Batteries: Who Will Take the Crown?” Advanced Energy Materials 13, no. 37 (2023): 2301975.

[175] Q. Liu, Z. Hu, M. Chen, et al., “The Cathode Choice for Commercialization of Sodium-Ion Batteries: Layered Transition Metal Oxides versus Prussian Blue Analogs,” Advanced Functional Materials 30, no. 14 (2020): 1909530.

[176] Y. Li, Y. Lu, L. Chen, and Y. S. Hu, “Failure Analysis With a Focus on Thermal Aspect towards Developing Safer Na-Ion Batteries*,” Chinese Physics B 29, no. 4 (2020): 048201.

[177] Y. Li, Y. Lu, C. Zhao, et al., “Recent Advances of Electrode Materials for Low-Cost Sodium-ion Batteries towards Practical Application for Grid Energy Storage,” Energy Storage Materials 7 (2017): 130-151.

[178] J. B. Robinson, D. P. Finegan, T. M. M. Heenan, et al., “Microstructural Analysis of the Effects of Thermal Runaway on Li-Ion and Na-Ion Battery Electrodes,” Journal of Electrochemical Energy Conversion and Storage 15, no. 1 (2018): 011010.

[179] Y. Ma, Z. Zhou, T. Brezesinski, Y. Ma, and Y. Wu, “Stabilizing Layered Cathodes by High-Entropy Doping,” Research 7 (2024): 0503.

[180] R. Zhang, C. Wang, P. Zou, et al., “Long-Life Lithium-ion Batteries Realized by Low-Ni, Co-Free Cathode Chemistry,” Nature Energy 8, no. 7 (2023): 695-702.

[181] R. Zhang, C. Wang, P. Zou, et al., “Compositionally Complex Doping for Zero-Strain Zero-Cobalt Layered Cathodes,” Nature 610, no. 7930 (2022): 67-73.

[182] Y. Ma, Y. Ma, H. Euchner, et al., “An Alternative Charge-Storage Mechanism for High-Performance Sodium-Ion and Potassium-Ion Anodes,” ACS Energy Letters 6, no. 3 (2021): 915-924.

[183] Y. Ma, Y. Ma, G. Giuli, H. Euchner, A. Groß, and G. O. Lepore, “Introducing Highly Redox-Active Atomic Centers Into Insertion-Type Electrodes for Lithium-Ion Batteries,” Advanced Energy Materials 10, no. 25 (2020): 2000783.

[184] Z. Zhou, Y. Ma, T. Brezesinski, B. Breitung, Y. Wu, and Y. Ma, “Improving Upon Rechargeable Battery Technologies: On the Role of High-Entropy Effects,” Energy & Environmental Science (2024).

RIGHTS & PERMISSIONS

2025 The Author(s). SusMat published by John Wiley & Sons Ltd. on behalf of Sichuan University.