普鲁士蓝基材料循环稳定性的瓶颈问题及在超级电容器应用中的性能优化路径

魏媛杰; 梁静; 吴伟

doi:10.19799/j.cnki.2095-4239.2026.0026

您当前的位置：

首页 >

文章列表页 >

普鲁士蓝基材料循环稳定性的瓶颈问题及在超级电容器应用中的性能优化路径

超级电容器关键材料与器件专刊 | 更新时间：2026-05-28

- 普鲁士蓝基材料循环稳定性的瓶颈问题及在超级电容器应用中的性能优化路径
- Bottlenecks in the cyclic stability of Prussian blue-based materials and performance optimization pathways for supercapacitor applications
- 储能科学与技术 2026年15卷第5期页码：1848-1861
- 作者机构：
  
  武汉大学物理科学与技术学院，湖北武汉 430072
- 作者简介：
  
  魏媛杰（2001—），女，博士研究生，研究方向为柔性超级电容器电极材料，E-mail：1053112128@qq.com；
  吴伟，教授，主要从事柔性印刷电子器件研究，E-mail：weiwu@whu.edu.cn。
- 基金信息：
  
  国家自然科学基金(52373252)
- DOI：10.19799/j.cnki.2095-4239.2026.0026
  中图分类号： TB 383
- 收稿：2026-01-09，
  
  修回：2026-02-03，
  
  纸质出版：2026-05-28
- 稿件说明：
移动端阅览
魏媛杰, 梁静, 吴伟. 普鲁士蓝基材料循环稳定性的瓶颈问题及在超级电容器应用中的性能优化路径[J]. 储能科学与技术, 2026, 15(5): 1848-1861.

WEI Yuanjie, LIANG Jing, WU Wei. Bottlenecks in the cyclic stability of Prussian blue-based materials and performance optimization pathways for supercapacitor applications[J]. Energy Storage Science and Technology, 2026, 15(5): 1848-1861.
魏媛杰, 梁静, 吴伟. 普鲁士蓝基材料循环稳定性的瓶颈问题及在超级电容器应用中的性能优化路径[J]. 储能科学与技术, 2026, 15(5): 1848-1861. DOI： 10.19799/j.cnki.2095-4239.2026.0026.

WEI Yuanjie, LIANG Jing, WU Wei. Bottlenecks in the cyclic stability of Prussian blue-based materials and performance optimization pathways for supercapacitor applications[J]. Energy Storage Science and Technology, 2026, 15(5): 1848-1861. DOI： 10.19799/j.cnki.2095-4239.2026.0026.

摘要

超级电容器凭借其高功率密度和长循环寿命，在新能源与便携式储能等领域扮演着不可替代的角色。普鲁士蓝类似物因具备开放框架结构、丰富的氧化还原活性位点、较高的理论容量，以及成本低廉、易于制备等优势，被认为是一类极具应用前景的电极材料。然而，该类材料在实际应用过程中普遍表现出较差的循环稳定性，其理论性能与长期循环寿命之间仍存在明显差距。本文首先介绍了普鲁士蓝材料在超级电容器中的储能机制，并阐述了评估其循环稳定性优劣的主要依据。在此基础上，系统归纳了造成普鲁士蓝类似物电极材料循环性能衰减的关键因素，主要包括反复离子脱嵌引发的晶格畸变与相变、过渡金属离子在电化学反应过程中的溶解以及材料结晶水或晶格空位诱发的副反应与结构形变，进一步综述了提升其结构稳定性的主要策略，例如晶格调控、界面改性、电解液体系优化及反应条件调整等，并对相关机制及研究进展进行了阐释。最后，对人工智能预测与原位表征技术等未来研究方向作出展望，指出这些途径有望突破材料性能瓶颈，为开发高性能普鲁士蓝基储能器件提供有力支撑。

Abstract

Supercapacitors are energy storage devices that integrate high power density with extended cycle life

making them central to applications in new energy vehicles

portable electronics

and smart grids. Prussian blue analogues

with their distinctive open framework

adjustable redox-active sites

and high theoretical specific capacity

stand out as particularly promising electrode materials for these devices

as the three-dimensional ion channels in these compounds enable swift insertion and extraction of electrolyte ions

yielding exceptional rate performance. They are also cost-effective

owing to the abundance of raw materials and relatively simple synthesis routes. Despite these advantages

their widespread use is hampered by insufficient cycling stability

where a considerable gap exists between theoretical potential and long-term operational durability. This fundamental limitation arises mainly from lattice distortions and phase transitions triggered by repeated ion intercalation and deintercalation during charge-discharge cycles

dissolution and leaching of transition metal ions

as well as side reactions and structural deterioration caused by inherent interstitial water and lattice defects. This contribution methodically examines these three principal degradation mechanisms and surveys recent advances aimed at improving structural integrity through lattice engineering

interface modification

and electrolyte design. The paper concludes by identifying prospective research avenues

such as artificial intelligence-assisted prediction and the deployment of in-situ characterization methods

to inform the future development of high-performance energy storage systems based on Prussian blue materials.

关键词

Keywords

references

DING X, JIANG R, WU J L, et al. Ni 3 N-CeO 2 heterostructure bifunctional catalysts for electrochemical water splitting[J ] . Advanced Functional Materials, 2023, 33(47): 2306786. DOI:10.1002/adfm.202306786.

ZUO W H, LI R Z, ZHOU C, et al. Battery-supercapacitor hybrid devices: Recent progress and future prospects[J]. Advanced Science, 2017, 4(7): 1600539. DOI:10.1002/advs.201600539.

LUO L, ZHANG F H, WANG L L, et al. Recent advances in shape memory polymers: Multifunctional materials, multiscale structures, and applications[J]. Advanced Functional Materials, 2024, 34(14): 2312036. DOI:10.1002/adfm.202312036.

NAKKHONG T, INPRASIT T, PANGON A. Zeolite imidazole framework-67 (ZIF-67)/phosphorus-doped carbon nanofiber hybrid materials for binder-free supercapacitor electrodes[J]. Chemical Engineering Journal, 2024, 497: 154655. DOI:10.1016/j.cej.2024.154655.

YASA S, BIROL B, DONMEZ K B, et al. Recovery of cobalt based materials from spent Li-ion batteries and their use as electrode material for supercapacitor[J]. Journal of Energy Storage, 2024, 81: 110291. DOI:10.1016/j.est.2023.110291.

SALUNKHE R R, KANETI Y V, YAMAUCHI Y. Metal-organic framework-derived nanoporous metal oxides toward supercapacitor applications: Progress and prospects[J]. ACS Nano, 2017, 11(6): 5293-5308.

MA Y P, XIE X B, YANG W Y, et al. Recent advances in transition metal oxides with different dimensions as electrodes for high-performance supercapacitors[J]. Advanced Composites and Hybrid Materials, 2021, 4(4): 906-924. DOI:10.1007/s42114-021-00358-2.

CHEN L F, FENG Y, LIANG H W, et al. Macroscopic-scale three-dimensional carbon nanofiber architectures for electrochemical energy storage devices[J]. Advanced Energy Materials, 2017, 7(23): 1700826. DOI:10.1002/aenm.201700826.

HU S J, LI Y, CHEN Y H, et al. Insight of a phase compatible surface coating for long-durable Li-rich layered oxide cathode[J]. Advanced Energy Materials, 2019, 9(34): 1901795. DOI:10.1002/aenm.201901795.

ZHANG D D, CAO J, YANG C W, et al. Highly stable aqueous Zn-ion batteries achieved by suppressing the active component loss in vanadium-based cathode[J]. Advanced Energy Materials, 2025, 15(15): 2404026. DOI:10.1002/aenm.202404026.

WANG Y C, YANG C, YAO L B, et al. Dissolution inhibition strategy stabilizes manganese Prussian blue analogs for high-energy sodium-ion batteries[J]. Advanced Functional Materials, 2025, 35(28): 2423867. DOI:10.1002/adfm.202423867.

ZHU X Q, ZHENG R X, YANG M M, et al. High-entropy Prussian blue analogues enable synergistic electronic coupling and charge compensation for efficient Li-CO 2 batteries[J ] . Advanced Functional Materials, 2026, 36(3): e10533. DOI:10.1002/adfm. 202510533.

LIU S H, YU H X, ZHAO Y, et al. Inhibiting phase transitions of Prussian blue analogs with high-entropy strategy for ultralong-life sodium-ion battery cathodes[J]. Small, 2025, 21(31): 2504893. DOI:10.1002/smll.202504893.

ZHOU Z H, DONG Y T, MA Y, et al. Innovative high-entropy strategy extending traditional metal substitution for optimizing Prussian blue analogues in rechargeable batteries[J]. SusMat, 2025, 5(2): e265. DOI:10.1002/sus2.265.

CHEN Z Y, ZHANG Y, LI F H, et al. Decoding intercalation-chemistry discrepancies to couple alkali cations with Prussian blue analogue cathodes[J]. Nano Energy, 2025, 141: 111097. DOI:10.1016/j.nanoen.2025.111097.

TAN Y C, CHEN D, KOTSIUBYNSKYI V, et al. Prussian blue and its analogues nanomaterials: A focused view on physicochemical properties and precise synthesis[J]. Journal of Energy Chemistry, 2025, 107: 393-406. DOI:10.1016/j.jechem.2025.03.035.

WANG J Y, HU Z W, QI Y J, et al. Prussian blue analogues for aqueous zinc-ion batteries: Recent process and perspectives[J]. Journal of Materials Science & Technology, 2025, 221: 302-320. DOI:10.1016/j.jmst.2024.10.002.

CHENG L, LUO Y Y, WANG H, et al. Optimized synthesis and electrochemical behaviors of Prussian blue analogues cathodes for potassium-ion batteries[J]. Materials Reports: Energy, 2025, 5(2): 100331. DOI:10.1016/j.matre.2025.100331.

ZHANG G X, FENG W C, DU G Y, et al. Thermodynamically-driven phase engineering and reconstruction deduction of medium-entropy Prussian blue analogue nanocrystals[J]. Advanced Materials, 2025, 37(26): 2503814. DOI:10.1002/adma. 202503814.

ZHOU W, HUANG T Q, ZHAO Y, et al. Ternary-metal Prussian blue analog hollow spheres/MXene electrode based on self-assembly enabling highly stable capacitive deionization[J]. Chemical Engineering Journal, 2025, 508: 161124. DOI:10.1016/j.cej.2025.161124.

ZHOU J N, LI Y L, LIN X M, et al. Prussian blue analogue-templated nanocomposites for alkali-ion batteries: Progress and perspective[J]. Nano-Micro Letters, 2024, 17(1): 9. DOI:10.1007/s40820-024-01517-y.

LIANG K, CHEN Y L, WANG S X, et al. Peanut shell waste derived porous carbon for high-performance supercapacitors[J]. Journal of Energy Storage, 2023, 70: 107947. DOI:10.1016/j.est.2023.107947.

HUANG X, SUN H X, LI X Y, et al. Eliminating charge transfer at cathode-electrolyte interface for ultrafast kinetics in Na-ion batteries[J]. Journal of the American Chemical Society, 2024, 146(43): 29391-29401.

WANG X, ZHAO M R, DU W J, et al. Boosting ultralong lifespan of Fe-based Prussian blue analogs cathode via element doping and crystal water capture[J ] . Chemical Engineering Journal, 2025, 508: 160997. DOI:10.1016/j.cej.2025.160997.

HEO J Y, LEE J H. Structural evolution and redox chemistry of Prussian blue analogues in rechargeable batteries[J]. ACS Applied Energy Materials, 2025, 8(13): 8862-8886.

WANG H, XU E Z, YU S M, et al. Reduced graphene oxide-anchored manganese hexacyanoferrate with low interstitial H 2 O for superior sodium-ion batteries[J ] . ACS Applied Materials & Interfaces, 2018, 10(40): 34222-34229.

RAZA W, ALI F, RAZA N, et al. Recent advancements in supercapacitor technology[J]. Nano Energy, 2018, 52: 441-473. DOI:10.1016/j.nanoen.2018.08.013.

YU J R, BIAN Y F, WANG R F, et al. Coconut shell carbon preparation for rhodamine B adsorption and mechanism study[J]. Molecules, 2024, 29(17): DOI:10.3390/molecules29174262.

WANG P Y, HU T R, GUO Y, et al. CoS 2 confined into N-doped coal-based carbon fiber as flexible anode for high performance potassium-ion capacitor[J ] . Journal of Alloys and Compounds, 2024, 970: 172618. DOI:10.1016/j.jallcom.2023.172618.

CHEN M X, UMER K, LI B N, et al. Metalloporphyrin based MOF-545 coupled with solid solution Zn x Cd 1- x S for efficient photocatalytic hydrogen production[J ] . Journal of Colloid and Interface Science, 2024, 653: 380-389. DOI:10.1016/j.jcis. 2023.09.080.

GE L N, CUI Y P, SONG Y J, et al. Inhibiting Mn dissolution of Mn-based Prussian blue analogue through cross-linking network for sustainable sodium-ion battery[J]. Advanced Energy Materials, 2025, 15(32): 2500544. DOI:10.1002/aenm.202500544.

CHEN Z R, WANG Y, WANG J, et al. A MXene modification strategy of Prussian blue cathodes toward a stable cathode electrolyte interphase and suppressed Mn dissolution[J]. Chemical Engineering Journal, 2025, 505: 159519. DOI:10.1016/j.cej.2025.159519.

CHEN L, SUN W L, XU K, et al. How Prussian blue analogues can be stable in concentrated aqueous electrolytes[J]. ACS Energy Letters, 2022, 7(5): 1672-1678.

JIA D H, ZHENG F, NIU Y Y, et al. Preparation of V 2 O 5 nanobelt arrays/NiO nanosheet arrays composite as supercapacitor electrode material[J ] . Journal of Alloys and Compounds, 2023, 969: 172283. DOI:10.1016/j.jallcom.2023.172283.

WANG W L, GANG Y, HU Z, et al. Reversible structural evolution of sodium-rich rhombohedral Prussian blue for sodium-ion batteries[J]. Nature Communications, 2020, 11: 980. DOI:10. 1038/s41467-020-14444-4.

SIMONOV A, DE BAERDEMAEKER T, BOSTRÖM H L B, et al. Hidden diversity of vacancy networks in Prussian blue analogues[J]. Nature, 2020, 578(7794): 256-260. DOI:10.1038/s41586-020-1980-y.

TAN X, GAO C Y, LUO Z F, et al. Unveiling aqueous potassium-ion batteries with Prussian blue analogue cathodes[J]. Small, 2025, 21(9): 2410350. DOI:10.1002/smll.202410350.

WANG Q C, LI J B, JIN H B, et al. Prussian-blue materials: Revealing new opportunities for rechargeable batteries[J]. InfoMat, 2022, 4(6): e12311. DOI:10.1002/inf2.12311.

GUARI Y, CAHU M, FÉLIX G, et al. Nanoheterostructures based on nanosized Prussian blue and its Analogues: Design, properties and applications[J]. Coordination Chemistry Reviews, 2022, 461: 214497. DOI:10.1016/j.ccr.2022.214497.

WU X Y, WU C H, WEI C X, et al. Highly crystallized Na 2 CoFe(CN) 6 with suppressed lattice defects as superior cathode material for sodium-ion batteries[J ] . ACS Applied Materials & Interfaces, 2016, 8(8): 5393-5399.

WANG J, YUAN Z Y, LIAO J Y, et al. Cesium-doped manganese-based Prussian blue analogue as a high-efficiency cathode material for potassium-ion batteries[J]. Journal of Energy Chemistry, 2024, 99: 120-127. DOI:10.1016/j.jechem.2024.07.042.

SHU W L, HAN C H, WANG X P. Prussian blue analogues cathodes for nonaqueous potassium-ion batteries: Past, present, and future[J]. Advanced Functional Materials, 2024, 34(1): 2309636. DOI:10.1002/adfm.202309636.

XIE J P, MA L, LI J L, et al. Self-healing of Prussian blue analogues with electrochemically driven morphological rejuvenation[J]. Advanced Materials, 2022, 34(44): 2205625. DOI:10.1002/adma.202205625.

CHEN Y, DENG J, YANG B, et al. Promoting toluene oxidation by engineering octahedral units via oriented insertion of Cu ions in the tetrahedral sites of MnCo spinel oxide catalysts[J ] . Chemical Communications, 2020, 56(48): 6539-6542. DOI:10.1039/d0cc 01615b.

GE J M, FAN L, RAO A M, et al. Surface-substituted Prussian blue analogue cathode for sustainable potassium-ion batteries[J]. Nature Sustainability, 2022, 5(3): 225-234. DOI:10.1038/s41893-021-00810-7.

YI T F, SARI H M K, LI X Z, et al. A review of niobium oxides based nanocomposites for lithium-ion batteries, sodium-ion batteries and supercapacitors[J]. Nano Energy, 2021, 85: 105955. DOI:10.1016/j.nanoen.2021.105955.

ZHENG L, YI R W, ZHENG N, et al. Review—Lithium carbon composite material for practical lithium metal batteries[J]. Chinese Journal of Chemistry, 2023, 41(7): 814-824. DOI:10.1002/cjoc.202200612.

LI W J, HAN C, XIA Q B, et al. Remarkable enhancement in sodium-ion kinetics of NaFe 2 (CN) 6 by chemical bonding with graphene[J ] . Small Methods, 2018, 2(4): 1700346. DOI:10.1002/smtd.201700346.

ZHAO J, LI Z J, YUAN X C, et al. Novel core-shell multi-dimensional hybrid nanoarchitectures consisting of Co(OH) 2 nanoparticles/Ni 3 S 2 nanosheets grown on SiC nanowire networks for high-performance asymmetric supercapacitors[J ] . Chemical Engineering Journal, 2019, 357: 21-32. DOI:10.1016/j.cej.2018. 09.107.

CHEN M J, LI X Q, YAN Y J, et al. Polypyrrole-coated K 2 Mn [Fe(CN) 6 ] stabilizing its interfaces and inhibiting irreversible phase transition during the zinc storage process in aqueous batteries[J ] . ACS Applied Mat erials & Interfaces, 2022, 14(1): 1092-1101.

XU X, LAN Y L, ZHANG B B, et al. Construction of polyaniline coated FeMnCu Co-doped Prussian blue analogue as cathode for sodium ion battery[J]. Electrochimica Acta, 2023, 471: 143375. DOI:10.1016/j.electacta.2023.143375.

ZHAO T K, XIN Q, YANG G Q, et al. Utilizing carboxymethyl cellulose sodium/sodium lignosulfonate hydrogel to build efficient electrolyte/electrode interfaces for multifunctional high-performance supercapacitors[J]. International Journal of Biological Macromolecules, 2025, 314: 144273. DOI:10.1016/j.ijbiomac.2025.144273.

HU H J, ABDYRAHYMOVA M, JOSHI B, et al. Flexible freestanding carbon nanofiber mats decorated with Zn/Co oxide nanostructures derived from zeolitic imidazolate frameworks as supercapacitor electrodes[J]. Chemical Engineering Journal, 2025, 505: 159589. DOI:10.1016/j.cej.2025.159589.

SHI J H, YANG Z X, NIE J H, et al. Regioselective super-assembly of Prussian blue analogue[J]. Journal of Colloid and Interface Science, 2024, 667: 44-53. DOI:10.1016/j.jcis.2024.04.065.

WANG S Q, HUO W Y, FENG H C, et al. Enhancing oxygen evolution reaction performance in Prussian blue analogues: Triple-play of metal exsolution, hollow interiors, and anionic regulation[J]. Advanced Materials, 2023, 35(45): 2304494. DOI:10.1002/adma.202304494.

ZHANG W, ZHAO Y Y, MALGRAS V, et al. Synthesis of monocrystalline nanoframes of Prussian blue analogues by controlled preferential etching[J]. Angewandte Chemie International Edition, 2016, 55(29): 8228-8234. DOI:10.1002/anie.201600661.

LIU Q Y, XU W, ZHENG D Z, et al. Structural and surface engineering promotes Zn-ion energy storage capability of commercial carbon cloth[J]. The Journal of Chemical Physics, 2023, 159(22): 224703. DOI:10.1063/5.0179293.

ZHOU M, YAN S X, WANG Q, et al. Walnut septum-derived hierarchical porous carbon for ultra-high-performance supercapacitors[J]. Rare Metals, 2022, 41(7): 2280-2291. DOI:10.1007/s12598-021-01957-0.

RAWAT S, MISHRA R K, BHASKAR T. Biomass derived functional carbon materials for supercapacitor applications[J]. Chemosphere, 2022, 286: 131961. DOI:10.1016/j.chemosphere.2021.131961.

ZHANG X Y, JIANG C Z, LIANG J, et al. Electrode materials and device architecture strategies for flexible supercapacitors in wearable energy storage[J]. Journal of Materials Chemistry A, 2021, 9(13): 8099-8128.

LIU Y J, WANG W Q, CHEN Q D, et al. Resorcinol-formaldehyde resin-coated Prussian blue core-shell spheres and their derived unique yolk-shell FeS 2 @C spheres for lithium-ion batteries[J ] . Inorganic Chemist ry, 2019, 58(2): 1330-1338.

LIU Q, ZHANG J W, LI Y, et al. Discovered the enhanced mechanism of surface passivation for core-shell NiCoFeS@PBA cubes in electrochemical energy storage[J]. Chemical Engineering Journal, 2025, 509: 161571. DOI:10.1016/j.cej.2025.161571.

XIAO M J. Research progress of Prussian blue analogues for cathode of sodium ion batteries[J]. Journal of Alloys and Compounds, 2025, 1036: 182014. DOI:10.1016/j.jallcom.2025. 182014.

XIE B X, WANG Y H, TAN Y B, et al. Prussian blue analogues as cathode materials for nonaqueous sodium-ion batteries: Fundamentals, mechanisms, and performance[J]. Energy Storage Materials, 2026, 84: 104802. DOI:10.1016/j.ensm.2025. 104802.

SUN A Q, CHEN W, YANG J, et al. Layered double hydroxides/Prussian blue analogs toward improved capacitive performances[J]. Journal of Colloid and Interface Science, 2025, 699: 138287. DOI:10.1016/j.jcis.2025.138287.

ZHAO C, ZHENG C H, YAO Z Q, et al. Solvation-tuned ternary eutectic electrolyte for stable Prussian blue-based sodium-ion batteries[J]. Chemical Engineering Journal, 2026, 527: 171476. DOI:10.1016/j.cej.2025.171476.

LIU Y Y, BAI Y, FU C J, et al. Degradation mechanism and suppression strategy of high-capacity Prussian blue analogue cathode for aqueous sodium-ion batteries[J]. Electrochimica Acta, 2026, 548: 147997. DOI:10.1016/j.electacta.2025.147997.

HUANG Y F, MU W N, BI X L, et al. Progress in defect engineering of high-performance Prussian blue analogues as cathode materials for sodium-ion batteries[J]. Journal of Energy Storage, 2025, 111: 115435. DOI:10.1016/j.est.2025.115435.

KHRAMTSOV P, KROPANEVA M, KISELKOV D, et al. Synthesis of Prussian blue nanoparticles in water/alcohol mixtures[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2024, 686: 133446. DOI:10.1016/j.colsurfa.2024.133446.

JEON S, LI C H, TALHAM D R. Design and synthesis of concentration gradient Prussian blue analogues[J]. Crystal Growth & Design, 2021, 21(2): 916-925.

JING Z X, KONG L T, MAMOOR M, et al. Rational design of Prussian blue analogues for ultralong and wide-temperature-range sodium-ion batteries[J]. Journal of the American Chemical Society, 2025, 147(4): 3702-3713.

HU X Y, JIAN W S, HONG N Y, et al. Confined element distribution with structure-driven energy coupling for enhanced Prussian blue analogue cathode[J]. Angewandte Chemie International Edition, 2024, 63(40): e202410420. DOI:10.1002/anie.202410420.

LI X N, YUAN L Z, WANG J H, et al. A "copolymer-co-morphology" conception for shape-controlled synthesis of Prussian blue analogues and as-derived spinel oxides[J]. Nanoscale, 2016, 8(4): 2333-2342.

WANG J, LI L, ZUO S L, et al. Synchronous crystal growth and etching optimization of Prussian blue from a single iron-source as high-rate cathode for sodium-ion batteries[J]. Electrochimica Acta, 2020, 341: 136057. DOI:10.1016/j.electacta.2020.136057.

浏览量

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

基于氧化钨和普鲁士蓝的可变色超级电容器

聚吡咯基齿形叉指全固态超级电容器的设计及性能优化

褶皱状少层Ti3C2 MXene的制备及超级电容性能研究

超级电容器盐包水电解质的研究进展

碳基超级电容器有机双阳离子电解液研究进展