广西大学石化资源加工及过程强化技术重点实验室,机械工程学院,广西 南宁 530004
贾亚坤(2002—),男,硕士研究生,研究方向为多孔碳超级电容器,E-mail:jiayakun2025@163.com;
莫唐明,副教授,研究方向为电化学储能器件,E-mail:motangming@gxu.edu.cn。
收稿:2026-03-16,
修回:2026-04-11,
纸质出版:2026-05-28
移动端阅览
贾亚坤, 韦峥宁, 覃琪, 等. 多孔碳超级电容器储能机理研究进展[J]. 储能科学与技术, 2026, 15(5): 1779-1796.
JIA Yakun, WEI Zhengning, QIN Qi, et al. Recent advances in understanding of energy storage mechanisms in porous carbon-based supercapacitors[J]. Energy Storage Science and Technology, 2026, 15(5): 1779-1796.
贾亚坤, 韦峥宁, 覃琪, 等. 多孔碳超级电容器储能机理研究进展[J]. 储能科学与技术, 2026, 15(5): 1779-1796. DOI: 10.19799/j.cnki.2095-4239.2026.0217.
JIA Yakun, WEI Zhengning, QIN Qi, et al. Recent advances in understanding of energy storage mechanisms in porous carbon-based supercapacitors[J]. Energy Storage Science and Technology, 2026, 15(5): 1779-1796. DOI: 10.19799/j.cnki.2095-4239.2026.0217.
双电层超级电容器因充放电速度快、功率密度高和循环寿命长等优势,在电力电子、交通运输及国防军事等领域展现出广阔的应用前景。多孔碳材料凭借高比表面积、高电导率及低成本等特点,成为当前最具商业价值的电极材料。多孔碳超级电容器通过在电压作用下吸附离子进入多孔电极内形成固液界面双电层,实现储能。因此,深入阐明多孔碳纳米限域空间中拓扑结构对离子传输与电荷储存机理的影响机制,对于多孔碳电极的理性设计具有重要意义。基于此,综述了多孔碳储能机理研究的最新进展,重点探讨了分子动力学等理论模拟方法在电荷存储及离子传输机理研究中的重要作用,特别强调了亚纳米孔电容反常增加、微孔碳充电速度随孔径振荡变化、介孔碳分工协作机制及分级多孔碳预存储-协同传输机理等最新进展。最后,指出未来研究应向实验约束电极模型构建、多尺度模拟方法发展、赝电容机理解析及数据驱动结构设计等方向推进。本文旨在深化对于多孔碳超级电容器储能机理的理解,为高性能超级电容器的研发提供理论基础。
Electric double-layer capacitors (EDLCs) have demonstrated broad application prospects in power electronics
transportation
and defense due to their fast charge-discharge rates
high power density
and long cycle life. Porous carbon materials
with their high specific surface area
excellent electrical conductivity
and low cost
have become the most commercially valuable electrode materials to date. In porous carbon supercapacitors
energy storage is achieved through the formation of an electric double layer at the solid-liquid interface as ions are adsorbed into the porous electrode under an applied voltage. Therefore
a thorough understanding of how the topology of confined nanoscale pores in porous carbon influences ion transport and charge storage mechanisms is crucial for the rational design of porous carbon electrodes. Based on this
this review summarizes the latest progress in energy storage mechanisms of porous carbons
emphasizing the critical role of theoretical simulation methods
such as molecular dynamics
in investigating charge storage and ion transport mechanisms. Special attention is given to recent advances including anomalous capacitance enhancement in subnanometer pores
oscillatory variation of charging rates in microporous carbons with pore size
cooperative mechanisms in mesoporous carbons
and pre-storage-synergistic transport mechanisms in hierarchical porous carbons. Finally
it is suggested that future research should advance toward experimentally constrained electrode model construction
the development of multiscale simulation methods
elucidation of pseudocapacitive mechanisms
and data-driven structural design. This review aims to deepen the understanding of energy storage mechanisms in porous carbon supercapacitors and provide a theoretical basis for the development of high-performance supercapacitors.
孙海鑫, 祁建磊, 于鲲鹏, 等. 超级电容器电解质用离子液体研究进展[J]. 化工新型材料, 2024, 52(9): 13-17.
SUN H X, QI J L, YU K P, et al. Research progress of ionic liquids for supercapacitor electrolytes[J]. New Chemical Materials, 2024, 52(9): 13-17.
ATTIA P M, MOCH E, HERRING P K. Challenges and opportunities for high-quality battery production at scale[J]. Nature Communications, 2025, 16: 611. DOI: 10.1038/s41467-025-55861-7.
ZHUANG L, CAI W B, JI H X, et al. Development trends and priority research fields of electrochemical discipline in the 15th five year plan period[J]. Journal of Electrochemistry, 2025, 31(10): 2510081. DOI: 10.61558/2993-074x.3590.
GE K K, SHAO H, LIN Z F, et al. Advanced characterization of confined electrochemical interfaces in electrochemical capacitors[J]. Nature Nanotechnology, 2025, 20(2): 196-208. DOI: 10.1038/s41565-024-01821-z.
NI M, ZHOU L, LIU Y C, et al. Advances in the synthesis and applications of porous carbon materials[J]. Frontiers in Chemistry, 2023, 11: 1205280. DOI: 10.3389/fchem.2023.120 5280.
HAN Z Y, FAN X K, ZHANG L X, et al. Regular mesoporous nanosheets with mesoscopic high surface pore curvature and accelerated ion-transport channels[J]. Matter, 2025, 8(7): DOI: 10.1016/j.matt.2025.102164.
WU L, LI Y, FU Z Y, et al. Hierarchically structured porous materials: Synthesis strategies and applications in energy storage[J]. National Science Review, 2020, 7(11): 1667-1701. DOI: 10. 1093/nsr/nwaa183.
LIU Y, CHEN H, LI L. Applications and challenges of porous carbon with different dimensions in supercapacitors—A mini review[J]. Frontiers in Energy Research, 2022, 10: DOI:10.3389/fenrg.2022.951701
KITTO D, KAMCEV J. Predicting the conductivity-selectivity trade-off and upper bound in ion-exchange membranes[J]. ACS Energy Letters, 2024, 9(4): 1346-1352.
HABER S, LESKES M. What can we learn from solid state NMR on the electrode–electrolyte interface?[J]. Advanced Materials, 2018, 30(41): DOI:10.1002/adma.201706496.
CHAI Y G, HU Z Q, JIA W S, et al. Ion transport in porous carbon electrode for supercapacitors probed by electrochemical quartz crystal microbalance[J]. Electrochimica Acta, 2020, 356: 136780. DOI: 10.1016/j.electacta.2020.136780.
LIU X Z, ZHAO P C, LIU F F, et al. Attenuated total reflection infrared spectroscopy for studying electrochemical cycling of hydrogen, carbon, and nitrogen-containing molecules[J]. Journal of Energy Chemistry, 2024, 99: 495-511. DOI: 10.1016/j.jechem. 2024.08.008.
ISLAM M T, FITZEK H, GOLLAS B, et al. A novel approach to describe the electric double layer structure of water-in-salt electrolytes in porous carbon electrodes[J]. Journal of Materials Chemistry A, 2025, 13(16): 11767-11781.
PREHAL C, WEINGARTH D, PERRE E, et al. Tracking the structural arrangement of ions in carbon supercapacitor nanopores using in situ small-angle X-ray scattering[J ] . Energy & Environmental Science, 2015, 8(6): 1725-1735.
LIN X B, TEE S R, SEARLES D J, et al. Molecular insights on optimizing nanoporous carbon-based supercapacitors with various electrolytes[J]. Electrochimica Acta, 2024, 474: 143500. DOI: 10.1016/j.electacta.2023.143500.
CHMIOLA J, YUSHIN G, GOGOTSI Y, et al. Anomalous increase in carbon capacitance at pore sizes less than 1 nanometer[J]. Science, 2006, 313(5794): 1760-1763. DOI: 10.1126/science.11 32195.
RAYMUNDO-PIÑERO E, KIERZEK K, MACHNIKOWSKI J, et al. Relationship between the nanoporous texture of activated carbons and their capacitance properties in different electrolytes[J]. Carbon, 2006, 44(12): 2498-2507. DOI: 10.1016/j.carbon. 2006.05.022.
YANG L, FISHBINE B H, MIGLIORI A, et al. Molecular simulation of electric double-layer capacitors based on carbon nanotube forests[J]. Journal of the American Chemical Society, 2009, 131(34): 12373-12376.
SHIM Y, KIM H J. Nanoporous carbon supercapacitors in an ionic liquid: A computer simulation study[J]. ACS Nano, 2010, 4(4): 2345-2355.
CHMIOLA J, LARGEOT C, TABERNA P L, et al. Desolvation of ions in subnanometer pores and its effect on capacitance and double-layer theory[J]. Angewandte Chemie International Edition, 2008, 47(18): 3392-3395. DOI: 10.1002/anie.200704894.
KONDRAT S, KORNYSHEV A. Superionic state in double-layer capacitors with nanoporous electrodes[J]. Journal of Physics: Condensed Matter, 2011, 23(2): 022201. DOI: 10.1088/0953-8984/23/2/022201.
KONDRAT S, GEORGI N, FEDOROV M V, et al. A superionic state in nano-porous double-layer capacitors: Insights from Monte Carlo simulations[J]. Physical Chemistry Chemical Physics, 2011, 13(23): 11359-11366.
FENG G, CUMMINGS P T. Supercapacitor capacitance exhibits oscillatory behavior as a function of nanopore size[J]. The Journal of Physical Chemistry Letters, 2011, 2(22): 2859-2864.
WU P, HUANG J S, MEUNIER V, et al. Complex capacitance scaling in ionic liquids-filled nanopores[J]. ACS Nano, 2011, 5(11): 9044-9051.
XING L D, VATAMANU J, BORODIN O, et al. On the atomistic nature of capacitance enhancement generated by ionic liquid electrolyte confined in subnanometer pores[J]. The Journal of Physical Chemistry Letters, 2013, 4(1): 132-140. DOI: 10.1021/jz301782f.
JIANG D E, JIN Z H, WU J Z. Oscillation of capacitance inside nanopores[J]. Nano Letters, 2011, 11(12): 5373-5377.
JIANG D E, JIN Z H, HENDERSON D, et al. Solvent effect on the pore-size dependence of an organic electrolyte supercapacitor[J]. The Journal of Physical Chemistry Letters, 2012, 3(13): 1727-1731.
LIAN C, JIANG D E, LIU H L, et al. A generic model for electric double layers in porous electrodes[J]. The Journal of Physical Chemistry C, 2016, 120(16): 8704-8710.
DESCHAMPS M, GILBERT E, AZAIS P, et al. Exploring electrolyte organization in supercapacitor electrodes with solid-state NMR[J]. Nature Materials, 2013, 12(4): 351-358. DOI: 10. 1038/nmat3567.
LIU X Y, LÜ D X, MERLET C, et al. Structural disorder determines capacitance in nanoporous carbons[J]. Science, 2024, 384(6693): 321-325. DOI: 10.1126/science.adn6242.
VATAMANU J, VATAMANU M, BEDROV D. Non-faradaic energy storage by room temperature ionic liquids in nanoporous electrodes[J]. ACS Nano, 2015, 9(6): 5999-6017.
MERLET C, PÉAN C, ROTENBERG B, et al. Highly confined ions store charge more efficiently in supercapacitors[J]. Nature Communications, 2013, 4: 2701. DOI: 10.1038/ncomms3701.
XING L D, VATAMANU J, SMITH G D, et al. Nanopatterning of electrode surfaces as a potential route to improve the energy density of electric double-layer capacitors: Insight from molecular simulations[J]. The Journal of Physical Chemistry Letters, 2012, 3(9): 1124-1129.
VATAMANU J, CAO L L, BORODIN O, et al. On the influence of surface topography on the electric double layer structure and differential capacitance of graphite/ionic liquid interfaces[J]. The Journal of Physical Chemistry Letters, 2011, 2(17): 2267-2272.
BEDROV D, VATAMANU J, HU Z Z. Ionic liquids at charged surfaces: Insight from molecular simulations[J]. Journal of Non-Crystalline Solids, 2015, 407: 339-348. DOI: 10.1016/j.jnoncrysol. 2014.08.007.
MERLET C, ROTENBERG B, MADDEN P A, et al. On the molecular origin of supercapacitance in nanoporous carbon electrodes[J]. Nature Materials, 2012, 11(4): 306-310. DOI: 10. 1038/nmat3260.
PENG J X, WU T Z, ZENG L, et al. Realistic atomic model for charge storage and charging dynamics of amorphous porous carbons[J]. Nature Communications, 2026, 17: 2425. DOI: 10. 1038/s41467-026-69231-4.
KILIC M S, BAZANT M Z, AJDARI A. Steric effects in the dynamics of electrolytes at large applied voltages. II. Modified Poisson-Nernst-Planck equations[J]. Physical Review E, 2007, 75(2): 021503. DOI: 10.1103/physreve.75.021503.
JIANG J, CAO D P, JIANG D E, et al. Time-dependent density functional theory for ion diffusion in electrochemical systems[J]. Journal of Physics: Condensed Matter, 2014, 26(28): 284102. DOI: 10.1088/0953-8984/26/28/284102.
TIVONY R, SAFRAN S, PINCUS P, et al. Charging dynamics of an individual nanopore[J]. Nature Communications, 2018, 9: 4203. DOI: 10.1038/s41467-018-06364-1.
BAZANT M Z, THORNTON K, AJDARI A. Diffuse-charge dynamics in electrochemical systems[J]. Physical Review E, Statistical, Nonlinear, and Soft Matter Physics, 2004, 70(2 Pt 1): 021506. DOI: 10.1103/PhysRevE.70.021506.
BI S, KNIJFF L, LIAN X L, et al. Modeling of nanomaterials for supercapacitors: Beyond carbon electrodes[J]. ACS Nano, 2024, 18(31): 19931-19949.
SALANNE M, BURIAK J M, CHEN X D, et al. Best practices for simulations and calculations of nanomaterials for energy applications: Avoiding "garbage In, garbage out"[J]. ACS Nano, 2023, 17(7): 6147-6149. DOI: 10.1021/acsnano.3c02368.
ZHU B Z, ZHOU J G, JIA Y K, et al. Super-slow charging dynamics of water-in-salt electrolytes in subnanopore[J]. Energy Materials, 2026, 6(1): 600001. DOI: 10.20517/energymater.2025.151.
CHABAN V V, PREZHDO O V. Nanoscale carbon greatly enhances mobility of a highly viscous ionic liquid[J]. ACS Nano, 2014, 8(8): 8190-8197. DOI: 10.1021/nn502475j.
KONDRAT S, WU P, QIAO R, et al. Accelerating charging dynamics in subnanometre pores[J]. Nature Materials, 2014, 13(4): 387-393. DOI: 10.1038/nmat3916.
HE Y D, QIAO R, VATAMANU J, et al. Importance of ion packing on the dynamics of ionic liquids during micropore charging[J]. The Journal of Physical Chemistry Letters, 2016, 7(1): 36-42.
PEAN C, DAFFOS B, ROTENBERG B, et al. Confinement, desolvation, and electrosorption effects on the diffusion of ions in nanoporous carbon electrodes[J]. Journal of the American Chemical Society, 2015, 137(39): 12627-12632.
BREITSPRECHER K, HOLM C, KONDRAT S. Charge me slowly, I Am in a hurry: Optimizing charge-discharge cycles in nanoporous supercapacitors[J]. ACS Nano, 2018, 12(10): 9733-9741.
LEE A A, KONDRAT S, OSHANIN G, et al. Charging dynamics of supercapacitors with narrow cylindrical nanopores[J]. Nanotechnology, 2014, 25(31): 315401. DOI: 10.1088/0957-4484/25/31/315401.
BREITSPRECHER K, JANSSEN M, SRIMUK P, et al. How to speed up ion transport in nanopores[J]. Nature Communications, 2020, 11: 6085. DOI: 10.1038/s41467-020-19903-6.
MO T M, PENG J X, DAI W L, et al. Horn-like pore entrance boosts charging dynamics and charge storage of nanoporous supercapacitors[J]. ACS Nano, 2023, 17(15): 14974-14980.
BI S, LI Z H, XIAO D W, et al. Pore-size-dependent capacitance and charging dynamics of nanoporous carbons in aqueous electrolytes[J]. The Journal of Physical Chemistry C, 2022, 126(15): 6854-6862.
LIU Y F, MERLET C, SMIT B. Carbons with regular pore geometry yield fundamental insights into supercapacitor charge storage[J]. ACS Central Science, 2019, 5(11): 1813-1823.
PÉAN C, MERLET C, ROTENBERG B, et al. On the dynamics of charging in nanoporous carbon-based supercapacitors[J]. ACS Nano, 2014, 8(2): 1576-1583.
MO T M, BI S, ZHANG Y, et al. Ion structure transition enhances charging dynamics in subnanometer pores[J]. ACS Nano, 2020, 14(2): 2395-2403.
MO T M, ZHOU J G, HE H Y, et al. Oscillation charging dynamics in nanopore supercapacitors with organic electrolyte[J]. ACS Applied Materials & Interfaces, 2023, 15(44): 51274-51280.
KRESS T, LIU X Y, FORSE A C. Pore network tortuosity controls fast charging in supercapacitors[J]. Nature Materials, 2026, 25(3): 440-446. DOI: 10.1038/s41563-025-02404-6.
BI S, BANDA H, CHEN M, et al. Molecular understanding of charge storage and charging dynamics in supercapacitors with MOF electrodes and ionic liquid electrolytes[J]. Nature Materials, 2020, 19(5): 552-558. DOI: 10.1038/s41563-019-0598-7.
MO T M, WANG Z X, ZENG L, et al. Energy storage mechanism in supercapacitors with porous graphdiynes: Effects of pore topology and electrode metallicity[J]. Advanced Materials, 2023, 35(33): 2301118. DOI: 10.1002/adma.202301118.
SYUGAEV A V, YAZOVSKIKH K A, MARATKANOVA A N. Electrochemical impedance of nitrogen-doped carbon with tunable mesoporous structure[J]. Electrochimica Acta, 2025, 535: 146570. DOI: 10.1016/j.electacta.2025.146570.
GOGOTSI Y, NIKITIN A, YE H H, et al. Nanoporous carbide-derived carbon with tunable pore size[J]. Nature Materials, 2003, 2(9): 591-594. DOI: 10.1038/nmat957.
PENG Z G, HE Y Y, LI N, et al. Snowflake pores enhance energy storage in hcb-COF supercapacitors: Molecular dynamics insights into shape-dependent charging[J]. Journal of Molecular Liquids, 2025, 430: 127764. DOI: 10.1016/j.molliq.2025.127764.
PENG Z G, LI N, HE Y Y, et al. Investigation of knot-linker effects on charge storage in triangular COF supercapacitors: A molecular dynamics investigation[J]. Journal of Energy Storage, 2025, 131: 117484. DOI: 10.1016/j.est.2025.117484.
WAYSENSON Z, FRANCE-LANORD A, SERVA A, et al. Electrode flexibility enhances electrolyte dynamics during supercapacitor charging[J]. ACS Nano, 2025, 19(32): 29462-29469.
DVOYASHKIN M, LEISTENSCHNEIDER D, EVANS J D, et al. Revealing the impact of hierarchical pore organization in supercapacitor electrodes by coupling ionic dynamics at micro- and macroscales[J]. Advanced Energy Materials, 2021, 11(24): 2100700. DOI: 10.1002/aenm.202100700.
LI W, LIU J, ZHAO D Y. Mesoporous materials for energy conversion and storage devices[J]. Nature Reviews Materials, 2016, 1: 16023. DOI: 10.1038/natrevmats.2016.23.
TAO S S, JIANG D L. Accelerating anhydrous proton transport in covalent organic frameworks: Pore chemistry and its impacts[J]. Angewandte Chemie International Edition, 2024, 63(33): e202408296. DOI: 10.1002/anie.202408296.
FORSE A C, GRIFFIN J M, MERLET C, et al. Direct observation of ion dynamics in supercapacitor electrodes using in situ diffusion NMR spectroscopy[J ] . Nature Energy, 2017, 2: 16216. DOI: 10.1038/nenergy.2016.216.
LIANG C L, FU J L, TANG S D, et al. Unlocking fast charging of supercapacitors: A job-sharing mechanism for ion transport and storage[J]. Energy Storage Materials, 2025, 83: 104685. DOI: 10.1016/j.ensm.2025.104685.
LIU T Y, ZHANG F, SONG Y, et al. Revitalizing carbon supercapacitor electrodes with hierarchical porous structures[J]. Journal of Materials Chemistry A, 2017, 5(34): 17705-17733.
BU Y F, SUN T, CAI Y J, et al. Compressing carbon nanocages by capillarity for optimizing porous structures toward ultrahigh-volumetric-performance supercapacitors[J]. Advanced Materials, 2017, 29(24): 1700470. DOI: 10.1002/adma.201700470.
BORCHARDT L, LEISTENSCHNEIDER D, HAASE J, et al. Revising the concept of pore hierarchy for ionic transport in carbon materials for supercapacitors[J]. Advanced Energy Materials, 2018, 8(24): 1800892. DOI: 10.1002/aenm.201800892.
DU J, MO T M, LI Y Y, et al. Prefilled and concerted ion transport mechanism in hierarchical porous carbons for ultra-fast energy storage[J]. ACS Nano, 2025, 19(24): 22217-22227.
YANG P Y, JU S P, HSIEH H S, et al. Electrolytic molecule in-pore structure and capacitance of supercapacitors with nanoporous carbon electrodes: A coarse-grained molecular dynamics study[J]. Computational Materials Science, 2019, 166: 293-302. DOI: 10.1016/j.commatsci.2019.05.010.
ABRAHAM M J, MURTOLA T, SCHULZ R, et al. GROMACS: High performance molecular simulations through multi-level parallelism from laptops to supercomputers[J]. SoftwareX, 2015, 1/2: 19-25. DOI: 10.1016/j.softx.2015.06.001.
QIAN S M, CHENG E, KAKARELIDIS O, et al. Multiscale modelling of supercapacitors with hierarchical structure[J]. Journal of Power Sources, 2026, 665: 238956. DOI: 10.1016/j.jpowsour.2025.238956.
WU Q S, MCDOWELL M T, QI Y. Effect of the electric double layer (EDL) in multicomponent electrolyte reduction and solid electrolyte interphase (SEI) formation in lithium batteries[J]. Journal of the American Chemical Society, 2023, 145(4): 2473-2484. DOI: 10.1021/jacs.2c11807.
LIN H, TRUHLAR D G. QM/MM: What have we learned, where are we, and where do we go from here?[J]. Theoretical Chemistry Accounts, 2007, 117(2): 185-199. DOI: 10.1007/s00214-006-0143-z.
DEEBANSOK S, DENG J, LE CALVEZ E, et al. Capacitive tendency concept alongside supervised machine-learning toward classifying electrochemical behavior of battery and pseudocapacitor materials[J]. Nature Communications, 2024, 15: 1133. DOI: 10.1038/s41467-024-45394-w.
JABLONKA K M, ONGARI D, MOOSAVI S M, et al. Big-data science in porous materials: Materials genomics and machine learning[J]. Chemical Reviews, 2020, 120(16): 8066-8129.
ZHU S, LI J J, MA L Y, et al. Artificial neural network enabled capacitance prediction for carbon-based supercapacitors[J]. Materials Letters, 2018, 233: 294-297. DOI: 10.1016/j.matlet. 2018.09.028.
ZHOU M S, VASSALLO A, WU J Z. Data-driven approach to understanding the in-operando performance of heteroatom-doped carbon electrodes[J ] . ACS Applied Energy Materials, 2020, 3(6): 5993-6000.
WANG Z X, WU T Z, ZENG L, et al. Machine learning relationships between nanoporous structures and electrochemical performance in MOF supercapacitors[J]. Advanced Materials, 2025, 37(15): 2500943. DOI: 10.1002/adma.202500943.
SAAD A G, EMAD-ELDEEN A, TAWFIK W Z, et al. Data-driven machine learning approach for predicting the capacitance of graphene-based supercapacitor electrodes[J]. Journal of Energy Storage, 2022, 55: 105411. DOI: 10.1016/j.est.2022.105411.
SU H P, LIN S, DENG S W, et al. Predicting the capacitance of carbon-based electric double layer capacitors by machine learning[J]. Nanoscale Advances, 2019, 1(6): 2162-2166.
0
浏览量
7
下载量
0
CSCD
关联资源
相关文章
相关作者
相关机构
京公网安备11010802024621