甲烷裂解碳的活化改性及其电化学性能研究

张帆; 牛国伟; 王虎林; 魏宇学; 孙松; 常强; 张成华

doi:10.12434/j.issn.2097-2547.20260036

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甲烷裂解碳的活化改性及其电化学性能研究

更新时间：2026-07-28

- 甲烷裂解碳的活化改性及其电化学性能研究
  增强出版
- Study on activation and modification of methane-pyrolyzed carbon and its electrochemical performances
- 低碳化学与化工 2026: 1-14.
- 作者机构：
  
  1.安徽大学化学化工学院，安徽合肥 230601
  2.中科合成油技术股份有限公司国家能源煤基液体燃料研发中心，北京101407
- 作者简介：
  
  张帆（1999—），硕士研究生，研究方向为电化学，E-mail：15735884839@163.com。
  常强（1989—），博士，高级工程师，研究方向为多相催化，E-mail：changqiang12@mails.ucas.ac.cn；
  张成华（1975—），博士，正高级工程师，研究方向为多相催化，E-mail：zhangchh@sxicc.ac.cn。
- 基金信息：
  
  国家重点研发计划(2022YFB4101204);国家自然科学基金(22179001;22102001;22302219);安徽省高校杰出青年科研项目(2022AH020007);安徽省高校协同创新项目(GXXT-2023-009)
- DOI：10.12434/j.issn.2097-2547.20260036
  中图分类号： TQ15;O643
- 收稿：2026-01-21，
  
  修回：2026-03-16，
  
  网络首发：2026-07-27，
- 稿件说明：
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张帆,牛国伟,王虎林等.甲烷裂解碳的活化改性及其电化学性能研究[J].低碳化学与化工,

ZHANG Fan,NIU Guowei,WANG Hulin,et al.Study on activation and modification of methane-pyrolyzed carbon and its electrochemical performances[J].Low-Carbon Chemistry and Chemical Engineering,
张帆,牛国伟,王虎林等.甲烷裂解碳的活化改性及其电化学性能研究[J].低碳化学与化工, DOI：10.12434/j.issn.2097-2547.20260036.

ZHANG Fan,NIU Guowei,WANG Hulin,et al.Study on activation and modification of methane-pyrolyzed carbon and its electrochemical performances[J].Low-Carbon Chemistry and Chemical Engineering, DOI：10.12434/j.issn.2097-2547.20260036.

摘要

甲烷裂解碳经活化处理后用作超级电容器电极材料，能够有效提升甲烷裂解工艺的经济性。基于这一背景，针对甲烷裂解碳碱活化工艺展开了研究，旨在优化活化条件以探究活性炭结构与比电容的相关性。采用正交实验结合极差分析法，探究了碱碳比（

(KOH)/

(甲烷裂解碳)）、活化温度和活化时间对活性炭结构和电化学性能的影响，随后固定碱碳比和活化时间，重点剖析了活化温度对活性炭的形貌、织构性质、物相和比电容等的影响。结果显示，随活化温度升高，活性炭的比表面积呈单调递增趋势，微孔比表面积则呈现“火山型”变化。C-4-600-2.0（600 ℃下活化2.0 h）的微孔比表面积达到最大值（1120.16 m

/g），微孔占比（微孔孔容/总孔孔容）也较大。当活化温度进一步升高，KOH会烧穿微孔壁，促使微孔联结形成大量孔径3 nm以上的介孔。电化学测试结果表明，活性炭的比电容与微孔比表面积呈正相关，证明微孔是影响其电化学性能的核心因素。C-4-600-2.0在三电极体系中比电容最高（193.71 F/g），双电极体系中比电容为176.4 F/g，且经5000次循环测试后，C-4-600-2.0依旧保持良好的电化学稳定性，比电容保持率为88.72%，库伦效率为87.02%。

Abstract

Methane-pyrolyzed carbon

after activation treatment

can be used as an electrode material for supercapacitors

effectively improving the economic efficiency of methane-pyrolyzed processes. Based on this background

research has been conducted on the alkali activation process of methane-pyrolyzed carbon

aiming to optimize the activation conditions and explore the correlation between structures and specific capacitances of activated carbon. Using orthogonal experiments combined with range analysis

the effects of alkali to carbon ratios (

(KOH)/

(methane-pyrolyzed carbon))

activation temperatures

and activation time on the structures and electrochemical performances of activated carbon were investigated. Subsequently

fixing the alkali to carbon ratios and activation time

the effects of activation temperatures on morphologies

textural properties

phases and specific capacitances of activated carbon were analyzed in detail. The re

sults indicate that with the increase of activation temperatures

the specific surface areas of activated carbon show a monotonic increasing trend

while the specific surface areas of micropores show a “volcanic-type” variation. The specific surface area of micropores of C-4-600-2.0 (activated at 600 ℃ for 2.0 h) reaches the maximum value (1120.16 m

/g)

and the proportion of micropores (micropore volume/total pore volume) is also relatively large. When the activation temperature further increases

KOH will burn through the micropore walls

promoting the connection of micropores to form a large number of mesopores with diameters exceeding 3 nm. The electrochemical test results demonstrate that specific capacitances of activated carbon are positively correlated with the specific surface areas of micropores

indicating that micropores are the core factor affecting their electrochemical performances. C-4-600-2.0 exhibits the highest specific capacitance (193.71 F/g) in the three-electrode system

and the specific capacitance in the two-electrode system is 176.4 F/g. After 5000 cycles of testing

C-4-600-2.0 maintains excellent electrochemical stability

with a specific capacitance retention rate of 88.72% and a coulombic efficiency of 87.02%.

关键词

Keywords

references

KHAN M H A , DAIYAN R , NEAL P , et al . A framework for assessing economics of blue hydrogen production from steam methane reforming using carbon capture storage & utilization [J ] . International Journal of Hydrogen Energy , 2021 , 44 ( 46 ): 22685 - 22706 .

HAFEEZ S , AL-SALEM S M , MANOS G , et al . Fuel production using membrane reactors: A review [J ] . Environmental Chemistry Letters , 2020 , 18 ( 5 ): 1477 - 1490 .

黄泽皑 , 周芸霄 , 张魁魁 , 等 . 甲烷裂解制氢和碳材料工艺研究进展 [J ] . 低碳化学与化工 , 2024 , 49 ( 9 ): 1 - 11 .

HUANG Z A , ZHOU Y X , ZHANG K K , et al . Research progress on methane pyrolysis process for hydrogen and carbon materials [J ] . Low-Carbon Chemistry and Chemical Engineering , 2024 , 49 ( 9 ): 1 - 11 .

SANCHEZ-BASTARDO N , SCHLOGL R , RULAND H . Methane pyrolysis for CO 2 -free H 2 production: A green process to overcome renewable energies unsteadiness [J ] . Chemie Ingenieur Technik , 2020 , 92 ( 10 ): 1596 - 1609 .

MACHHAMMER O , BODE A , HORMUTH W . Financial and ecological evaluation of hydrogen production processes on large scale [J ] . Chemical Engineering & Technology , 2016 , 39 ( 6 ): 1185 - 1193 .

MSHEIK M , RODAT S , ABANADES S . Methane cracking for hydrogen production: A review of catalytic and molten media pyrolysis [J ] . Energies , 2021 , 14 ( 11 ): 3107 .

唐文强 , 刘晨龙 , 杨薪颖 , 等 . 甲烷裂解制多壁碳纳米管的Ni基催化剂研究进展 [J ] . 低碳化学与化工 , 2025 , 50 ( 10 ): 1 - 9 .

TANG W Q , LIU C L , YANG X Y , et al . Research progress on Ni-based catalysts for methane cracking to multi-walled carbon nanotubes [J ] . Low-Carbon Chemistry and Chemical Engineering , 2025 , 50 ( 10 ): 1 - 9 .

DASIREDDY V D B C , LIKOZAR B . Activation and decomposition of methane over cobalt-, copper-, and iron-based heterogeneous catalysts for CO x -free hydrogen and multiwalled carbon nanotube production [J ] . Energy Technology , 2017 , 5 ( 8 ): 1344 - 1355 .

GUIL-LOPEZ R , BOTAS J A , FIERRO J L G , et al . Comparison of metal and carbon catalysts for hydrogen production by methane decomposition [J ] . Applied Catalysis A General , 2011 , 396 ( 1/2 ): 40 - 51 .

GUTTA N , VELISOJU V K , TARDIO J , et al . CH 4 cracking over the Cu-Ni/Al-MCM-41 catalyst for the simultaneous production of H 2 and highly ordered graphitic carbon nanofibers [J ] . Energy & Fuels , 2019 , 33 ( 12 ): 12656 - 12665 .

KEIPI T , TOLVANEN K E S , TOLVANEN H , et al . Thermo-catalytic decomposition of methane: The effect of reaction parameters on process design and the utilization possibilities of the produced carbon [J ] . Energy Conversion and Management , 2016 , 126 : 923 - 934 .

GOLIKAND A N , ASGARI M , LOHRASBI E . Study of oxygen reduction reaction kinetics on multi-walled carbon nano-tubes supported Pt-Pd catalysts under various conditions [J ] . International Journal of Hydrogen Energy , 2011 , 36 ( 20 ): 13317 - 13324 .

QIAN J X , CHEN T W , ENAKONDA L R , et al . Methane decomposition to pure hydrogen and carbon nano materials: State-of-the-art and future perspectives [J ] . International Journal of Hydrogen Energy , 2020 , 45 ( 32 ): 15721 - 15743 .

MENG X Y , ZHANG C C , DONG C Z , et al . Carbon quantum dots assisted strategy to synthesize Co@NC for boosting photocatalytic hydrogen evolution performance of CdS [J ] . Chemical Engineering Journal , 2020 , 389 : 124432 .

DONG D , XIAO Y . Recent progress and challenges in coal-derived porous carbon for supercapacitor applications [J ] . Chemical Engineering Journal , 2023 , 470 : 144441 .

GAO D , LUO Z L , LIU C H , et al . A survey of hybrid energy devices based on supercapacitors [J ] . Green Energy & Environment , 2023 , 8 ( 4 ): 972 - 988 .

AKHTER R , MAKTEDAR S S . MXenes: A comprehensive review of synthesis, properties, and progress in supercapacitor applications [J ] . Journal of Materiomics , 2023 , 9 ( 6 ): 1196 - 1241 .

DUBEY R , GURUVIAH V . Review of carbon-based electrode materials for supercapacitor energy storage [J ] . Ionics , 2019 , 25 ( 4 ): 1419 - 1445 .

POHLMANN S , BELÉN LOBATO , CENTENO T A , et al . The influence of pore size and surface area of activated carbons on the performance of ionic liquid based supercapacitors [J ] . Physical Chemistry Chemical Physics , 2013 , 15 ( 40 ): 17287 - 17294 .

KRISHNAMOORTHY K , SUDHAKARAN M S P , PAZHAMALAI P , et al . A highly efficient 2D siloxene coated Ni foam catalyst for methane dry reforming and an effective approach to recycle the spent catalyst for energy storage applications [J ] . Journal of Materials Chemistry A , 2019 , 7 ( 32 ): 18950 - 18958 .

BAPTISTA J , SHACKLOCK J , SHABAN M , et al . Superior rate capability of high mass loading supercapacitors fabricated with carbon recovered from methane cracking [J ] . Inorganics , 2023 , 11 ( 8 ): 316 .

ZHANG J B , GE Y J , GAO F L , et al . Synergistic conversion of coal char and methane for syngas and carbon-based supercapacitor electrodes [J ] . Journal of Colloid and Interface Science , 2020 , 562 : 235 - 243 .

FELLINGER T P . Sol-gel carbons from ionothermal syntheses [J ] . Journal of Sol-Gel Science and Technology , 2017 , 81 ( 1 ): 52 - 58 .

PALLARÉS J , GONZÁLEZ-CENCERRADO A ， ARAUZO I . Production and characterization of activated carbon from barley straw by physical activation with carbon dioxide and steam [J ] . Biomass and Bioenergy , 2018 , 115 : 64 - 73 .

ZOU Y L , WANG H F , XU L F , et al . Synergistic effect of CO 2 and H 2 O co-activation of Zhundong coal at a low burn-off rate on high performance supercapacitor [J ] . Journal of Power Sources , 2023 , 556 : 232509 .

曲伟强 , 赵佳辉 , 王双 , 等 . 超级电容器用生物质基碳材料研究进展 [J ] . 低碳化学与化工 , 2024 , 49 ( 10 ): 38 - 46 .

QU W Q , ZHAO J H , WANG S , et al . Research progress of biomass-based carbon materials for supercapacitors [J ] . Low-Carbon Chemistry and Chemical Engineering , 2024 , 49 ( 10 ): 38 - 46 .

SHI M , XIN Y F , CHEN X X , et al . Coal-derived porous activated carbon with ultrahigh specific surface area and excellent electrochemical performance for supercapacitors [J ] . Journal of Alloys and Compounds , 2021 , 859 : 157856 .

HAN G X , JIA J B , LIU Q R , et al . Template-activated bifunctional soluble salt ZnCl 2 assisted synthesis of coal-based hierarchical porous carbon for high-performance supercapacitors [J ] . Carbon , 2022 , 186 : 380 - 390 .

CHEN W , GONG M , LI K X , et al . Insight into KOH activation mechanism during biomass pyrolysis: Chemical reactions between O-containing groups and KOH [J ] . Applied Energy , 2020 , 278 : 115730 .

LI J J , QU J J , YANG R , et al . A sensitive and selective electrochemical sensor based on graphene quantum dot/gold nanoparticle nanocomposite modified electrode for the determination of quercetin in biological samples [J ] . Electroanalysis , 2016 , 28 ( 6 ): 1322 - 1330 .

LI Y B , ZHANG D Y , ZHANG Y M , et al . Biomass-derived microporous carbon with large micropore size for high-performance supercapacitors [J ] . Journal of Power Sources , 2020 , 448 : 227396 .

ZHANG L L , ZHAO X S . Carbon-based materials as supercapacitor electrodes [J ] . Chemical society reviews , 2009 , 38 ( 9 ): 2520 - 2531 .

周娅兰 , 王建友 , 杨文成 , 等 . 煤焦-Ni复合物催化甲烷干重整及其反应后形成碳材料的电化学性能研究 [J ] . 低碳化学与化工 , 2024 , 49 ( 6 ): 54 - 62 .

ZHOU Y L , WANG J Y , YANG W C , et al . Study on dry reforming of methane catalyzed by coal char-Ni composite and electrochemical performance of formed carbon materials after reaction [J ] . Low-Carbon Chemistry and Chemical Engineering , 2024 , 49 ( 6 ): 54 - 62 .

MAHATO M , NAM S , TABASSIAN R , et al . Electronically conjugated multifunctional covalent triazine framework for unprecedented CO 2 selectivity and high-power flexible supercapacitor [J ] . Advanced Functional Materials , 2022 , 32 ( 5 ): 2107442 .

NIU L Y , SHEN C , YAN L J , et al . Waste bones derived nitrogen-doped carbon with high micropore ratio towards supercapacitor applications [J ] . Journal of Colloid and Interface Science , 2019 , 547 : 92 - 101 .

ZHANG L , YANG X , ZHANG F , et al . Controlling the effective surface area and pore size distribution of sp 2 carbon materials and their impact on the capacitance performance of these materials [J ] . Journal of the American Chemical Society , 2013 , 135 ( 15 ): 5921 - 5929 .

ZHANG P F , ZHANG Z Y , CHEN J H , et al . Ultrahigh surface area carbon from carbonated beverages: Combining self-templating process and in situ activation [J ] . Carbon , 2015 , 93 : 39 - 47 .

WANG J Y , HUO T , ZHAO Y H , et al . Recent advances in heteroatoms-doped porous carbon electrode materials for supercapacitors: A review [J ] . Journal of Energy Storage , 2025 , 110 : 115216 .

WANG L J , SUN F , HAO F , et al . A green trace K 2 CO 3 induced catalytic activation strategy for developing coal-converted activated carbon as advanced candidate for CO 2 adsorption and supercapacitors [J ] . Chemical Engineering Journal , 2020 , 383 : 123205 .

ZHANG J F , WANG Y , SHU X , et al . One-pot synthesis of nickel-cobalt hydroxyfluorides nanowires with ultrahigh energy density for an asymmetric supercapacitor [J ] . Science Bulletin , 2018 , 63 ( 5 ): 322 - 330 .

BARBIERI O , HAHN M , HERZOG A , et al . Capacitance limits of high surface area activated carbons for double layer capacitors [J ] . Carbon , 2005 , 43 ( 6 ): 1303 - 1310 .

LIU C , LI F , MA L P , et al . Advanced materials for energy storage [J ] . Advanced materials , 2010 , 22 ( 8 ): E28 - E62 .

CONWAY B E . Electrochemical supercapacitors: Scientific fundamentals and technological applications [M ] . Germany : Springer Science & Business Media , 2013 .

SEKAR M , SAKTHI V , RENGARAJ S . Kinetics and equilibrium adsorption study of lead(II) onto activated carbon prepared from coconut shell [J ] . Journal of Colloid & Interface Science , 2004 , 279 ( 2 ): 307 - 313 .

MIAO L , ZHU D Z , LIU M X , et al . Cooking carbon with protic salt: Nitrogen and sulfur self-doped porous carbon nanosheets for supercapacitors [J ] . Chemical Engineering Journal , 2018 , 347 : 233 - 242 .

SHAN D D , YANG J , LIU W , et al . Biomass-derived three-dimensional honeycomb-like hierarchical structured carbon for ultrahigh energy density asymmetric supercapacitors [J ] . Journal of Materials Chemistry A , 2016 , 4 ( 35 ): 13589 - 13602 .

ZOU K Y , LI N , DAI X , et al . Lightweight freestanding CeF 3 nanorod/carbon nanotube composite interlayer for lithium-sulfur batteries [J ] . ACS Applied Nano Materials , 2020 , 3 ( 6 ): 5732 - 5742 .

YANG W , YANG W , DING F , et al . Template-free synthesis of ultrathin porous carbon shell with excellent conductivity for high-rate supercapacitors [J ] . Carbon , 2017 , 111 : 419 - 427 .

LIU X , CHOI J , XU Z , et al . Raman spectroscopy measurements support disorder-driven capacitance in nanoporous carbons [J ] . Journal of the American Chemical Society , 2024 , 146 ( 45 ): 30748 - 30752 .

EL-KHODARY S A , ABOMOHRA E F , EL-ENANY G M , et al . Sonochemical assisted fabrication of 3D hierarchical porous carbon for high-performance symmetric supercapacitor [J ] . Ultrasonics Sonochemistry , 2019 , 58 : 104617 .

ZHANG D D , HE C , WANG Y Z , et al . Oxygen-rich hierarchically porous carbons derived from pitch-based oxidized spheres for boosting the supercapacitive performance [J ] . Journal of Colloid and Interface Science , 2019 , 540 : 439 - 447 .

LING Z , WANG Z Y , ZHANG M D , et al . Sustainable synthesis and assembly of biomass-derived b / n co-doped carbon nanosheets with ultrahigh aspect ratio for high-performance supercapacitors [J ] . Advanced Functional Materials , 2016 , 26 ( 1 ): 111 - 119 .

LI H Q , LIU R L , ZHAO D Y , et al . Electrochemical properties of an ordered mesoporous carbon prepared by direct tri-constituent co-assembly [J ] . Carbon , 2007 , 45 ( 13 ): 2628 - 2635 .

HE X J , ZHAO N , QIU J S . Synthesis of hierarchical porous carbons for supercapacitors from coal tar pitch with nano-Fe 2 O 3 as template and activation agent coupled with KOH activation [J ] . Journal of Materials Chemistry A , 2013 , 1 ( 33 ): 9440 - 9448 .

YUAN C , ZHOU L , ZHU S Q , et al . Albumen-derived hierarchical porous N-and O-enriched carbon towards high-performance electrochemical capacitors [J ] . Journal of The Electrochemical Society , 2015 , 162 ( 4 ): 781 - 786 .

CHENG J X , LU Z J , ZHAO X F , et al . Green needle coke-derived porous carbon for high-performance symmetric supercapacitor [J ] . Journal of Power Sources , 2021 , 494 : 229770 .

WANG H , WANG M , ZHANG J S , et al . Preparation of fly ash-based cobalt-iron silicate as supercapacitor electrode material [J ] . Chemical Engineering Journal , 2022 , 434 : 134661 .

YANG Y K , WANG J S , ZUO P P , et al . Layer-stacked graphite-like porous carbon for flexible all-solid-state supercapacitor [J ] . Chemical Engineering Journal , 2021 , 425 : 130609 .

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