前驱体机械压实制备高密度活性炭及其致密电容储能性能

doi:10.3866/PKU.WHXB202406009

物理化学学报 >> 2025, Vol. 41 >> Issue (3): 100028.doi: 10.3866/PKU.WHXB202406009

前驱体机械压实制备高密度活性炭及其致密电容储能性能

李齐齐¹^,†, 张苏¹^,*^,†(), 江娱婷², 朱琳娜³, 郭楠楠³, 张晶¹, 李禹彤¹, 魏彤¹^,⁴, 范壮军¹^,⁴^,*()

¹ 中国石油大学(华东)材料科学与工程学院, 山东青岛 266580
² 辽宁师范大学化学化工学院, 辽宁大连 116029
³ 新疆大学化学学院, 碳基能源资源化学与利用国家重点实验室, 乌鲁木齐 830017
⁴ 合肥综合性国家科学中心能源研究院, 合肥 230031

收稿日期:2024-06-11 修回日期:2024-07-29 录用日期:2024-07-30 发布日期:2024-12-14
通讯作者: Email: suzhangs@163.com (张苏)fanzhj666@163.com (范壮军)
作者简介:
^†These authors contributed equally to this work.
基金资助:
国家自然科学基金项目(52062046); 国家自然科学基金项目(52302336); 山东省泰山学者计划(tsqn202306131); 山东省泰山学者计划(tsqn202312123); 山东省自然科学基金重大基础研究项目(ZR2019ZD51)

Preparation of High Density Activated Carbon by Mechanical Compression of Precursors for Compact Capacitive Energy Storage

Qiqi Li¹, Su Zhang¹^,*(), Yuting Jiang², Linna Zhu³, Nannan Guo³, Jing Zhang¹, Yutong Li¹, Tong Wei¹^,⁴, Zhuangjun Fan¹^,⁴^,*()

¹ School of Material Science and Engineering, China University of Petroleum (East China), Qingdao 266580, Shandong Province, China
² School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, Liaoning Province, China
³ State Key Laboratory of Chemistry and Utilization of Carbon Based Energy Resources, College of Chemistry, Xinjiang University, Urumqi 830017, China
⁴ Institute of Energy, Hefei Comprehensive National Science Center, Hefei 230031, China

Received:2024-06-11 Revised:2024-07-29 Accepted:2024-07-30 Published:2024-12-14
Contact: Email: suzhangs@163.com (Su Zhang)fanzhj666@163.com (Zhuangjun Fan)
Supported by:
the National Natural Science Foundation of China(52062046); the National Natural Science Foundation of China(52302336); the Taishan Scholar Project of Shandong Province(tsqn202306131); the Taishan Scholar Project of Shandong Province(tsqn202312123); the Key Basic Research Projects of Natural Science Foundation of Shandong Province(ZR2019ZD51)

摘要/Abstract

摘要：

大比表面积活性炭的密度普遍较低、体积储能性能不佳，难以满足超级电容器的小型化发展需求。针对此，本工作提出在活化前对炭前驱体进行机械压实以提高活性炭密度的普适性方法，并研究了机械压实对由外而内活化(炭粉/KOH混合物)和均匀离子活化(热解含钾盐类)所制备活性炭的比表面积、孔结构和电容储能性能的影响规律。结果表明，对前驱体进行机械压实能够提高活化反应效率、活性炭密度和体积电容储能性能。随着机械压力升高，由外而内活化所得活性炭的比表面积和孔隙率先升高后降低，原因在于机械压实能够消除颗粒间的空隙以增加前驱体与活化剂之间的接触，进而显著提高了活化效率。对于均匀离子活化，活性炭的比表面积和孔隙率呈现先降低后升高的趋势，这可能是由于致密前驱体抑制了热解过程中产生的活性气体分子(H₂O、CO₂等)快速散逸，使之继续参与活化反应，提高了活化刻蚀效率。本工作为大比表面积和高密度活性炭的设计制备提供了简单思路。

关键词: 活性炭, 机械压实, 活化, 超级电容器, 体积比容量

Abstract:

Activated carbons are widely used as the electrode material for supercapacitors owing to their large surface area, moderate conductivity, and outstanding electrochemical stability. However, large-surface-area activated carbons usually show low density and poor volumetric energy storage performance, which is difficult to meet the development of devices miniaturization. Mechanical compression is a simple and effective method to improve the density of the activated carbons. However, most of the studies focus on mechanical compression of the as-prepared porous carbon materials. Preparation of high-density activated carbons by mechanical compression of the carbon precursors has been proposed. But the surface area and porous structure evolution, and the possible mechanism have rarely investigated. Herein, we propose a universal method to improve the density of the activated carbons by mechanical compression of the precursors before activation. The influence of mechanical compression on the surface area, porous structure, and capacitive energy storage performance of the activated carbons prepared by two typical methods, outside-in activation (carbon powder/KOH mixture) and homogeneous ion activation (pyrolysis of potassium-containing salts), are studied. Mechanical compression of the precursors can generally improve the activation reaction efficiency, as well as the density and volumetric capacitive performance of the activated carbons. However, the surface area and porous structure evolution mainly depend on the carbon precursor and pore-forming process. For outside-in activation, the surface area and porosity of the activated carbons show a first increasing and then decreasing trend with the increase of mechanical pressure. This is because mechanical compression enhances the contact between the carbon precursors and activator through eliminating the voids between particles, significantly improves the activation efficiency. For homogeneous ion activation, the surface area and porosity of activated carbons show a trend of decreasing first and then increasing. The reason is deduced as compressed precursors inhibit the rapid release of active gas molecules (H₂O, CO₂ etc.) produced during pyrolysis. These gas molecules further participate in the activation etching reaction and promote the activation efficiency. The optimized sample shows high gravimetric and volumetric capacitances of 316 F·g^-1/291 F·cm^-3 and 131 F·g^-1/92 F·cm^-3 at 1 A·g^-1 in aqueous and organic electrolytes, respectively. This work provides a simple way for design and preparation of activated carbons with large surface area and high density.

Key words: Activated carbon, Mechanical compression, Activation, Supercapacitor, Volumetric capacitance

李齐齐, 张苏, 江娱婷, 朱琳娜, 郭楠楠, 张晶, 李禹彤, 魏彤, 范壮军. 前驱体机械压实制备高密度活性炭及其致密电容储能性能[J]. 物理化学学报, 2025, 41(3), 100028. doi: 10.3866/PKU.WHXB202406009

Qiqi Li, Su Zhang, Yuting Jiang, Linna Zhu, Nannan Guo, Jing Zhang, Yutong Li, Tong Wei, Zhuangjun Fan. Preparation of High Density Activated Carbon by Mechanical Compression of Precursors for Compact Capacitive Energy Storage[J]. Acta Phys. -Chim. Sin. 2025, 41(3), 100028. doi: 10.3866/PKU.WHXB202406009

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202406009

https://www.whxb.pku.edu.cn/CN/Y2025/V41/I3/100028

图/表 8

图1

图2

图3

图4

图5

图6

图7

图8

参考文献 60

1	Simon P.; Gogotsi Y. Nat. Mater. 2008, 7, 845. doi: 10.1038/nmat2297
2	Wang Y.; Song Y.; Xia Y. Chem. Soc. Rev 2016, 45, 5925. doi: 10.1039/c5cs00580a
3	Wang G.; Zhang L.; Zhang J. Chem. Soc. Rev 2012, 41, 797. doi: 10.1039/c1cs15060j
4	Sevilla M.; Mokaya R. Energy Environ. Sci. 2014, 7, 1250. doi: 10.1039/c3ee43525c
5	Shao H.; Wu Y.; Lin Z.; Taberna P. L.; Simon P. Chem. Soc. Rev 2020, 49, 3005. doi: 10.1039/d0cs00059k
6	杨越; 朱加伟; 王鹏彦; 刘海咪; 曾炜豪; 陈磊; 陈志祥; 木士春. 物理化学学报, 2022, 38, 2106002. doi: 10.3866/PKU.WHXB202106002
	Yang Y.; Zhu J.; Wang P.; Liu H.; Zeng W.; Chen L.; Chen Z.; Mu S. Acta Phys.-Chim. Sini. 2022, 38, 2106002.
7	叶萍; 覃玲霜; 贺萌瑶; 巫方方; 陈增烨; 梁明星; 邓立波. 物理化学学报, 2024, 40, 2311032. doi: 10.3866/PKU.WHXB202311032
	Ye P.; Qin L.; He M.; Wu F.; Chen Z.; Liang M.; Deng L. Acta Phys.-Chim. Sini. 2024, 40, 2311032.
8	张威; 梁海琛; 朱科润; 田泳; 刘瑶; 陈佳音; 李伟. 物理化学学报, 2022, 38, 2105024. doi: 10.3866/PKU.WHXB202105024
	Zhang W.; Liang H.; Zhu K.; Tian Y.; Liu Y.; Chen J.; Li W. Acta Phys.-Chim. Sini. 2022, 38, 2105024.
9	Guo W.; Yu C.; Li S.; Qiu J. Energy Environ. Sci. 2021, 14, 576. doi: 10.1039/d0ee02649b
10	Wu J.; Zhang X.; Ju Z.; Wang L.; Hui Z.; Mayilvahanan K.; Takeuchi K. J.; Marschilok A. C.; West A. C.; Takeuchi E. S., et al. Adv. Mater. 2021, 33, 2101275. doi: 10.1002/adma.202101275
11	Zhang C.; Lv W.; Tao Y.; Yang Q. Energy Environ. Sci. 2015, 8, 1390. doi: 10.1039/c5ee00389j
12	Li H.; Tao Y.; Zheng X.; Luo J.; Kang F.; Cheng H.; Yang Q. Energy Environ. Sci. 2016, 9, 3135. doi: 10.1039/c6ee00941g
13	Li Z.; Gadipelli S.; Li H.; Howard C. A.; Brett D. J. L.; Shearing P. R.; Guo Z.; Parkin I. P.; Li F. Nat. Energy 2020, 5, 160. doi: 10.1038/s41560-020-0560-6
14	Xu Y.; Lin Z.; Zhong X.; Huang X.; Weiss N. O.; Huang Y.; Duan X. Nat. Commun. 2014, 5, 4554. doi: 10.1038/ncomms5554
15	Li H.; Tao Y.; Zheng X.; Li Z.; Liu D.; Xu Z.; Luo C.; Luo J.; Kang F.; Yang Q. Nanoscale 2015, 7, 18459. doi: 10.1039/c5nr06113j
16	Murali S.; Quarles N.; Zhang L. L.; Potts J. R.; Tan Z.; Lu Y.; Zhu Y.; Ruoff R. S. Nano Energy 2013, 2, 764. doi: 10.1016/j.nanoen.2013.01.007
17	Li P.; Li H.; Han D.; Shang T.; Deng Y.; Tao Y.; Lv W.; Yang Q. H. Adv. Sci. 2019, 6, 1802355. doi: 10.1002/advs.201802355
18	Zhang S.; Zhu J.; Qing Y.; Wang L.; Zhao J.; Li J.; Tian W.; Jia D.; Fan Z. Adv. Funct. Mater. 2018, 28, 1805898. doi: 10.1002/adfm.201805898
19	Jiang Y.; Jiang Z.; Shi M.; Liu Z.; Liang S.; Feng J.; Sheng R.; Zhang S.; Wei T.; Fan Z. Carbon 2021, 182, 559. doi: 10.1016/j.carbon.2021.06.039
20	Tian W.; Zhu J.; Dong Y.; Zhao J.; Li J.; Guo N.; Lin H.; Zhang S.; Jia D. Carbon 2020, 161, 89. doi: 10.1016/j.carbon.2020.01.044
21	Guo H.; Ding B.; Dong X.; Dong S.; Zhang Y.; Zhu J.; Dou H.; Zhang X. Energy Technol.-Ger. 2019, 7, 1900209. doi: 10.1002/ente.201900209
22	Adeniran B.; Mokaya R. Nano Energy 2015, 16, 173. doi: 10.1016/j.nanoen.2015.06.022
23	Balahmar N.; Mitchell A. C.; Mokaya R. Adv. Energy Mater. 2015, 5, 1500867. doi: 10.1002/aenm.201500867
24	Wu X.; Ding B.; Zhang C.; Li B.; Fan Z. Carbon 2019, 153, 225. doi: 10.1016/j.carbon.2019.07.020
25	Sevilla M.; Fuertes A. B. ACS Nano 2014, 8, 5069. doi: 10.1021/nn501124h
26	Li J.; Kossmann J.; Zeng K.; Zhang K.; Wang B.; Weinberger C.; Antonietti M.; Odziomek M.; López-Salas N. Angew. Chem. Int. Ed. 2023, 62, e202217808. doi: 10.1002/anie.202217808
27	Liu Q.; Wu D.; Wang T.; Wang C.; Jia D. Adv. Funct. Mater. 2024, 34, 2400556. doi: 10.1002/adfm.202400556
28	Peng Q.; Wang K.; Gong Y.; Zhang X.; Xu Y.; Ma Y.; Zhang X.; Sun X.; Ma Y. Adv. Funct. Mater. 2023, 33, 2308284. doi: 10.1002/adfm.202308284
29	Liu X.; Lyu D.; Merlet C.; Leesmith M. J. A.; Hua X.; Xu Z.; Grey C. P.; Forse A. C. Science 2024, 384, 321. doi: 10.1126/science.adn6242
30	唐诗怡; 鹿高甜; 苏毅; 王广; 李炫璋; 张广琦; 魏洋; 张跃钢. 物理化学学报, 2020, 38, 2001007. doi: 10.3866/PKU.WHXB202001007
	Tang S.; Lu G.; Su Y.; Wang G.; Li X.; Zhang G.; Wei Y.; Zhang Y. Acta Phys.-Chim. Sin. 2020, 38, 2001007.
31	Li Q.; Jiang Y.; Jiang Z.; Zhu J.; Gan X.; Qin F.; Tang T.; Luo W.; Guo N.; Liu Z.; et al Carbon 2022, 191, 19. doi: 10.1016/j.carbon.2022.01.042
32	Liu W.; Jiang H.; Yu H. Chem. Rev. 2015, 115, 12251. doi: 10.1021/acs.chemrev.5b00195
33	Shi J.; Huang T.; Wu R.; Wu J.; Li Y.; Kuang Y.; Xing H.; Zhang W. Int. J. Biol. Macromol. 2024, 264, 130460. doi: 10.1016/j.ijbiomac.2024.130460
34	Choudhary N.; Li C.; Moore J.; Nagaiah N.; Zhai L.; Jung Y.; Thomas J. Adv. Mater. 2017, 29, 1605336. doi: 10.1002/adma.201605336
35	Zhang J.; Tang T.; Gan X.; Yuan R.; Li Q.; Zhu L.; Guo N.; Zhu J.; Li Y.; Zhang S.; et al Chem. Eng. J. 2023, 470, 144257. doi: 10.1016/j.cej.2023.144257
36	Liu B.; Liu Y.; Chen H.; Yang M.; Li H. J. Power Sources 2017, 341, 309. doi: 10.1016/j.jpowsour.2016.12.022
37	Dong Y.; Zhang S.; Du X.; Hong S.; Zhao S.; Chen Y.; Chen X.; Song H. Adv. Funct. Mater. 2019, 29, 1901127. doi: 10.1002/adfm.201901127
38	Qin F.; Li Q.; Tang T.; Zhu J.; Gan X.; Chen Y.; Li Y.; Zhang S.; Huang X.; Jia D. Fuel 2022, 322, 124216. doi: 10.1016/j.fuel.2022.124216
39	Liang Q.; Ye L.; Huang Z.; Xu Q.; Bai Y.; Kang F.; Yang Q. Nanoscale 2014, 6, 13831. doi: 10.1039/c4nr04541f
40	Jiang Y.; Li J.; Jiang Z.; Shi M.; Sheng R.; Liu Z.; Zhang S.; Cao Y.; Wei T.; Fan Z. Carbon 2021, 175, 281. doi: 10.1016/j.carbon.2021.01.016
41	Xie Q.; Bao R.; Zheng A.; Zhang Y.; Wu S.; Xie C.; Zhao P. ACS Sustain. Chem. Eng. 2016, 4, 1422. doi: 10.1021/acssuschemeng.5b01417
42	Wang R.; Wang P.; Yan X.; Lang J.; Peng C.; Xue Q. ACS Appl. Mater. Interf. 2012, 4, 5800. doi: 10.1021/am302077c
43	Pritzl D.; Bumberger A. E.; Wetjen M.; Landesfeind J.; Solchenbach S.; Gasteiger H. A. J. Electrochem. Soc. 2019, 166, 582. doi: 10.1149/2.0451904jes
44	Landesfeind J.; Pritzl D.; Gasteiger H. A. J. Electrochem. Soc. 2017, 164, 1773. doi: 10.1149/2.0131709jes
45	Zou K.; Cai P.; Deng X.; Wang B.; Liu C.; Li J.; Hou H.; Zou G.; Ji X. J. Energy Chem. 2021, 60, 209. doi: 10.1016/j.jechem.2020.12.039
46	Wang Q.; Qu Y.; Bai J.; Chen Z.; Luo Q.; Li H.; Li J.; Yang W. Nano Energy 2024, 120, 109147. doi: 10.1016/j.nanoen.2023.109147
47	Zhang F.; Liu T.; Hou G.; Kou T.; Yue L.; Guan R.; Li Y. Nano Res. 2016, 9, 2875. doi: 10.1007/s12274-016-1173-z
48	Dang Z.; Li X.; Li Y.; Dong L. J. Colloid Interf. Sci. 2023, 644, 221. doi: 10.1016/j.jcis.2023.04.074
49	Peng X.; Li Y.; Kang F.; Li X.; Zheng Z.; Dong L. Small 2024, 20, 2305547. doi: 10.1002/smll.202305547
50	Irham M. A.; Septianto R. D.; Wulandari R. D.; Majima Y.; Iskandar F.; Iwasa Y.; Bisri S. Z. ACS Appli. Mater. Interfaces 2024, 16, 24889. doi: 10.1021/acsami.4c02517
51	Liu C.; Yan X.; Hu F.; Gao G.; Wu G.; Yang X. Adv. Mater. 2018, 30, 1705713. doi: 10.1002/adma.201705713
52	Alexander C. F.; Griffin J. M.; Merlet C.; Carretero-Gonzalez J.; Raji A.-R. O.; Trease N. M.; Grey C. P. Nat. Energy 2017, 2, 16216. doi: 10.1038/nenergy.2016.216
53	Béguin F.; Presser V.; Balducci A.; Frackowiak E. Adv. Mater. 2014, 26, 2219. doi: 10.1002/adma.201304137
54	Chmiola J.; Yushin G.; Gogotsi Y.; Portet C.; Simon P.; Taberna P. L. Science 2006, 313, 1760. doi: 10.1126/science.1132195
55	Chmiola J.; Largeot C.; Taberna P. L.; Simon P.; Gogotsi Y. Angew. Chem. Int. Ed. 2008, 120, 3440. doi: 10.1002/ange.200704894
56	Stoller M. D.; Park S.; Zhu Y.; An J.; Rodney R. S. Nano Lett. 2008, 8, 3498. doi: 10.1021/nl802558y
57	Díez N.; Sevilla M.; Fuertes A. B. Chem. Electro. Chem. 2020, 7, 3798. doi: 10.1002/celc.202000960
58	Ferrero G. A.; Fuertes A. B.; Sevilla M. Electrochim. Acta 2015, 168, 320. doi: 10.1016/j.electacta.2015.04.052
59	Huang L.; Key J.; Shen P. K. J. Power Sources 2019, 414, 76. doi: 10.1016/j.jpowsour.2018.12.060
60	Chen Q.; Sun J.; Wang Z.; Zhao Z.; Zhang Y.; Liu Y.; Hou L.; Yuan C. RSC Adv. 2018, 8, 9181. doi: 10.1039/c8ra00858

[1]	刘华艳, 陈逸飞, 杨梦召, 顾佳俊. 二维材料基超级电容器的容量与倍率性能提升策略[J]. 物理化学学报, 2025, 41(6): 100063 - .
[2]	王慧, LabidiAbdelkader, 任梦涵, ShaikFeroz, 王传义. 微观结构调控的g-C₃N₄在光催化NO转化中的最新进展：吸附/活化位点的关键作用[J]. 物理化学学报, 2025, 41(5): 100039 - .
[3]	吕卓岩, 丁杨铭, 康磊磊, 李林, 刘晓艳, 王爱琴, 张涛. 光增强CuO_x/TiO₂催化丙烯氧气直接环氧化反应[J]. 物理化学学报, 2025, 41(4): 100038 - .
[4]	张晶, 张苏, 李齐齐, 纪麟肯, 李禹彤, 任宇康, 臧小蓓, 曹宁, 胡涵, 梁鹏, 范壮军. 基于选择性化学刻蚀的低缺陷炭导电网络原位构筑及其对活性炭比表面积与导电性的协同增强[J]. 物理化学学报, 2025, 41(10): 100114 - .
[5]	王烨, 葛瑞翔, 刘翔, 李敬, 段昊泓. 一种阴离子浸出策略合成金属羟基氧化物用于电催化甘油氧化[J]. 物理化学学报, 2024, 40(7): 2307019 - .
[6]	曹爽, 钟博, 别传彪, 程蓓, 徐飞燕. WO₃/Zn_0.5Cd_0.5S S型异质结光催化产氢耦合有机物转化机理研究[J]. 物理化学学报, 2024, 40(5): 2307016 - .
[7]	许义飞, 杨瀚文, 常晓侠, 徐冰君. 电催化动力学简介[J]. 物理化学学报, 2023, 39(4): 2210025 -0 .
[8]	姜美慧, 盛利志, 王超, 江丽丽, 范壮军. 超级电容器用石墨烯薄膜：制备、基元结构及表面调控[J]. 物理化学学报, 2022, 38(2): 2012085 - .
[9]	周浩, 景亚轩, 王艳芹. 生物质转化中C―O/C―C键的活化断裂[J]. 物理化学学报, 2022, 38(10): 2203016 - .
[10]	王伟, 王瑶, 占自祥, 谭天, 邓卫平, 张庆红, 王野. 纤维素及其衍生物催化脱氧转化制化学品[J]. 物理化学学报, 2022, 38(10): 2205032 - .
[11]	刘源, 段增晖, 李隽, 常春然. 基于ReaxFF的甲烷无氧转化气相机理研究[J]. 物理化学学报, 2021, 37(11): 2011012 - .
[12]	张赛, 张铭凯, 瞿永泉. 二氧化铈表面构建固体“受阻”Lewis酸碱对用于小分子活化[J]. 物理化学学报, 2020, 36(9): 1911050 - .
[13]	王玖,吴南石,刘涛,曹少文,余家国. 用于超级电容器的锰钴氧化物/碳纤维材料[J]. 物理化学学报, 2020, 36(7): 1907072 - .
[14]	佟永丽, 戴美珍, 邢磊, 刘恒岐, 孙婉婷, 武祥. 基于NiCo₂O₄纳米片电极的非对称混合电容器[J]. 物理化学学报, 2020, 36(7): 1903046 - .
[15]	任宁,王昉,张建军,郑新芳. 热分析动力学研究方法的新进展[J]. 物理化学学报, 2020, 36(6): 1905062 - .

前驱体机械压实制备高密度活性炭及其致密电容储能性能

Preparation of High Density Activated Carbon by Mechanical Compression of Precursors for Compact Capacitive Energy Storage

RichHTML

PDF

赞

可视化

摘要/Abstract

引用本文

使用本文

图/表 8

参考文献 60

相关文章 15

Metrics

推荐阅读 0