Article(id=1319973106018529351, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1319973069423231598, articleNumber=null, orderNo=null, doi=10.14062/j.issn.0454-5648.20230604, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1691942400000, receivedDateStr=2023-08-14, revisedDate=1696608000000, revisedDateStr=2023-10-07, acceptedDate=null, acceptedDateStr=null, onlineDate=1792635712388, onlineDateStr=2026-10-22, pubDate=1716134400000, pubDateStr=2024-05-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1792635712388, onlineIssueDateStr=2026-10-22, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1792635712388, creator=13701087609, updateTime=1792635712388, updator=13701087609, issue=Issue{id=1319973069423231598, tenantId=1146029695717560320, journalId=1263187385517883426, year='2024', volume='52', issue='5', pageStart='1477', pageEnd='1788', issueExtLink='null', onlineDate='null', pubDate='1716134400000', pubDateStr='2024-05-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1792635703664, creator='13701087609', updateTime=1792641791199, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1319998602462741464, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1319973069423231598, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1319998602462741465, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1319973069423231598, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=1631, endPage=1642, ext={EN=ArticleExt(id=1319973106228244552, articleId=1319973106018529351, tenantId=1146029695717560320, journalId=1263187385517883426, language=EN, title=Electrochemical Properties of Hierarchical Porous Carbon by Activation of Tripotassium Phosphate, columnId=1319726165087077079, journalTitle=Journal of the Chinese Ceramic Society, columnName=Research Article, runingTitle=null, highlight=null, articleAbstract=
Introduction

The surface properties, pore size distribution and specific surface area of porous carbon are the main factors affecting its electrochemical performance. To further improve the electrochemical properties of porous carbon materials, two commonly used strategies are activation and doping with non-metallic heteroatoms. In this paper, a hierarchical porous carbon (HPC) was prepared by a one-step carbonation-activation method with poly(vinylpyrrolidone) as a carbon source, fibrous brucite as a template, and trispotassium phosphate as an activator to achieve the passive regulation of the pore structure and surface properties of porous carbon. The pore structure and specific surface area of hierarchical porous carbon were modulated, and the in-situ doping of nitrogen atoms were achieved. In addition, the influence of tripotassium phosphate addition on the pore size distribution, specific surface area, pore structure and electrochemical properties of the porous carbon was also investigated.

Methods

A certain amount of polyvinylpyrrolidone (PVP), tripotassium phosphate and fibrous brucite were mixed with deionised water under ultrasonication and stirring, obtaining a homogeneously dispersed mixture. The mixture as a precursor was sintered in a tube furnace via high-temperature carbonization to obtain a template/carbon composite. Afterwards, the composite was acid washed to remove the template and dried, obtaining a hierarchical porous carbon. The physical phase, pore structure, morphology and elemental composition of the hierarchical porous carbon were analysed by X-ray difffraction (XRD), scanning electron microscopy (SEM), specific surface area measurement (BET), X-ray photoelectron spectroscopy (XPS) and energy dispersive spectroscopy (EDS). The electrochemical properties of hierarchical porous carbon were determined by galvanostatic charge-discharge (GCD), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) in a three-electrode system using Hg/HgO, Pt sheet and the obtained hierarchical porous carbon as reference, counter and working electrodes, respectively. For the preparation process of the working electrode, the synthesised hierarchical porous carbon, conductive carbon black and PTFE emulsion were mixed in a mortar at a mass ratio of 8∶1∶1, and the mixture with an appropriate amount of ethanol solution was ground into a homogeneous slurr. The slurry was coated on the nickel foam collector, dried, and then pressed in a manual hydraulic press for 5 min to obtain the working electrode.

Results and discussion

The results of XRD and EDS show that the characteristic diffraction peaks of potassium fluorosilicate appear in the synthesised hierarchical porous carbon in addition to the amorphous carbon, but their contrast capacitance hardly contributes. The hierarchical porous carbon has a one-dimensional hollow carbon tube stacked reticular structure, which is conducive to the rapid transfer of electrons. Meanwhile, the hierarchical porous carbon obtained after the activation of tripotassium phosphate contains abundant pores, which can provide a large number of active sites for the electrolyte ions and a convenient channel for the rapid diffusion and transport of ions. In addition, the microporosity and specific surface area of the activated hierarchical porous carbon increase significantly, compared with those of the unactivated porous carbon. The specific surface area and pore volume are 707.9 m2/g and 1.65 cm3/g, respectively. The large specific surface area and pore volume can lead to more active sites and diffusion channels. The results of XPS demonstrate that element N also appears in the hierarchical porous carbon, indicating that nitrogen in-situ doping is realised during the carbonisation process. The introduction of nitrogen improves the electrical conductivity and wettability of the carbon material, and also has active sites and pseudocapacitance. Compared with the unactivated porous carbon, the activated hierarchical porous carbon exhibits superior electrochemical properties due to its rich pore structure, suitable heteroatom doping and hierarchical porous structure.

Conclusions

Nitrogen-doped hierarchical porous carbon was synthesized by a one-step carbonation-activation method with fibrous brucite as a template and tripotassium phosphate as an activator. Meanwhile, the different additions of tripotassium phosphate could achieve the regulation of the morphology, specific surface area, pore structure and electrochemical properties of the hierarchical porous carbon. The hierarchical porous carbon with an appropriate addition of tripotassium phosphate exhibited high specific surface area and superior electrochemical properties. The results showed that the specific capacitance of HPC/K3 activated by tripotassium phosphate could reach 281.94 F/g at a current density of 0.5 A/g, which was greater than that of non-activated HPC/K0 (i.e., 200.31 F/g). The capacity retention rate after 8 000 charge-discharge cycles reached 84.7%. This study demonstrated that tripotassium phosphate activation could improve the electrochemical performance of porous carbon. In addition, this study could also provide some insights for the high value-added application of natural mineral fibrous brucite.

, authors=Fangfang LIU, Fushuo ZHANG, Li SUN, Jinan NIU, authorsList=Fangfang LIU, Fushuo ZHANG, Li SUN, Jinan NIU, authorCompany=null, correspAuthors=Jinan NIU, authorNote=

LIU Fangfang (1995-), female, Ph.D., Associate Professor. E-mail:

, correspAuthorsNote=
NIU Jinan (1981-), male, Ph.D., Associate Professor. E-mail:
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多孔炭的表面性质、孔径分布及比表面积是影响其电化学性能的主要因素。为了对多孔炭孔结构及电化学性能等进行调控,采用聚乙烯吡咯烷酮为碳源、纤维水镁石为模板、磷酸三钾为活化剂,通过一步炭化-活化法制备了分级多孔炭(HPC),并研究了磷酸三钾添加量对多孔炭孔径分布、比表面积及电化学性能的影响。基于X射线衍射、氮气吸脱附、扫描电镜、X射线光电子能谱、X射线能谱仪、横流充放电、循环伏安及交流阻抗等测试,结果表明:磷酸三钾活化后样品HPC/K3在0.5 A/g电流密度下比电容可达281.94 F/g,远高于未活化HPC/K0的200.31 F/g;经过8 000次充放电循环后容量保持率可达84.7%。研究表明磷酸三钾活化可以显著改善多孔炭的电化学性能,此外,以纤维水镁石为模板合成多孔炭,还可以为天然矿物纤维水镁石的高附加值应用提供新思路。

, authors=刘芳芳, 张富硕, 孙力, 牛继南, authorsList=刘芳芳, 张富硕, 孙力, 牛继南, authorCompany=null, correspAuthors=牛继南, authorNote=

刘芳芳(1995—),女,博士,副教授。

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牛继南(1981—),男,博士,副教授。
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磷酸三钾活化合成分级多孔炭及其电化学性能
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刘芳芳 , 张富硕 , 孙力 , 牛继南
硅酸盐学报 | 研究论文 2024,52(5): 1631-1642
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硅酸盐学报 |研究论文 2024 , 52 (5) : 1631 -1642
磷酸三钾活化合成分级多孔炭及其电化学性能
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刘芳芳 , 张富硕, 孙力, 牛继南
作者信息
  • 中国矿业大学材料与物理学院,江苏 徐州 221116
通讯作者:
牛继南(1981—),男,博士,副教授。
作者简介:

刘芳芳(1995—),女,博士,副教授。

Electrochemical Properties of Hierarchical Porous Carbon by Activation of Tripotassium Phosphate
Fangfang LIU , Fushuo ZHANG, Li SUN, Jinan NIU
Affiliations
  • School of Materials Science and Physics, China University of Mining and Technology, Xuzhou 221116, Jiangsu, China
  • Corresponding Author:
    NIU Jinan (1981-), male, Ph.D., Associate Professor. E-mail:

    LIU Fangfang (1995-), female, Ph.D., Associate Professor. E-mail:

出版时间: 2024-05-20 doi: 10.14062/j.issn.0454-5648.20230604
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多孔炭的表面性质、孔径分布及比表面积是影响其电化学性能的主要因素。为了对多孔炭孔结构及电化学性能等进行调控,采用聚乙烯吡咯烷酮为碳源、纤维水镁石为模板、磷酸三钾为活化剂,通过一步炭化-活化法制备了分级多孔炭(HPC),并研究了磷酸三钾添加量对多孔炭孔径分布、比表面积及电化学性能的影响。基于X射线衍射、氮气吸脱附、扫描电镜、X射线光电子能谱、X射线能谱仪、横流充放电、循环伏安及交流阻抗等测试,结果表明:磷酸三钾活化后样品HPC/K3在0.5 A/g电流密度下比电容可达281.94 F/g,远高于未活化HPC/K0的200.31 F/g;经过8 000次充放电循环后容量保持率可达84.7%。研究表明磷酸三钾活化可以显著改善多孔炭的电化学性能,此外,以纤维水镁石为模板合成多孔炭,还可以为天然矿物纤维水镁石的高附加值应用提供新思路。

纤维水镁石  /  磷酸三钾  /  多孔炭  /  电化学性能
Introduction

The surface properties, pore size distribution and specific surface area of porous carbon are the main factors affecting its electrochemical performance. To further improve the electrochemical properties of porous carbon materials, two commonly used strategies are activation and doping with non-metallic heteroatoms. In this paper, a hierarchical porous carbon (HPC) was prepared by a one-step carbonation-activation method with poly(vinylpyrrolidone) as a carbon source, fibrous brucite as a template, and trispotassium phosphate as an activator to achieve the passive regulation of the pore structure and surface properties of porous carbon. The pore structure and specific surface area of hierarchical porous carbon were modulated, and the in-situ doping of nitrogen atoms were achieved. In addition, the influence of tripotassium phosphate addition on the pore size distribution, specific surface area, pore structure and electrochemical properties of the porous carbon was also investigated.

Methods

A certain amount of polyvinylpyrrolidone (PVP), tripotassium phosphate and fibrous brucite were mixed with deionised water under ultrasonication and stirring, obtaining a homogeneously dispersed mixture. The mixture as a precursor was sintered in a tube furnace via high-temperature carbonization to obtain a template/carbon composite. Afterwards, the composite was acid washed to remove the template and dried, obtaining a hierarchical porous carbon. The physical phase, pore structure, morphology and elemental composition of the hierarchical porous carbon were analysed by X-ray difffraction (XRD), scanning electron microscopy (SEM), specific surface area measurement (BET), X-ray photoelectron spectroscopy (XPS) and energy dispersive spectroscopy (EDS). The electrochemical properties of hierarchical porous carbon were determined by galvanostatic charge-discharge (GCD), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) in a three-electrode system using Hg/HgO, Pt sheet and the obtained hierarchical porous carbon as reference, counter and working electrodes, respectively. For the preparation process of the working electrode, the synthesised hierarchical porous carbon, conductive carbon black and PTFE emulsion were mixed in a mortar at a mass ratio of 8∶1∶1, and the mixture with an appropriate amount of ethanol solution was ground into a homogeneous slurr. The slurry was coated on the nickel foam collector, dried, and then pressed in a manual hydraulic press for 5 min to obtain the working electrode.

Results and discussion

The results of XRD and EDS show that the characteristic diffraction peaks of potassium fluorosilicate appear in the synthesised hierarchical porous carbon in addition to the amorphous carbon, but their contrast capacitance hardly contributes. The hierarchical porous carbon has a one-dimensional hollow carbon tube stacked reticular structure, which is conducive to the rapid transfer of electrons. Meanwhile, the hierarchical porous carbon obtained after the activation of tripotassium phosphate contains abundant pores, which can provide a large number of active sites for the electrolyte ions and a convenient channel for the rapid diffusion and transport of ions. In addition, the microporosity and specific surface area of the activated hierarchical porous carbon increase significantly, compared with those of the unactivated porous carbon. The specific surface area and pore volume are 707.9 m2/g and 1.65 cm3/g, respectively. The large specific surface area and pore volume can lead to more active sites and diffusion channels. The results of XPS demonstrate that element N also appears in the hierarchical porous carbon, indicating that nitrogen in-situ doping is realised during the carbonisation process. The introduction of nitrogen improves the electrical conductivity and wettability of the carbon material, and also has active sites and pseudocapacitance. Compared with the unactivated porous carbon, the activated hierarchical porous carbon exhibits superior electrochemical properties due to its rich pore structure, suitable heteroatom doping and hierarchical porous structure.

Conclusions

Nitrogen-doped hierarchical porous carbon was synthesized by a one-step carbonation-activation method with fibrous brucite as a template and tripotassium phosphate as an activator. Meanwhile, the different additions of tripotassium phosphate could achieve the regulation of the morphology, specific surface area, pore structure and electrochemical properties of the hierarchical porous carbon. The hierarchical porous carbon with an appropriate addition of tripotassium phosphate exhibited high specific surface area and superior electrochemical properties. The results showed that the specific capacitance of HPC/K3 activated by tripotassium phosphate could reach 281.94 F/g at a current density of 0.5 A/g, which was greater than that of non-activated HPC/K0 (i.e., 200.31 F/g). The capacity retention rate after 8 000 charge-discharge cycles reached 84.7%. This study demonstrated that tripotassium phosphate activation could improve the electrochemical performance of porous carbon. In addition, this study could also provide some insights for the high value-added application of natural mineral fibrous brucite.

fibrous brucite  /  tripotassium phosphate  /  porous carbon  /  electrochemical
刘芳芳, 张富硕, 孙力, 牛继南. 磷酸三钾活化合成分级多孔炭及其电化学性能. 硅酸盐学报, 2024 , 52 (5) : 1631 -1642 . DOI: 10.14062/j.issn.0454-5648.20230604
Fangfang LIU, Fushuo ZHANG, Li SUN, Jinan NIU. Electrochemical Properties of Hierarchical Porous Carbon by Activation of Tripotassium Phosphate[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (5) : 1631 -1642 . DOI: 10.14062/j.issn.0454-5648.20230604
  • 中央高校基本科研业务费专项资金资助(2023QN1038)
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2024年第52卷第5期
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doi: 10.14062/j.issn.0454-5648.20230604
  • 接收时间:2023-08-14
  • 首发时间:2026-10-22
  • 出版时间:2024-05-20
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  • 收稿日期:2023-08-14
  • 修回日期:2023-10-07
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中央高校基本科研业务费专项资金资助(2023QN1038)
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    中国矿业大学材料与物理学院,江苏 徐州 221116

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牛继南(1981—),男,博士,副教授。
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2种不同金属材料的力学参数
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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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