钾铁协同活化煤基多孔炭的制备及其电化学性能

张浩然; 姚素玲; 董宪姝; 付元鹏; 樊玉萍

doi:10.12476/kczhly.202403210109

钾铁协同活化煤基多孔炭的制备及其电化学性能

太原理工大学　矿业工程学院，山西　太原　030024

基金项目: 山西省重点研发计划（202202090301009）；山西省基础研究计划项目（202103021223045）

详细信息

作者简介: 张浩然（1997-），男，硕士，从事煤基碳材料方面的科研工作

通讯作者: 姚素玲（1969-），女，副教授，从事矿物材料方面的研究工作

中图分类号: TD985

收稿日期: 2024-03-21

刊出日期: 2025-08-25

Preparation of Potassium-iron Co-activated Coal-based Porous Carbon and its Electrochemical Performance

School of Mining Engineering, Taiyuan University of Science and Technology, Taiyuan, Shanxi 030024, China

More Information

Corresponding author: YAO Suling, yaosuling@tyut.edu.cn

Received Date: 21 March 2024

Publish Date: 25 August 2025

摘要

摘要:
以晋城无烟煤为研究对象，并以绿色无污染的高铁酸钾（K₂FeO₄）作为活化剂，其中钾基物质作为活化造孔剂，铁基物质催化石墨化，通过一次活化获得了孔隙丰富且具有一定的石墨微晶结构的电容器用煤基多孔炭。研究了较佳的活化温度与药剂用量，并通过扫描电镜、氮吸附测试、Raman 光谱、XRD 等手段对典型样品的理化结构进行了分析，评价了其电化学储能特性。在此基础上，尝试探究N、P元素掺杂对多孔炭的结构及电化学性能的影响。结果表明，在K₂FeO₄一步化学活化过程中，多孔炭孔隙结构由极微孔向微孔和分级孔演变，炭微晶由无定形向石墨化结构演变；当煤与K₂FeO₄按质量1∶1，活化温度为900 ℃时，多孔炭的比表面积达到1 220.82 m²/g；在0.5 A/g 电流密度时，其电容值为149.47 F/g ，即使在10 A/g高电流密度时，仍有77.39%的比电容保持率；掺杂N、P元素后的多孔炭电化学性能也得到一定提升，比电容可达167.45 F/g，比电容保持率提升至87.98%。该多孔炭具有价格低廉、易获取、绿色环保等优势，具备潜在的工业应用价值。
- 无烟煤 /
- 煤基多孔炭 /
- 钾铁协同活化 /
- 氮磷掺杂 /
- 电极材料 /
- 超级电容器
Abstract:
A coal-based porous carbon was prepared through a single activation process. Jincheng smokeless coal was taken as the research object and ferrate (K₂FeO₄) as the activator. Meanwhile, potassium-based substances were served as pore-forming agents and iron-based substances contributed to the catalyzing graphitization. The optimal activation temperature and activator dosage were investigated, and the physicochemical structure of representative samples was analyzed using techniques including Scanning Electron Microscopy(SEM), nitrogen adsorption testing, Raman spectroscopy and X-ray diffraction(XRD). The electrochemical energy storage characteristics were evaluated. On this basis, the effect of N and P element doping on the structure and electrochemical performance of the porous carbon was investigated. The results indicate that, the pore structure of the porous carbon evolves from ultra-micropores to micropores and hierarchical pores, while the carbon microcrystals transition from amorphous to graphitic structures during the one-step chemical activation process with K₂FeO₄. Specifically, with a coal-to-K₂FeO₄ mass ratio of 1:1 and an activation temperature of 900 ℃, the porous carbon attains a specific surface area of 1 220.82 m²/g. At a current density of 0.5 A/g, its capacitance reaches 149.47 F/g, and even at a high current density of 10 A/g, a capacitance retention rate of 77.39% is maintained. The electrochemical performance of the porous carbon is also enhanced to a certain extent after N and P element doping, with a specific capacitance reaching 167.45 F/g, and the capacitance retention rate increased to 87.98%. This porous carbon material, which is characterized by its cost-effectiveness, accessibility, and environmental friendliness, has great potential for industrial applications.
- smokeless coal /
- coal-based porous carbon /
- co-activation of potassium and iron /
- nitrogen and phosphorus doping /
- electrode material /
- supercapacitor

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图 1 不同活化温度样品的XRD

Figure 1.

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图 2 不同活化温度样品的Raman

Figure 2.

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图 3 不同活化温度制得多孔炭的SEM

Figure 3.

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图 4 不同K₂FeO₄用量样品的XRD

Figure 4.

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图 5 不同K₂FeO₄用量样品的Raman

Figure 5.

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图 6 不同K₂FeO₄用量制得多孔炭的SEM

Figure 6.

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图 7 CV测试曲线

Figure 7.

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图 8 GCD测试曲线

Figure 8.

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图 9 活化温度对多孔炭比电容的影响

Figure 9.

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图 10 K₂FeO₄用量对多孔炭比电容的影响

Figure 10.

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图 11 掺杂元素前后多孔炭的XRD

Figure 11.

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图 12 掺杂元素对比电容的影响

Figure 12.

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图 13 K₂FeO₄活化造孔和石墨化以及N、P掺杂机理

Figure 13.

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表 1 晋城无烟煤工业分析与元素分析

Table 1. Proximate and elemental analysis of Jincheng smokeless coal

工业分析/(%，ad)				元素分析/(%，daf)
M	A	V	FC	C	H	N	St	O
0.69	5.91	8.81	84.59	92.07	3.79	1.27	0.31	2.56

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表 2 不同活化温度样品的Raman参数及产率

Table 2. Raman parameters and yields of samples at different activation temperature

活化温度/℃	700	800	900	1 000
I_D/I_G	0.999 7	0.993 4	0.985 8	0.977 1
产率/%	28.70	22.26	21.17	18.46

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表 3 活化温度对多孔炭孔结构参数的影响

Table 3. Effect of activation temperature on pore structure parameters of porous carbon

样品	S_BET/(m²/g)	V_total/(cm³/g)	D_ave/nm	<2 nm		2～50 nm		>50 nm
样品	S_BET/(m²/g)	V_total/(cm³/g)	D_ave/nm	V_mic/(cm³/g)	占比/%	V_mec/(cm³/g)	占比/%	V_mac/(cm³/g)	占比/%
原煤	7.03	0.012	6.66	0.000 4	3.42	0.01	77.04	0.002	19.54
C-700	865.92	0.42	1.73	0.34	81.25	0.08	18.29	0.002	0.47
C-800	1 221.13	0.62	1.80	0.47	76.17	0.14	23.09	0.005	0.74
C-900	1 220.83	0.63	1.80	0.49	77.24	0.13	21.27	0.009	1.49
C-1000	1 169.80	0.67	1.92	0.47	69.88	0.197	29.45	0.005	0.67

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表 4 不同K₂FeO₄用量样品的Raman参数、产率及Fe元素含量

Table 4. Raman parameters, yields and Fe content of samples with different K₂FeO₄ dosages

M_煤:${{\rm{M}}_{{{\rm{K}}_{\rm{2}}}{\rm{Fe}}{{\rm{O}}_{\rm{4}}}}} $	2∶1	2∶2	2∶3	2∶4
I_D/I_G	0.995 6	0.985 8	1.002 2	0.999 1
产率/%	46.10	21.17	14.58	11.30
Fe元素含量/%	0.55	0.35	1.60	2.06

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表 5 K₂FeO₄用量对多孔炭孔结构参数的影响

Table 5. Effect of K₂FeO₄ dosage on pore structure parameters of porous carbon

样品	S_BET	V_total	D_ave	<2 nm		2～50 nm		>50 nm
	/（m²/g）	/(cm³/g)	/nm	V_mic/(cm³/g)	占比/%	V_mec/(cm³/g)	占比/%	V_mac/(cm³/g)	占比/%
KFe-1	656.85	0.30	1.73	0.25	83.02	0.05	16.05	0.003	0.93
KFe-2	1 220.83	0.63	1.81	0.49	77.24	0.13	21.27	0.009	1.49
KFe-3	1 411.78	0.97	2.80	0.18	18.36	0.78	79.85	0.018	1.80
KFe-4	1 494.24	0.88	2.34	0.29	33.39	0.58	65.67	0.008	0.94

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表 6 掺杂元素前后多孔炭的O、N、P含量对比/%

Table 6. Comparison of O, N and P content of porous carbon before and after element doping

样品	O	N	P
C-900	5.81	0.76	0.01
NP-900	7.19	1.60	1.66

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