高负载梓树豆荚壳衍生多孔碳材料的电化学性能研究

doi:10.11949/0438-1157.20250463

摘要/Abstract

摘要：

以梓树豆荚壳为碳源，KOH为活化剂，制备了分层多孔生物质碳材料（ACPSC），并通过改变KOH的比例对多孔碳孔结构及性能进行调控。结构表征和性能测试结果表明：当梓树豆荚壳与KOH质量比为1∶1时获得ACPSC-1∶1样品表现出最优的比表面积（1140.8 m²·g^-1）和电化学性能（在1 A·g^-1电流密度下，比容量为271 F·g^-1）；在13 mg·cm^-2的高负载下，ACPSC-1∶1的质量比容量和面积比容量分别为125 F·g^-1和1392.3 mF·cm^-2。组装的对称超级电容器，在664 W·kg^-1的功率密度下表现出7.84 Wh·kg^-1的能量密度，即使在12.9 kW·kg^-1的超高功率密度下，能量密度仍高达6.07 Wh·kg^-1，充分展现了其在高功率、高负载超级电容器中的应用潜力。

关键词: 梓树豆荚壳, 生物质衍生碳材料, 多孔碳, KOH活化, 超级电容器

Abstract:

Hierarchical porous biomass carbon materials (ACPSCs) were prepared using Catalpa chinensis pods as the carbon source and KOH as the activator. The pore structure and properties of the porous carbons were tunable by varying the KOH ratio. Structural characterization and performance testing results indicated that the ACPSC-1∶1 sample, obtained at a mass ratio of catalpa pod shells to KOH of 1∶1, exhibited the highest specific surface area (1140.8 m²·g⁻¹) and electrochemical performance (a specific capacitance of 271 F·g⁻¹ at a current density of 1 A·g⁻¹). Under a high mass loading of 13 mg·cm⁻², ACPSC-1∶1 had gravimetric and areal specific capacitances of 125 F·g⁻¹ and 1392.3 mF·cm⁻², respectively. The assembled symmetric supercapacitor exhibited an energy density of 7.84 Wh·kg⁻¹ at a power density of 664 W·kg⁻¹; even at an ultrahigh power density of 12.9 kW·kg⁻¹, the energy density still reached 6.07 Wh·kg⁻¹. These results fully demonstrate its great potential for high-power and high-mass-loading supercapacitor applications.

Key words: catalpa pod shells, biomass derived carbon materials, porous carbon, KOH activation, supercapacitor

中图分类号:

TM 53

王煜晨, 王万宗, 张鑫, 郭茂强, 周晓明, 盛利志. 高负载梓树豆荚壳衍生多孔碳材料的电化学性能研究[J]. 化工学报, 2025, 76(12): 6748-6760.

Yuchen WANG, Wanzong WANG, Xin ZHANG, Maoqiang GUO, Xiaoming ZHOU, Lizhi SHENG. Electrochemical performance of high-mass-loading porous carbons derived from catalpa pod shells[J]. CIESC Journal, 2025, 76(12): 6748-6760.

图/表 14

图1 （a）CPSC；（b）ACPSC-1∶1；（c）ACPSC-2∶1；（d）ACPSC-1∶2的SEM图像；（e）~（h）ACPSC-1∶1 的元素映射谱图

Fig.1 SEM images of (a) CPSC， (b) ACPSC-1∶1， (c) ACPSC-2∶1， (d) ACPSC-1∶2; (e)~(h) Element mapping spectrum of ACPSC-1∶1

图2 ACPSC-1∶1的TEM图像

Fig.2 TEM image of ACPSC-1∶1

图3 CPSC和ACPSC-X系列样品的（a）XRD谱图和（b）拉曼光谱谱图

Fig.3 (a) XRD and (b) Raman patterns of the CPSC and ACPSC-X series samples

图4 CPSC和ACPSC-X系列样品的（a）N2吸附-脱附等温线和（b）孔径分布

Fig.4 (a) N2 adsorption and desorption isotherms and (b) pore size distributions of CPSC and ACPSC-X series samples

图5 （a）不同样品的XPS全谱图；（b）ACPSC-1∶1的C 1s；（c）O 1s；（d）N 1s高分辨XPS谱图

Fig.5 (a) Full XPS spectra of different samples; (b) ACPSC-1∶1 C 1s; (c) O 1s; (d) High-resolution XPS spectra of N 1s

图6 CPSC和ACPSC- X系列样品（a）在100 mV·s-1扫描速率下的CV曲线；（b）在1 A·g-1电流密度下的GCD曲线

Fig.6 (a) CV curves of CPSC and ACPSC- X series samples at a scanning rate of 100 mV·s-1; (b) The GCD curves at current density of 1 A·g-1

图7 （a）ACPSC-1∶1的CV曲线；（b）充放电电流与扫描速率的函数关系图；（c）GCD曲线和（d）不同样品在不同电流密度下的比容量

Fig.7 (a) CV curve of ACPSC-1∶1; (b) Functional relationship graph of charge and discharge current and scanning rate; (c) GCD curve and (d) specific capacitance of different samples at different current densities

图8 CPSC和ACPSC- X系列样品的（a）EIS曲线；（b）电荷转移电阻值；（c）频率响应；（d）弛豫时间

Fig.8 (a) EIS curves; (b) charge transfer resistance values; (c) frequency response; (d) relaxation time of CPSC and ACPSC- X series samples

表1 CPSC与ACPSC-X系列样品阻抗拟合值

Table 1 Impedance fitting values of CPSC and ACPSC-X series samples

Sample	R_s/Ω	R_ct/Ω	W_O-R	W_O-T	W_O-P
CPSC	0.25	0.203	0.822	0.048	0.443
ACPSC-2∶1	0.178	0.096	0.479	0.053	0.463
ACPSC-1∶1	0.142	0.046	0.373	0.039	0.472
ACPSC-1∶2	0.163	0.059	0.42	0.049	0.469

图9 ACPSC-1∶1不同负载量的（a）CV曲线和（b）GCD曲线

Fig.9 (a) CV curves and (b) GCD curves of ACPSC-1∶1 with different mass loadings

图10 ACPSC-1∶1负载为13 mg·cm-2的（a）CV曲线；（b）GCD曲线；在不同负载量下的（c）质量比容量和（d）面积比容量

Fig.10 (a) CV curve; (b) GCD curve of ACPSC-1∶1 loading at 13 mg·cm-2; (c) specific capacitance and (d) area-to-capacitance of different mass loading capacities

表2 ACPSC-1∶1与已报道文献中高质量负载电极电化学性能对比

Table 2 Comparison of the electrochemical performance of ACPSACPSC-1∶1 with previously reported high-mass-loading electrodes

电极	质量负载/(mg·cm^-2)	1 A·g^-1电流密度下电化学性能/(F·g^-1)	文献
MGC-700	13	110	[34]
N,S co-doped carbon nanoflowers	13	39	[35]
SL/W-2	13	122	[36]
ACPSC-1∶1	13	125	—

图11 ACPSC-1∶1电流密度为10 A·g-1时的循环稳定性

Fig.11 Cyclic stability of ACPSC-1∶1 at 10 A·g-1 current density

图12 ACPSC-1∶1//ACPSC-1∶1对称超级电容器的（a）CV曲线；（b）GCD曲线；（c）Ragone图

Fig.12 (a) CV curves; (b) GCD curves; (c)Ragone plots for ACPSC-1∶1//ACPSC-1∶1 symmetric supercapacitor

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