非溶剂致相转换法诱导制备分级多孔碳材料用于提升电化学储能性质

doi:10.19799/j.cnki.2095-4239.2025.0320

摘要/Abstract

摘要：

氮掺杂碳材料兼具双电层和赝电容储能机制，是组装超级电容器理想的电极材料，孔隙率和氮掺杂水平是调控该材料性能的关键。在煅烧过程中，碳材料面临着孔隙率不高，内部结构易塌陷形成大孔的情况，影响电解质离子的储存。本工作利用非溶剂致相转换法和模板法，通过冷冻干燥和两步煅烧，制备了具有分级多孔结构的氮掺杂碳材料。采用扫描电子显微技术、比表面及孔隙分析和电化学测试，比较了不同制备方式和组分比例对于产物构效关系的影响。大孔结构为电解质离子迁移提供了快速通道，丰富的微介孔结构则为电解质离子创造了存储空间，更暴露出更多氮掺杂的活性位点。对照实验表明，使用非溶剂致相转换法且添加有100 mg改性ZIF-8颗粒的PC-PZ100具有明显的储能优势，在0.1 A/g的电流密度下，比电容高达766.0 F/g，经过7000次循环充放电测试后，比电容仍为初始值的105.5%，循环稳定性优越。将PC-PZ100组装为对称型超级电容器时，能量密度为18.5 Wh/kg(功率密度为249.5 W/kg)，展现出了优异的储能性质。

关键词: 分级多孔碳, 非溶剂致相转换, 氮掺杂, 超级电容器

Abstract:

Nitrogen-doped carbon materials store charge through both electric double-layer capacitance and pseudocapacitance, making them promising electrode candidates for supercapacitors. Their performance strongly depends on porosity and nitrogen-doping level. However, carbon materials often undergo structural collapse during calcination, leading to low porosity and large pore sizes, which hinder electrolyte ion transport and storage. In this study, nitrogen-doped carbon materials with hierarchical porous structures were fabricated using a non-solvent phase inversion technique combined with a template method. Scanning electron microscopy, specific surface area and porosity analyses, and electrochemical measurements were employed to investigate the structure-performance relationships of materials prepared with different methods and components. The macroporous structure provided rapid ion transport channels, while the abundant microporous and mesoporous structures offered ion storage sites and exposed additional nitrogen-doped active centers. Experimental results demonstrated that the sample prepared via non-solvent phase inversion with the addition of 100 mg of modified ZIF-8 particles (PC-PZ100) exhibited superior energy storage performance. The specific capacitance reached 766.0 F/g at 0.1 A/g. After 7000 charge-discharge cycles, the capacitance retention remained at 105.5%, indicating excellent cycling stability. When assembled into a symmetric supercapacitor, PC-PZ100 achieved an energy density of 18.5 Wh/kg at a power density of 249.5 W/kg, confirming its outstanding electrochemical energy storage capability.

Key words: hierarchical porous carbon, non-solvent phase inversion, nitrogen doping, supercapacitor

中图分类号:

TM 53

徐钟韵, 严丽霞, 秦羽, 郭敬轩. 非溶剂致相转换法诱导制备分级多孔碳材料用于提升电化学储能性质[J]. 储能科学与技术, 2025, 14(11): 4112-4122.

Zhongyun XU, Lixia YAN, Yu QIN, Jingxuan GUO. Hierarchical porous carbon via non-solvent phase inversion for enhancing electrochemical energy storage[J]. Energy Storage Science and Technology, 2025, 14(11): 4112-4122.

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处理方式	PC	PC-PZ50	PC-PZ100	PC-PZ200	P-PZ	PC-Z8	(H)PC-PZ	(G)PC-PZ
使用前驱体(含量)	0	PZ(50 mg)	PZ(100 mg)	PZ(200 mg)	PZ(100 mg)	PZ(100 mg)	PZ(100 mg)	PZ(100 mg)
是否使用CNT	是	是	是	是	否	是	是	是
制备方法	●	●	●	●	●	●	●	◎
浸泡溶液	饱和NaCl	饱和NaCl	饱和NaCl	饱和NaCl	饱和NaCl	饱和NaCl	去离子水	无

Electrode material	Content of doped elements(at) /%	Specific surface area /(m²/g)	Specific capacitance /(F/g)	Ref.
N, P co-doped porous carbon	N-5.42 P-5.35	286.5	160 (1 A/g)	26
N, O co-doped carbon nanofibers	N-5.26 O-10.38	492.5	125.2 (1 A/g)	27
B, N co-doped carbon nanofibers	N-11.24 B-1.3	351.3	295 (0.5 A/g)	28
N, P co-doped carbon aerogel	pyridinic N and pyrrolic N-3.53	332.05	235 (0.5 A/g)	29
N, S, co-doped porous carbon	N-12.45 S-4.19	473	159 (1 A/g)	30
N, P co-doped carbon	N-5.18	461.61	227 (1 A/g)	31
N, co-doped carbon	N-13.93	365	326 (1 A/g)	32
PC-PZ100	N-13.33	356.99	315.1 (1 A/g)	This work

电阻值	PC	PC-PZ50	PC-PZ100	PC-PZ200	P-PZ
R1(Ω)	1.88	1.22	1.49	2.98	2.14
R2(Ω)	0.92	0.76	0.82	0.79	1.40