碱/尿素溶解体系制备氮掺杂活性炭及其电化学性能研究

doi:10.3969/j.issn.0253-2417.2021.02.002

林产化学与工业 ›› 2021, Vol. 41 ›› Issue (2): 10-16.doi: 10.3969/j.issn.0253-2417.2021.02.002

碱/尿素溶解体系制备氮掺杂活性炭及其电化学性能研究

杨旋¹(), 郑新宇³, 吕建华¹, 应浩⁴, 黄彪¹, 林冠烽¹^,²^,*()

1. 福建农林大学材料工程学院, 福建福州 350002
2. 福建农林大学金山学院, 福建福州 350002
3. 福建农林大学生命科学学院, 福建福州 350002
4. 中国林业科学研究院林产化学工业研究所, 江苏南京 210042

收稿日期:2020-11-11 出版日期:2021-04-28 发布日期:2021-05-08
通讯作者: 林冠烽 E-mail:fafuyxYX@163.com;feton.lin@hotmail.com
作者简介:林冠烽, 副教授, 硕士生导师, 主要从事林产化学与工业的研究; E-mail: feton.lin@hotmail.com
杨旋(1994-), 男, 湖北襄阳人, 博士生, 研究方向为生物质能源与炭材料; E-mail: fafuyxYX@163.com
基金资助:
国家重点研发计划资助项目(2017YFD0601006);国家自然科学基金资助项目(31770611);国家自然科学基金资助项目(31870561)

Preparation of Nitrogen-doped Activated Carbon from Alkali/Urea Dissolution System and Its Electrochemical Properties

Xuan YANG¹(), Xinyu ZHENG³, Jianhua LYU¹, Hao YING⁴, Biao HUANG¹, Guanfeng LIN¹^,²^,*()

1. College of Material Engineering, Fujian Agriculture and Forestry University, Fuzhou 350002, China
2. Jinshan College, Fujian Agriculture and Forestry University, Fuzhou 350002, China
3. College of Life Science, Fujian Agriculture and Forestry University, Fuzhou 350002, China
4. Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, Nanjing 210042, China

Received:2020-11-11 Online:2021-04-28 Published:2021-05-08
Contact: Guanfeng LIN E-mail:fafuyxYX@163.com;feton.lin@hotmail.com

摘要/Abstract

摘要：

以杉木屑为原料，三聚氰胺固体废弃物（OAT）为氮源，基于碱/尿素体系溶解纤维素，通过一步热解制备氮掺杂活性炭，并考察活化温度和OAT加入量对活性炭的吸附性能和电化学性能的影响。通过X射线光电子能谱（XPS）和比表面积分析仪分析材料的表面结构和孔结构；采用循环伏安（CV）、恒流充放电（GCD）和交流阻抗（EIS）等测试手段表征其电化学性能。研究结果表明：随着OAT质量分数的增加，活性炭样品得率和吸附性能先增加后减小；OAT的添加有利于提高氮掺杂活性炭的得率、氮含量、吸附性能和电化学性能；炭材料的比表面积及其孔隙结构促进活性炭样品电化学性能的提升。当活化温度900℃，OAT质量分数为15%下，制备的氮掺杂活性炭的得率为34.2%，碘吸附值为1 116 mg/g，亚甲基蓝吸附值为165 mg/g，比表面积为1 324 m²/g，含氮量3.5%。在6 mol/L KOH电解液中，当电流密度1 A/g时，比电容可达193 F/g。

关键词: OAT, 碱/尿素体系, 氮掺杂活性炭, 电化学性能

Abstract:

Nitrogen-doped activated carbon was fabricated by one-step pyrolysis with Chinese fir sawdust as raw material, melamine solid waste(oxhydryl and amino triazine, OAT) as nitrogen-rich source, alkali/urea system as solvent. The effects of activation temperatures and melamine solid waste dosage on adsorption performance and electrochemistry performance of activated carbon were investigated. X-ray photoelectron spectroscopy(XPS) and specific surface area analyzer were used to study the surface structure and pore structure of the material. Cyclicvoltammetry(CV) curves, galvanostatical charge/discharge(GCD) and electrochemical impedance spectroscopy(EIS) were used to test the electrochemical performance of samples. The results showed that with the increase of melamine solid waste content, the yield and adsorption performance of activated carbon samples increased first and then decreased; the addition of melamine solid waste was beneficial to increase the yield, nitrogen content, adsorption performance and electrochemical performance of nitrogen-doped activated carbon. The specific surface area and pore structure of carbon materials affected the electrochemical performance of activated carbon samples. When the activation temperature was 900 ℃ and the melamine solid waste content was 15%, the yield of nitrogen-doped activated carbon was 34.2%, the iodine adsorption value was 1 116 mg/g, and the methylene blue adsorption value was 165 mg/g, specific surface area was 1 324 m²/g, nitrogen content was 3.5%. In the 6 mol/L KOH electrolyte, the specific capacitance could reach 193 F/g when the current density was 1 A/g.

Key words: OAT, alkali/urea system, nitrogen-doped activated carbon, electrochemical performance

中图分类号:

杨旋, 郑新宇, 吕建华, 应浩, 黄彪, 林冠烽. 碱/尿素溶解体系制备氮掺杂活性炭及其电化学性能研究[J]. 林产化学与工业, 2021, 41(2): 10-16.

Xuan YANG, Xinyu ZHENG, Jianhua LYU, Hao YING, Biao HUANG, Guanfeng LIN. Preparation of Nitrogen-doped Activated Carbon from Alkali/Urea Dissolution System and Its Electrochemical Properties[J]. Chemistry and Industry of Forest Products, 2021, 41(2): 10-16.

图/表 8

图1

图2

表1

图3

表2

图4

图5

图6

参考文献 24

1	LI X , LE Z , HE G . Fe₃O₄ doped double-shelled hollow carbon spheres with hierarchical pore network for durable high-performance supercapacitor[J]. Carbon, 2016, 99, 514- 522. doi: 10.1016/j.carbon.2015.12.076
2	CHEN C U, QIN H, CONG H I, et al. A highly stretchable and real-time healable supercapacitor[J/OL]. Advanced Materials, 2019, 31: 1-10[2020-03-20]. https://doi.org/10.1002/adma.201900573.
3	WANG Y, SU S, CAI L, et al. Monolithic integration of all-in-one supercapacitor for 3D electronics[J/OL]. Advanced Energy Materials, 2019, 9(15): 1-9[2020-03-20]. https://doi.org/10.1002/aenm.201900037.
4	GUARDIA L , SUREZ L , QUEREJETA N , et al. Biomass waste-carbon/reduced graphene oxide composite electrodes for enhanced supercapacitors[J]. Electrochimica Acta, 2019, 298, 910- 917. doi: 10.1016/j.electacta.2018.12.160
5	ZHU Y Y , CHEN M M , ZHANG Y , et al. A biomass-derived nitrogen-doped porous carbon for high-energy supercapacitor[J]. Carbon, 2018, 140, 404- 412. doi: 10.1016/j.carbon.2018.09.009
6	LI L , ZHONG Q F , KIM N D , et al. Nitrogen-doped carbonized cotton for highly flexible supercapacitors[J]. Carbon, 2016, 105, 260- 267. doi: 10.1016/j.carbon.2016.04.031
7	吴登鹏, 姚路, 林烨, 等. 氮掺杂活性炭的制备及其性能研究[J]. 电源技术, 2019, 43 (9): 1478- 1481. doi: 10.3969/j.issn.1002-087X.2019.09.019
	WU D P , YAO L , LIN Y , et al. Synthesis and electrochemical performance of nitrogen-doped activated carbon[J]. Chinese Journal of Power Sources, 2019, 43 (9): 1478- 1481. doi: 10.3969/j.issn.1002-087X.2019.09.019
8	CAI J , ZHANG L , LIU S , et al. Dynamic self-assembly induced rapid dissolution of cellulose at low temperatures[J]. Macromolecules, 2008, 41 (23): 9345- 9351. doi: 10.1021/ma801110g
9	CAI J , ZHANG L , ZHOU J , et al. Multifilament fibers based on dissolution of cellulose in NaOH/urea aqueous solution: Structure and properties[J]. Advanced Materials, 2007, 19 (6): 821- 825. doi: 10.1002/adma.200601521
10	CAI Z H , YANG X , LIN G F , et al. On preparing highly abrasion resistant binderless and in situ N-doped granular activated carbon[J]. RSC Advances, 2018, 8 (36): 20327- 20333. doi: 10.1039/C8RA03243B
11	YANG X, WANG Q, LAI J J, et al. Nitrogen-doped activated carbons via melamine-assisted NaOH/KOH/urea aqueous system for high performance supercapacitors[J/OL]. Materials Chemistry and Physics, 2020, 250: 1-10[2020-03-25]. https://doi.org/10.1016/j.matchemphys.2020.123201.
12	杨旋, 何晨露, 熊永志, 等. 基于碱/尿素溶解体系的自黏结颗粒活性炭的制备[J]. 林产化学与工业, 2020, 40 (3): 130- 134.
	YANG X , HE C L , XIONG Y Z , et al. Preparation of self-bonding granular activated carbon by alkali/urea dissolution system[J]. Chemistry and Industry of Forest Products, 2020, 40 (3): 130- 134.
13	董妍妍. 三聚氰胺生产过程中的固体废弃物资源化利用研究[D]. 郑州: 郑州大学, 2012.
	DONG Y Y. The resource utilization of soild waste from melamine production process[D]. Zhengzhou: Zhengzhou University, 2012.
14	陈明. 固体废弃物利用现状及管理对策研究[J]. 农业与技术, 2013, 33 (9): 228- 231. doi: 10.3969/j.issn.1671-962X.2013.09.194
	CHEN M . Research on current situation of solid waste utilization and management countermeasures[J]. Agriculture and Technology, 2013, 33 (9): 228- 231. doi: 10.3969/j.issn.1671-962X.2013.09.194
15	CHEN Y , HUANG B , HUANG M , et al. Sticky rice lime mortar-inspired in situ sustainable design of novel calcium-rich activated carbon monoliths for efficient SO₂ capture[J]. Journal of Cleaner Production, 2018, 183, 449- 457. doi: 10.1016/j.jclepro.2018.02.167
16	ZHONG C G , GONG S L , JIN L , et al. Preparation of nitrogen-doped pitch-based carbon materials for supercapacitors[J]. Materials Letters, 2015, 156, 1- 6. doi: 10.1016/j.matlet.2015.04.127
17	ZHOU J H, MA F, GUO H J. Adsorption behavior of tetracycline from aqueous solution on ferroferric oxide nanoparticles assisted powdered activated carbon[J/OL]. Chemical Engineering Journal, 2020, 384: 1-8[2020-04-02]. https://doi.org/10.1016/j.cej.2019.123290.
18	孙康, 蒋剑春, 卢辛成, 等. 高温自生压活化制备高微孔率活性炭研究[J]. 林产化学与工业, 2015, 35 (4): 53- 58.
	SUN K , JIANG J C , LU X C , et al. Preparation of high microporosity activated carbon by autogenic pressure under high temperature[J]. Chemistry and Industry of Forest Products, 2015, 35 (4): 53- 58.
19	ZHOU M , PU F , WANG Z , et al. Nitrogen-doped porous carbons through KOH activation with superior performance in supercapacitors[J]. Carbon, 2014, 68, 185- 194. doi: 10.1016/j.carbon.2013.10.079
20	YANG M, ZHOU Z. Recent breakthroughs in supercapacitors boosted by nitrogen-rich porous carbon materials[J/OL]. Advanced Science, 2017, 4(8): 1-10[2020-05-21]. https://doi.org/10.1002/advs.201600408.
21	GUO D D , XIN R R , ZHANG Z , et al. N-doped hierarchically micro- and mesoporous carbons with superior performance in supercapacitors[J]. Electrochimica Acta, 2018, 291, 103- 113. doi: 10.1016/j.electacta.2018.08.109
22	毕宏晖, 焦帅, 魏风, 等. 珊瑚状氮掺杂多孔碳的制备及其超电容性能[J]. 化工学报, 2020, 71 (6): 2880- 2888.
	BI H H , JIAO S , WEI F , et al. Preparation of coral-like nitrogen-doped porous carbons and its supercapacitive properties[J]. Journal of Chemical Industry and Engineering, 2020, 71 (6): 2880- 2888.
23	牛文娟, 冯雨欣, 钟菲, 等. 秸秆微波水热炭和活性炭理化及电化学特性[J]. 农业工程学报, 2020, 36 (17): 202- 211.
	NIU W J , FENG Y X , ZHONG F , et al. Physicochemical and electrochemical properties of microwave-assisted hydrochars and activated carbons from straws[J]. Transactions of the Chinese Society of Agricultural Engineering, 2020, 36 (17): 202- 211.
24	BAO J P , LIANG C , LU H Y , et al. Facile fabrication of porous carbon microtube with surrounding carbon skeleton for long-life electrochemical capacitive energy storage[J]. Energy, 2018, 155, 899- 908. doi: 10.1016/j.energy.2018.04.151

样品sample	温度/℃temperature	OAT/%	S_BET/(m²·g^-1)	总孔孔容/(cm³·g^-1)total pore volume	微孔孔容/(cm³·g^-1)micropore volume	介孔孔容/(cm³·g^-1)mesopore volume	平均孔径/nmaverage pore size
No.1	900	0	1256	0.76	0.53	0.23	2.36
No.2	800	15	1034	0.54	0.46	0.08	2.31
No.3	850	15	1120	0.62	0.51	0.11	2.30
No.4	900	15	1324	0.92	0.58	0.34	2.34

样品samples	C	N	O	N-6(吡啶型)N-6(pyridinic)	N-5(吡咯型)N-5(pyrrolic)	N-Q(季氮型)N-Q(quaternary)
No.1	85.07	1.88	13.05	37.1	54.4	8.5
No.2	78.23	4.59	17.20	40.8	28.2	21.0
No.3	87.70	3.94	8.27	39.2	42.7	18.1
No.4	83.84	3.50	12.66	47.0	31.7	21.3

[1]	钟伟婷, 韩尊强, 刘畅, 王堃. 降解木基多孔炭材料的制备及其性能研究[J]. 林产化学与工业, 2021, 41(2): 86-92.
[2]	杨旋,何晨露,熊永志,林冠烽,陈燕丹,黄彪. 基于碱/尿素溶解体系的自黏结颗粒活性炭的制备[J]. 林产化学与工业, 2020, 40(3): 130-134.
[3]	张文, 许升, 吕宗泽, 李志国. 氮氧掺杂木质素基炭材料的制备及其电化学性能[J]. 林产化学与工业, 2018, 38(3): 55-62.
[4]	杨喜, 孔令宇, 刘杏娥, 马建锋, 江泽慧. 纤维素导电气凝胶及其复合材料在超级电容器中应用的研究进展[J]. 林产化学与工业, 2018, 38(1): 1-8.
[5]	侯敏, 孙康, 邓先伦, 肖凤龙, 林冠烽. 氧化-超声波除钾对活性炭材料电化学性能的影响[J]. 林产化学与工业, 2016, 36(4): 49-54.
[6]	陈继锡, 左宋林, 王永芳, 郝婧. 磷酸法活性炭的三聚氰胺表面改性及其电化学性能研究[J]. 林产化学与工业, 2016, 36(2): 37-44.
[7]	司红燕, 商士斌, 廖圣良, 王丹, 宋湛谦. 水可分散型松香基聚酯多元醇的制备及耐热性研究[J]. 林产化学与工业, 2016, 36(1): 42-48.
[8]	孙云娟, 蒋剑春, 王燕杰, 应浩, 戴伟娣, 许乐. Coats-Redfern积分法研究生物质与煤单独热解和共热解动力学特性[J]. 林产化学与工业, 2014, 34(5): 8-14.
[9]	陈名柱;刘洪波;张东升;邓丛静;夏笑虹;何月德. 活化剂用量对竹基活性炭孔结构及电化学性能的影响[J]. 林产化学与工业, 2011, 31(4): 63-68.

碱/尿素溶解体系制备氮掺杂活性炭及其电化学性能研究

Preparation of Nitrogen-doped Activated Carbon from Alkali/Urea Dissolution System and Its Electrochemical Properties

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 8

参考文献 24

相关文章 9

编辑推荐

Metrics

本文评价

关于本刊

投稿指南

在线期刊

相关单位

联系我们