PAN/MXene同轴纤维电极的制备及性能

doi:10.16085/j.issn.1000-6613.2023-1291

摘要/Abstract

摘要：

采用单片层MXene、聚甲基丙烯酸甲酯（PMMA）和聚丙烯腈（PAN）粉末为原料制备不同纺丝液，经过同轴湿法纺丝成型、高温炭化制备出一系列不同壳芯组分同轴纤维电极；分析不同壳层、芯层材料对纤维电极微观结构以及力学、电学、电化学等性能的影响规律。结果表明，当以PAN/MXene为壳层、PAN/PMMA为芯层时，可以实现电极材料力学性能与电化学性能的平衡，拉伸强度、电导率和比电容分别为可达到14.4MPa、322.7S/m和113.18F/g，经过1000次恒电流充放电测试（GCD）循环后，比电容保持率可达到95.7%。

关键词: 纤维电极, MXene, 同轴纤维, 湿法纺丝, 电化学储能

Abstract:

A series of coaxial fiber electrode samples with different sheath and core component were prepared through wet-spinning method combined with subsequent high temperature carbonization. Single-layer MXene sheets, polymethyl methacrylate (PMMA) and polyacrylonitrile (PAN) were applied in this study for making various spinning solution. The influence of different material constitution of the sheath and core layer on the property of as-prepared fiber electrodes, including microstructure, mechanical strength, electrical conductivity and electrochemical performance, was discussed and analyzed. The results showed that the fiber electrode sample with PAN/MXene sheath layer and PAN/PMMA core layer could achieve balance between the electrochemical performance and mechanical strength. The tensile breaking strength, specific conductance and specific capacitance reached 14.4MPa, 322.7S/m and 113.18F/g, respectively. In addition, the fiber electrode also had good cycle stability with capacitance retention rate at 95.7% after 1000 GCD cycles.

Key words: fiber electrode, MXene, coaxial fiber, wet-spinning, electrochemical energy storage

中图分类号:

TB34

屈芸, 成丽媛, 代国亮, 王刚, 郭羽晴, 孙洁. PAN/MXene同轴纤维电极的制备及性能[J]. 化工进展, 2024, 43(9): 5113-5122.

QU Yun, CHENG Liyuan, DAI Guoliang, WANG Gang, GUO Yuqing, SUN Jie. Preparation and properties of PAN/MXene coaxial fiber electrode[J]. Chemical Industry and Engineering Progress, 2024, 43(9): 5113-5122.

图/表 13

图1 同轴纺丝流程图及纤维设计思路

表1 同轴纺丝纤维壳芯设计

样品种类	样品名称	样品编号	壳层纺丝液	芯层纺丝液
同轴纤维	PAN/PMMA@PAN/MXene	A	PAN/PMMA	PAN/MXene
同轴纤维	PAN/MXene@PAN/PMMA	B	PAN/MXene	PAN/PMMA
中空纤维	PAN/PMMA	C	PAN/PMMA	PVA/H₂O
中空纤维	PAN/MXene	D	PAN/MXene	PVA/H₂O

图2 制得MXene的微观结构特征

图3 PAN/MXene@PAN/PMMA纤维

图4 各同轴纤维的微观形貌

图5 同轴纤维及其元素分布

图6 各同轴纤维的红外光谱图

图7 各同轴纤维的拉曼光谱

图8 各同轴纤维的X射线衍射谱

图9 各同轴纤维炭化前后力学性能A—PAN/PMMA@PAN/MXene同轴纤维；B—PAN/MXene@PAN/PMMA同轴纤维；C—PAN/PMMA中空纤维；D—PAN/MXene中空纤维

图10 各同轴纤维的电导率对比A—PAN/PMMA@PAN/MXene同轴纤维；B—PAN/MXene@PAN/PMMA同轴纤维；C—PAN/PMMA中空纤维；D—PAN/MXene中空纤维

图11 各同轴纤维的电化学性能A—PAN/PMMA@PAN/MXene同轴纤维；B—PAN/MXene@PAN/PMMA同轴纤维；C—PAN/PMMA中空纤维；D—PAN/MXene中空纤维

图12 PAN/MXene@PAN/PMMA炭化纤维的电化学性能

参考文献 28

1	邢宝林, 黄光许, 谌伦建, 等. 超级电容器电极材料的研究现状与展望[J]. 材料导报, 2012, 26(19): 21-25.
	XING Baolin, HUANG Guangxu, CHEN Lunjian, et al. Current situation and prospect of research on electrode materials for supercapacitor[J]. Materials Review, 2012, 26(19): 21-25.
2	LI Xin, WEI Bingqing. Supercapacitors based on nanostructured carbon[J]. Nano Energy, 2013, 2(2): 159-173.
3	Tian LYU, LIU Mingxian, ZHU Dazhang, et al. Nanocarbon-based materials for flexible all-solid-state supercapacitors[J]. Advanced Materials, 2018, 30(17): 1705489.
4	François BÉGUIN, PRESSER Volker, BALDUCCI Andrea, et al. Carbons and electrolytes for advanced supercapacitors[J]. Advanced Materials, 2014, 26(14): 2219-2251.
5	ZHANG Lili, ZHAO X S. Carbon-based materials as supercapacitor electrodes[J]. Chemical Society Reviews, 2009, 38(9): 2520-2531.
6	PANDOLFO A G, HOLLENKAMP A F. Carbon properties and their role in supercapacitors[J]. Journal of Power Sources, 2006, 157(1): 11-27.
7	FRACKOWIAK Elzbieta, François BÉGUIN. Carbon materials for the electrochemical storage of energy in capacitors[J]. Carbon, 2001, 39(6): 937-950.
8	张诚. 基于复合纳米材料的超级电容器的设计、制备和电化学性能研究[D]. 南京: 南京大学, 2018.
	ZHANG Cheng. Design, preparation and electrochemical performance of supercapacitors based on composite nanomaterials[D]. Nanjing: Nanjing University, 2018.
9	阮英鹏. 超级电容器用石墨烯/聚丙烯腈同轴纤维电极的制备与性能研究[D]. 上海: 东华大学, 2021.
	RUAN Yingpeng. Preparation and properties of graphene/polyacrylonitrile coaxial fiber electrode for supercapacitors[D]. Shanghai: Donghua University, 2021.
10	CAI Shengying, HUANG Tieqi, CHEN Hao, et al. Wet-spinning of ternary synergistic coaxial fibers for high performance yarn supercapacitors[J]. Journal of Materials Chemistry A, 2017, 5(43): 22489-22494.
11	胡文鑫. 用于超级电容器的基于木质素基生物质碳/石墨烯基纤维电极结构与电化学性能研究[D]. 上海: 东华大学, 2021.
	HU Wenxin. Study on structure and electrochemical performance of lignin-based biomass carbon/graphene-based fiber electrode for supercapacitors[D]. Shanghai: Donghua University, 2021.
12	成丽媛, 代国亮, 屈芸, 等. PAN/MXene复合纤维电极制备及性能研究[J]. 功能材料, 2023, 54(6): 6146-6154.
	CHENG Liyuan, DAI Guoliang, QU Yun, et al. Preparation and properties of PAN/MXene composite fiber electrode[J]. Journal of Functional Materials, 2023, 54(6): 6146-6154.
13	SONG Yanping, ZHANG Jixiang, LI Nian, et al. Design of a high performance electrode composed of porous nickel-cobalt layered double hydroxide nanosheets supported on vertical graphene fibers for flexible supercapacitors[J]. New Journal of Chemistry, 2020, 44: 6623-6634.
14	YU Feng, PANG Le, WANG Hongxia. Preparation of mulberry-like RuO₂ electrode material for supercapacitors[J]. Rare Metals, 2021, 40(2): 440-447.
15	EL-DEEN Ahmed G, MOHAMED El-Newehy, CHEOL Sang Kim, et al. Nitrogen-doped, FeNi alloy nanoparticle-decorated graphene as an efficient and stable electrode for electrochemical supercapacitors in acid medium[J]. Nanoscale Research Letters, 2015, 10(1): 104.
16	WANG Dawei, LI Feng, YIN Lichang, et al. Nitrogen-doped carbon monolith for alkaline supercapacitors and understanding nitrogen-induced redox transitions[J]. Chemistry—A European Journal, 2012, 18(17): 5345-5351.
17	唐承贵. 氮掺杂多孔碳材料的制备及其在超级电容器中的应用[D]. 湘潭: 湘潭大学, 2017.
	TANG Chenggui. Preparation of nitrogen-doped porous carbon materials and its application in supercapacitors[D]. Xiangtan: Xiangtan University, 2017.
18	刘茵沁. 氮掺杂碳电极材料的制备及其超级电容器应用研究[D]. 重庆: 西南大学, 2016.
	LIU Yinqin. Preparation of nitrogen-doped carbon electrode materials and its application in supercapacitors[D]. Chongqing: Southwest University, 2016.
19	GUAN Wei, JI Fangying, CHEN Qingkong, et al. Synthesis and enhanced phosphate recovery property of porous calcium silicate hydrate using polyethyleneglycol as pore-generation agent[J]. Materials, 2013, 6(7): 2846-2861.
20	SARMA Pranab Jyoti, MOHANTY Kaustubha. Epipremnum aureum and Dracaena braunii as indoor plants for enhanced bio-electricity generation in a plant microbial fuel cell with electrochemically modified carbon fiber brush anode[J]. Journal of Bioscience and Bioengineering, 2018, 126(3): 404-410.
21	LI Youbing, ZHOU Xiaobing, WANG Jing, et al. Facile preparation of in situ coated Ti₃C₂T _x /Ni_0.5Zn_0.5Fe₂O₄ composites and their electromagnetic performance[J]. RSC Advances, 2017, 7(40): 24698-24708.
22	MAHMOOD Majid, RASHEED Aamir, AYMAN Imtisal, et al. Synthesis of ultrathin MnO₂ nanowire-intercalated 2D-MXenes for high-performance hybrid supercapacitors[J]. Energy & Fuels, 2021, 35(4): 3469-3478.
23	CYGAN Tomasz, WOZNIAK Jaroslaw, PETRUS Mateusz, et al. Microstructure and mechanical properties of alumina composites with addition of structurally modified 2D Ti₃C₂ (MXene) phase[J]. Materials, 2021, 14(4): 829.
24	BOKOBZA Liliane, BRUNEEL Jean-Luc, COUZI Michel. Raman spectroscopy as a tool for the analysis of carbon-based materials (highly oriented pyrolitic graphite, multilayer graphene and multiwall carbon nanotubes) and of some of their elastomeric composites[J]. Vibrational Spectroscopy, 2014(74): 57-63.
25	LI Zhengyang, WANG Libo, SUN Dandan, et al. Synthesis and thermal stability of two-dimensional carbide MXene Ti₃C₂ [J]. Materials Science and Engineering: B, 2015(191): 33-40.
26	FUKUMORI Taishi, NAKAOKI Takahiko. High-tensile-strength polyvinyl alcohol films prepared from freeze/thaw cycled gels[J]. Journal of Applied Polymer Science, 2014, 131(15): 40578.
27	MAINKA Julia, GAO Wei, HE Nanfei, et al. A General equivalent electrical circuit model for the characterization of MXene/graphene oxide hybrid-fiber supercapacitors by electrochemical impedance spectroscopy—Impact of fiber length[J]. Electrochimica Acta, 2022(404): 139740.
28	NAVALPOTRO Paula, ANDERSON Marc, MARCILLA Rebeca, et al. Insights into the energy storage mechanism of hybrid supercapacitors with redox electrolytes by electrochemical impedance spectroscopy[J]. Electrochimica Acta, 2018(263): 110-117.

[1]	王帅晴, 杨思文, 李娜, 孙占英, 安浩然. 元素掺杂生物质炭材料在电化学储能中的研究进展[J]. 化工进展, 2023, 42(8): 4296-4306.
[2]	万茂华, 张小红, 安兴业, 龙垠荧, 刘利琴, 管敏, 程正柏, 曹海兵, 刘洪斌. MXene在生物质基储能纳米材料领域中的应用研究进展[J]. 化工进展, 2023, 42(4): 1944-1960.
[3]	朱晟, 彭怡婷, 闵宇霖, 刘海梅, 徐群杰. 电化学储能材料及储能技术研究进展[J]. 化工进展, 2021, 40(9): 4837-4852.
[4]	侯璐, 胡友仁, 李文翠, 董晓玲, 陆安慧. 富氧多孔炭的合成及其在电化学储能中的作用[J]. 化工进展, 2021, 40(6): 3020-3033.
[5]	李瑞, 谢芳霞, 朱巧霞, 陈露, 简选. 基于聚苯胺改性构建三维MXene复合材料及其电容性能[J]. 化工进展, 2021, 40(11): 6211-6218.
[6]	张素珍, 杨蓉, 龚乐, 樊潮江, 燕映霖, 许云华. 二维金属有机框架材料的制备及其应用[J]. 化工进展, 2021, 40(11): 6195-6210.
[7]	张向倩, 何斌, 董晓玲, 叶成玉, 陆安慧. 多孔炭材料设计合成及电化学储能应用[J]. 化工进展, 2019, 38(01): 404-420.