无机酸掺杂聚苯胺/碳纤维复合海洋电场传感器电极

doi:10.16183/j.cnki.jsjtu.2022.156

摘要/Abstract

摘要：

碳纤维电极具有成本低、化学稳定性好、性能可调控等优点,可用于开发高性能海洋电场传感器.利用电化学原位聚合法制备盐酸、硫酸、磷酸掺杂的聚苯胺/碳纤维(PANI/CF)复合电场电极,提高其电化学性能与电场响应性能.结果表明:碳纤维表面生成致密的导电聚苯胺膜,并在循环伏安测试中出现特征氧化还原峰;电化学阻抗分析显示PANI/CF复合电极低频(0.01 Hz)阻抗值至少降低为空白电极的1/118,利于对水下微弱电场信号进行响应.在电场响应性能测试中,盐酸掺杂PANI/CF复合电极电位漂移量最低达1.77 mV/d;能够较好地响应1 mV/10 mHz的低频率低强度电场信号;误差线性度最小值为0.111%,在同类电极中具有最好响应灵敏度.该新型复合电场电极制备方法简单、成本低廉,有助开发新一代低成本、高性能海洋电场传感器.

关键词: 碳纤维电极, 碳纤维/聚苯胺复合材料, 无机酸掺杂, 电化学性能, 电场响应性能

Abstract:

Carbon fiber electrode has the advantages of low cost, good chemical stability, and tunable performance, which can be utilized to develop high performance marine electric field sensors. Polyaniline/carbon fiber (PANI/CF) composite electrode doped with hydrochloric acid, sulfuric acid, and phosphoric acid are respectively fabricated by electrochemical in-situ polymerization, and their electrochemical performance and electric field response of the composite electrodes are studied respectively. The results show that conductive polyaniline film is uniformly formed on the surface of carbon fiber, and the characteristic redox peak occurs in the cyclic voltammetry test. Electrochemical impedance analysis shows that the low frequency (0.01 Hz) impedance of PANI/CF composite electrode decreases to at most 1/118 of that of the blank electrode, which is conducive to the quick response to weak underwater electric field signal. In the electric field response performance test, the potential drift of hydrochloric acid doped PANI/CF composite electrode is as low as 1.77 mV/d and it can better respond to 1 mV/10 mHz low-frequency and low-intensity electric field signal. It also has the minimum linearity error (0.111%), indicating the best response sensitivity among these modified electrodes. The preparation method of the composite electrode is simple and low-cost. Therefore, it is expected to be developed into a new generation of marine electric field sensor with low cost and high performance.

Key words: carbon fiber (CF) electrode, carbon fiber/polyaniline composite (PANI/CF), inorganic acid doping, electrochemical performance, electric field response performance

中图分类号:

TB332
P738

侯晓帆, 孙久哲, 许嘉威, 胡承儒, 付玉彬. 无机酸掺杂聚苯胺/碳纤维复合海洋电场传感器电极[J]. 上海交通大学学报, 2024, 58(3): 391-399.

HOU Xiaofan, SUN Jiuzhe, XU Jiawei, HU Chengru, FU Yubin. Inorganic Acid Doped Polyaniline/Carbon Fiber Composite Electrode as a Marine Electric Field Sensor[J]. Journal of Shanghai Jiao Tong University, 2024, 58(3): 391-399.

图/表 18

图1

表1

图2

表2

表3

图3

表4

图4

表5

电极电位漂移量

电极	v/ (mV·d^-1)	$V -$ / mV
Blank	3.66	95.45
PANI/CF-HCl	1.77	34.96
PANI/CF-H₂SO₄	4.52	143.51
PANI/CF-H₃PO₄	0.38	78.66

表5

图5

图6

图7

表6

图8

图1

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图2

表2

参考文献 24

[1]	杨国义. 舰船水下电磁场国外研究现状[J]. 舰船科学技术, 2011, 33(12): 138-143.
	YANG Guoyi. Situation on underwater electromagnetic field researches of ships abroad[J]. Ship Science & Technology, 2011, 33(12): 138-143.
[2]	COMMER M, NEWMAN G A. New advances in three-dimensional controlled-source electromagnetic inversion[J]. Geophysical Journal International, 2008, 172(2): 513-535. doi: 10.1111/gji.2008.172.issue-2 URL
[3]	SONG Y, LI H, WANG Y M. Ocean electric field tests of carbon fiber electrodes prepared by nitric acid oxidation[J]. Materials Science, 2021, 27(1): 96-102. doi: 10.5755/j02.ms.20907 URL
[4]	LIU A, FU Y B, ZAI J Z, et al. Electrochemical and electric field response properties of highly sensitive electrodes based on carbon fiber with oxygen and nitrogen surface groups[J]. IEEE Sensors Journal, 2019, 19(11): 3966-3974. doi: 10.1109/JSEN.7361 URL
[5]	WANG Z D, DENG M, CHEN K, et al. Development and evaluation of an ultralow-noise sensor system for marine electric field measurements[J]. Sensors & Actuators A: Physical, 2014, 213: 70-78.
[6]	李红霞, 宋玉苏, 申振, 等. Ag/AgCl电极海洋电场探测机理研究[J]. 海军工程大学学报, 2020, 32(1): 57-61.
	LI Hongxia, SONG Yusu, SHEN Zhen, et al. Research on mechanism of marine electric field detection based on Ag/AgCl electrode[J]. Journal of Naval University of Engineering, 2020, 32(1): 57-61.
[7]	ZAI X R, LIU A, TIAN Y H, et al. Oxidation modification of polyacrylonitrile-based carbon fiber and its electro-chemical performance as marine electrode for electric field test[J]. Journal of Ocean University of China, 2020, 19(2): 361-368. doi: 10.1007/s11802-020-4178-x
[8]	李洋, 李佳, 毛楚儒, 等. 聚苯胺及其高温碳化对海底微生物燃料电池阴极电化学性能影响[J]. 材料开发与应用, 2020, 35(4): 62-68.
	LI Yang, LI Jia, MAO Churu, et al. Effect of pyrolyzed polyaniline modified cathode on the electrochemical performance of marine sediment microbial fuel cells[J]. Development & Application of Materials, 2020, 35(4): 62-68.
[9]	WEI G, GONG S S, TANG J, et al. Preparation by pulsed current electrochemical polymerisation and properties of ordered comb-shaped polyaniline/carbon fibres composites for flexible supercapacitor electrodes[J]. Transactions of the IMF, 2020, 98(2): 98-104. doi: 10.1080/00202967.2020.1728051 URL
[10]	BOOTA M, GOGOSI Y. MXene-conducting polymer asymmetric pseudocapacitors[J]. Advanced Energy Materials, 2019, 9(7): 1802917. doi: 10.1002/aenm.v9.7 URL
[11]	AHMAD F, DAUD W M A W, AHMAD M A, et al. The effects of acid leaching on porosity and surface functional groups of cocoa (Theobroma cacao)-shell based activated carbon[J]. Chemical Engineering Research & Design, 2013, 91(6): 1028-1038.
[12]	ABDIRYIM T, ZHANG X G, JAMAL R. Comparative studies of solid-state synthesized polyaniline doped with inorganic acids[J]. Materials Chemistry & Physics, 2005, 90(2/3): 367-372.
[13]	KUMAR S N, GAILLARD F, BOUYSSOUX G, et al. High-resolution XPS studies of electrochemically synthesized conducting polyaniline films[J]. Synthetic Metals, 1990, 36(1): 111-127. doi: 10.1016/0379-6779(90)90240-L URL
[14]	GOLCZAK S, KANCIURZEWSKA A, FAHLMAN M, et al. Comparative XPS surface study of polyaniline thin films[J]. Solid State Ionics, 2008, 179(39): 2234-2239. doi: 10.1016/j.ssi.2008.08.004 URL
[15]	KANG E T, NEOH K G, TAN K L, et al. Protonation of the amine nitrogens in emeraldine-evidence from X-ray photoelectron spectroscopy[J]. Synthetic Metals, 1992, 46(2): 227-233. doi: 10.1016/0379-6779(92)90346-K URL
[16]	KANG E T, NEOH K G, TAN K L, et al. X-ray photoelectron spectroscopy studies of some polyaniline-halogen complexes[J]. Molecular Crystals & Liquid Crystals Incorporating Nonlinear Optics, 1990, 178(1): 219-230.
[17]	HATCHETT D W, JOSOWICZ M, JANATA J. Acid doping of polyaniline: Spectroscopic and electrochemical studies[J]. The Journal of Physical Chemistry B, 1999, 103(50): 10992-10998. doi: 10.1021/jp991110z URL
[18]	黄惠, 郭忠诚. 导电聚苯胺基复合阳极材料的制备[M]. 北京: 冶金工业出版社, 2016: 222.
	HUANG Hui, GUO Zhongcheng. Preparation of conductive polyaniline matrix composite anode material[M]. Beijing: Metallurgical Industry Press, 2016: 222.
[19]	黄惠, 郭忠诚. 导电聚苯胺的制备及应用[M]. 北京: 科学出版社, 2010: 87.
	HUANG Hui, GUO Zhongcheng. Preparation and application of conductive polyaniline[M]. Beijing: Science Press, 2010: 87.
[20]	LI J, LIU K, XUE G B, et al. Electricity generation from water droplets via capillary infiltrating[J]. Nano Energy, 2018, 48: 211-216. doi: 10.1016/j.nanoen.2018.02.061 URL
[21]	LI J, LIU K, DING T P, et al. Surface functional modification boosts the output of an evaporation-driven water flow nanogenerator[J]. Nano Energy, 2019, 58: 797-802. doi: 10.1016/j.nanoen.2019.02.011 URL
[22]	申振, 宋玉苏, 王月明. 高性能碳纤维水下电场电极制备及其性能测量[J]. 兵工学报, 2017, 38(11): 2190-2197. doi: 10.3969/j.issn.1000-1093.2017.11.015
	SHEN Zhen, SONG Yusu, WANG Yueming. Preparation and performance measurement of high performance underwater carbon fiber electric field electrode[J]. Acta Armamentarii, 2017, 38(11): 2190-2197. doi: 10.3969/j.issn.1000-1093.2017.11.015
[23]	潘龙. 用于目标探测的水下电场传感器研究[D]. 长沙: 国防科学技术大学, 2015.
	PAN Long. Study on the underwater electric field sensor used in target detection[D]. Changsha: National University of Defense Technology, 2015.
[24]	PENG Q Y, LI Y B, HE X D, et al. Interfacial enhancement of carbon fiber composites by poly (amido amine) functionalization[J]. Composites Science & Technology, 2013, 74: 37-42.

样品	r_C/%	r_O/%	r_N/%	r_Cl/%	r_S/%	r_P/%	n_C/n_N
PANI/CF-HCl	68.38	16.22	12.77	2.62			5.35
PANI/CF-H₂SO₄	64.73	25.36	8.20		1.70		7.89
PANI/CF-H₃PO₄	65.50	22.33	11.44			0.72	5.73

样品	贡献率/%				贡献值
	—N=	—NH—	N⁺	N⁺/N	—N=/—NH—
	398.5 eV	399.6 eV	401.1 eV 402.6 eV	N⁺/N	—N=/—NH—
PANI/CF-HCl	11.91	55.55	32.54	32.54	0.21
PANI/CF-H₂SO₄	18.51	47.51	33.98	33.98	0.39
PANI/CF-H₃PO₄	15.62	51.82	32.56	32.56	0.30

电极	比电容值/(F·g^-1)	电容提升倍率
Blank	0.39	1.00
PANI/CF-HCl	55.17	141.46
PANI/CF-H₂SO₄	65.37	167.62
PANI/CF-H₃PO₄	31.85	81.67

电极	R_s/Ω	R_ct/Ω	\|Z\|/Ω
Blank	1.36		729
PANI/CF-HCl	1.987	0.041	3.651
PANI/CF-H₂SO₄	1.696	0.035	3.153
PANI/CF-H₃PO₄	1.703	0.014	6.128

配对电极	k	γ/%
PANI/CF-HCl	0.113	0.111
PANI/CF-H₂SO₄	0.078	0.383
PANI/CF-H₃PO₄	0.106	0.144