基于聚苯胺碳纳米管的柔性NH3传感器的研究与应用

  在工业化的今天，有害气体的大量排放，人类面临着严峻的大气污染挑战。氨气（NH3）作为一种无色的有毒气体，过量吸入会导致人体受损，危害生命安全。因此，高灵敏度、低功耗的传感器的研究显得尤为重要。研究证明，聚苯胺基复合材料对氨气有明显的响应特性，且无需加热、功耗低，在氨气传感方面有着巨大的应用潜力。本文选择基于聚苯胺/碳纳米管的柔性传感器，对其气敏性能和柔性特性开展了一些列研究，并通过系统设计验证其在可穿戴设备的应用潜力。

  本文采用化学氧化聚合法制备了聚苯胺以及聚苯胺/碳纳米管氨敏材料，通过柔性印刷技术在PET柔性衬底上打印导电银电极，最后制得柔性NH3传感器。传感器对NH3有着极好的响应灵敏度，100 ppm浓度下响应可达到5.5，同时检测下限达到了300 ppb，满足人体呼出微量气体的检测需求；传感器表现出良好的重复性和稳定性，30天内灵敏度无明显变化；研究了传感器的湿度特性，并分析了其反应机理；该柔性NH3传感器在经过10000次弯折后，依然保持良好的灵敏度；设计了基于STM32的单片机系统，集成本文中的柔性NH3传感器，实现了基本的氨气监测功能，证明了该柔性NH3传感器在可穿戴设备中的巨大应用潜力。

[1]ABDULLA S, LAZZAR T and PULLITHADATHIL M. Highly sensitive, room temperature gas sensorbased on polyaniline-multiwalled carbonnanotubes (PANI/MWCNTs) nanocomposite fortrace-level ammonia detection[J]. Sensors and Actuators B: Chemical, 2015, 211:1523-1534.
[2]印刷技术术语第1部分:基本术语(国家标准(GB)).GB/T9851.1-1990.
[3]印刷技术术语第1部分:基本术语(国家标准(GB)).GB/T9851.1-2008.
[4]ZANT P V. Microchip Fabrication[J]. 2014, 68:566.
[5]王宗辉.喷墨打印图案化导电薄膜及其在柔性电子器件中的应用[J].南京邮电大学,2022.
[6]WANG K, ZHANG W N, ZHAN Y, et al. Preparation and conductive properties of nano silver conductive ink[J]. Electr. Compon. Mater, 2018, 37:31-373.
[7]刘兰兰,张兴业,宋延林.印刷电子:引领电子工业新革命[J].印刷工业, 2015(4):38-41.
[8]史冬梅,杨斌,刘红丽,等.印刷与柔性显示材料与器件技术发展现状与趋势[J].科技中国, 2018(3):16-18.
[9]杨英花,余隽,吴昊,等.氧化锡气敏薄膜的喷墨打印技术研究[J].传感技术学报,2017,30(4):496-499.
[10]CUMMINS G, DESMULLIEZ M P Y. Inkjet printing of conductive materials: a review[J]. Circuit world, 2012, 38(4):193-213.
[11]ALSHAMMARI A S, ALENEZI M R, LAI K T, et al. Inkjet Printing of Polymer Functionalized CNT Gas Sensor with Enhanced Sensing Properties[J]. Materials Letters, 2016, 189.
[12]BEEDASY V, SMITH P J. Printed electronics as prepared by inkjet printing[J]. Materials, 2020, 13(3):704.
[13]SWEET R G. High frequency recording with electrostatically deflected ink jets[J]. Review of scientific instruments, 1965, 36(2):131-136.
[14]BUEHNER W L, HILL J D, WILLIAMS T H, et al. Application of ink jet technology to a word processing output printer[J]. IBM Journal of research and development, 1977, 21(1):2-9.
[15]WANG H N, YAN G F. Design of the motion control system for Inkjet printers Based on EtherCAT[C]. 2020 Chinese Control And Decision Conference (CCDC). IEEE, 2020:4608-4612.
[16]高晓静.浅谈喷墨印刷技术的现状及其发展.科印网,2016,http://www.keyin.cn/.
[17]HIBBARD T, CROWLEY K. Point of care monitoring of hemodialysis patients with abreathammonia measurement device based on printed polyaniline nanoparticle sensors[J]. Anal. Chem, 2013, 85:12158-12165.
[18]YAN H, ZHONG J M, LV Z, et al. Stretchable electronic sensors of nanocomposite networkfilms for ultrasensitive chemical vapor sensing[J]. Small, 2017, 1701697:1-8.
[19]刘艳花,申溯,周小红,等.微纳柔性制造与印刷电子材料[J].中国材料进展,2014,33(3):129-134.
[20]林中德.基于氧化锌基纳米材料的柔性氨气传感器[J].上海应用技术大学,2021.
[21]XUE L, WANG W, GUO Y L, et al. Flexible polyaniline/carbon nanotube nanocompositefilm-based electronic gas sensors[J]. Sensors Actuators B: Chemical, 2017, 244:47-53.
[22]EISING M, CAVAB C E. Doping effect on self-assembled films of polyaniline and carbonnanotube applied as ammonia gas sensor[J]. Sensors Actuators B: Chemical, 2017, 245:25-33.
[23]杨楠楠.基于碳纳米管的柔性湿度/气体传感器制备[J].西安工程大学,2021.
[24]田民波.材料学概论.清华大学出版社,2015.
[25]BURGESS S L, WILSON S D R. Spin-coating of a viscoplastic material[J]. Physics of Fluids, 1996, 8(9):2291-2297.
[26]YONKOKI R K, SOANE D S. Model for spin coating in microelectronic appliciations[J]. J. Appl. Phys, 1992, 72(2):725-740.
[27]XIA D Y, BISWAS A, LI D, et al. Directed self-assembly of silica nanoparticles intonanometer-scale patterned surfaces using spin-coating[J]. Adv. Mater, 2004, 16(16):1427-1432.
[28]吴立全.基于丝网印刷电极的电化学传感器在细菌16S rRNA基因检测中的研究[J].南京邮电大学,2022.
[29]朱崇绘.聚苯胺基纳米材料的制备及其氨敏性能研究[J].黑龙江大学,2019.
[30]张倩,王伟,季翔,等.氧化石墨烯/Er2O3复合阻氚涂层制备工艺及性能研究[J].现代化工,2020,40(1):124-128.
[31]CHUNG W Y, SAKAI G, SHINANOE K, et al. Preparation of indium oxide thin film by spin-coating method and its gas-sensing properties[J]. Sensors and Actuators B: Chemical, 1998, 46(2):139-145.
[32]KANO S, KIM K, FUJII M. Fast-response and flexible nanocrystal-based humidity sensorfor monitoring human respiration and water evaporation on skin[J]. ACS sensors, 2017, 2(6):828-833.
[33]李萌.柔性聚吡咯复合薄膜的电化学沉积与热点性能调控.江西科技师范大学[J],2022.
[34]CARDENAS L, GUTZLER R, et al. Synthesis and Electronic Structure of a Two Dimensional π-Conjugated Polythiophene[J]. Chemical Science, 2013, 4(8):3263.
[35]CHO J H, YU J B, KIM J S, et al. Sensing behaviors of polypyrrole sensor under humidity condition[J]. Sensors and Actuators B: Chemical, 2004, 1(2):389-392.
[36]KIM D, YOO B Y. A novel electropolymerization method for Ppy nanowire-based NH3 gas sensor with low contact resistance[J]. Sensors and Actuators B: Chemical, 2011, 160(1):1168-1173.
[37]刘丽华.功能化聚噻吩的设计合成及传感、成像与抗菌应用研究[D].天津理工大学,2022.
[38]DIAZ A F. Electrochemical preparation and characterization of conductingpolymers [J]. Chemica Scripta, 1981, 17:145-148.
[39]SUGIMOTO R I, TAKETA S, GU H B, et al. Preparation of soluble polythiophenederivatives utilizing transition metal halides as catalysts and their property [J]. Chemistry Express, 1986, 1:635-638.
[40]KANETO K, YOSHINO K, INUISHI Y. Electrical and optical properties of polythiphene prepared by electrochemical polymerization[J]. Solid State Communications, 1983, 46(5):389-391.
[41]MA X F, LI G, XU H Z, et al. Preparation of plythiophene composite film by in situ polymerization at room temperature and its gas response studies[J]. Thin Solid Films, 2006, 4:2700-2704.
[42]LI D, HUANG J, KANER R B. Polyaniline Nanofibers: A Unique PolymerNanostructure for Versatile Applications[J]. Acc. Chem. Res, 2009, (42):135-145.
[43]OSTERHOLM J E, CAO Y, KLAVETTER F, et al. Emulsion polymerization ofaniline[J]. Polymer, 1994, (35):2902-2907.
[44]HUANG J, KANER R B. A General Chemical Route to Polyaniline Nanofibers[J]. J. Am. Chem. Soc, 2004, (126):851-855.
[45]李思琦.基于聚苯胺纳米复合敏感材料的室温柔性NH3传感器研究[J].吉林大学,2019.
[46]BAI H, SHI G. Gas Sensors Based on Conducting Polymers[J]. Sensors, 2007, 7:267-307.
[47]MACDIARMID A G, CHIANG J C, RICHTER A F, et al. Polyaniline: a new conceptin conducting polymers[J]. Synthetic Metals, 1987, 18:285-290.
[48]HIRATA M, SUN L. Characteristics of an organic semiconductor polyaniline film asa sensor for NH3 gas[J]. Sensors and Actuators A: Physics, 1994, 40:159-163.
[49]KUKLA A L, SHISHOV Y M, PILETSKY S A. Ammonia sensors based on sensitivepolyaniline films[J]. Sensors and Actuators B: Chemical, 1996, 37:135-140.
[50]POPOV V. Carbon nanotubes: properties and application[J]. Materials Science andEngineering: R: Reports, 2004, 43(3):61-102.
[51]吴宏禄.基于碳纳米管的复合材料及其超级电容器性能的研究[J].北京交通大学,2020.
[52]LI W Z, QIAN L X, CHANG B H, et al. Large-Scale Synthesis of Aligned Carbon Nanotubes[J]. Science, 1996, 274:1701-1703.
[53]XIE S S, PAN Z W, CHANG B H, et al. Carbon nanotube arrays[J]. Materials Science and Engineering, 2000,286:11-15.
[54]MATSUGUCHI M, IO J, SUGIYAMA G, et al. Effect of NH3 gas on the electricalconductivity of polyaniline blend films[J]. Synthetic Metals, 2002, 128(1):15-19.
[55]MAITY D, et al. Polyaniline anchored MWCNTs on facric for high performance wearable ammonia sensor[J]. ACS Sens, 2018, 3, 9:1822–1830.
[56]ALHARTHY R D, SALEH A. A Novel Trace-Level Ammonia Gas Sensing Based on Flexible PAni-CoFe2O4 Nanocomposite Film at Room Temperature[J]. Polymers 2021, 13:3077.
[57]JIA A, LIU B, LIU H, et al. Interfase design of SnO2@PANI nanotubes with enhanced sensing performance for ammonia detection at room temperature[J]. Frontiers in Chemistry, 2020, 8.
[58]BANGDGAR D K, NAVALE S T , NAUSHAD M, et al. Ultra-sensitive polyaniline-iron onxide nanocomposite room temperature flexible ammonia sensor[J]. RSC Adv, 2015, 5:68964-68967.
[59]PAWAR S G, et al. Room Temperature Ammonia Gas Sensor Based on Polyaniline-TiO2 Nanocomposite. IEEE Sensors Journal, 2011, 11(2):3417-3423, .
[60]WANG J, WEI L M, ZHANG LY, et al. Preparation of high aspect ratio nickel oxidenanowires and their gas sensing devices with fast response and high sensitivity [J]. Journal of Materials Chemistry , 2012, 22(17):8327-8335.
[61]WU Q, SHEN W, LV D, et al. An enhanced room temperature ammonia gas sensor based on GP-PANI/PVDF multi-hierarchical nanocomposite film[J]. Sensors and Actuators B: Chemical, 2021, 334:129630.
[62]KE F, ZHANG Q, JI L, et al. Electrostatic adhesion of polyaniline on carboxylated polyacrylonitrile fabric for high-performance wearable ammonia sensor. Composite Communications, 2021, 27:100817.
[63]郭倩莹,王晓,吴佳糠,等.基于丝网印刷的柔性湿度传感器研究[J].传感技术学报,2022,35(12).
[64]樊 祥洪,陈淘,何宇廷,喻健,宋雨健.柔性涡流阵列传感器深层裂纹监测技术研究[J].中国力学大会,2019.
[65]张铖.基于纳米技术的柔性可穿戴电子皮肤的制备和应用研究[J].电子科技大学,2022.
[66]李思莹.导电聚合物氨气传感器器件的制备工艺、特性及系统应用的研究[J].上海交通大学,2018.
[67]聂清欢.SiO2/PANI复合柔性纳米纤维的制备及其氨敏性能研究[J].江南大学,2018.
[68]IIJIMA S. Helical microtubules of graphitic carbon. Nature, 1991, 354:56–58.
[69]JAIN S, CHAKANE S, SAMUI AB, et al. Humidity sensing with weak acid-doped polyaniline and its composites[J]. Sensors and Actuators B:Chemical, 2003, 96(a):124-129.
[70]TRAVERS J P, NECHTSCHEIN M. Water effects in polyaniline:A new conduction process[J]. Synthetic Metals, 1987, 21(1):135-141.ZHANG W Y, CAO S, WU Z F, et al. High-performance gas sensor of polyaniline/carbon nanotube composites promoted by interface engineering[J]. Sensors, 2020, 20(a):149.