聚苯胺基导电纳米纤维的制备及应用研究

聚苯胺 (PANI) 是一种重要的传统本征导电高分子材料。聚苯胺具有廉价易得的单体、良好的环境稳定性、可调节的电导率、独特的氧化还原性质以及可逆的掺杂-去掺杂等性能，是一种具有广阔应用前景的有机导电材料。但是，聚苯胺分子链固有的刚性，使其具有较高的熔点和较差的溶解性，进而影响其加工性。因此，合成具有高强度、高柔韧性以及高电导率的聚苯胺及其复合材料仍是一个重大的挑战。本论文从高分子量的聚苯胺的合成到聚苯胺基导电复合纳米纤维的静电纺丝加工及原位修饰进行了系统的研究，探索了超高分子量聚苯胺的合成工艺，并使用静电纺丝的方法制备了聚苯胺/热塑性聚氨酯 (TPU) 复合纳米纤维膜，另外以静电纺丝结合原位聚合的方式制备了核壳结构的PVDF/PANI@PANI复合纳米纤维膜。研究了聚苯胺合成条件对分子量、结晶度、溶液粘度以及电导率的影响。系统表征了聚苯胺/TPU、PVDF/PANI@PANI纤维膜的表面形貌、结晶度、力学性能和导电性。结果表明，聚苯胺/TPU纳米纤维复合膜具有良好的机械性能和导电性，可应用在抗静电领域。PVDF/PANI@PANI纤维膜结合了PVDF的高强度和柔韧性以及PANI的良好的导电性，展示了优异的电磁屏蔽性能，复合膜的最佳屏蔽效果达到了56 dB (屏蔽效率大于99.999%)，可应用于便携式设备、柔性电子器件等领域。本论文为制备聚苯胺基核壳结构导电纳米纤维、开发高性能电磁屏蔽材料提供了一种新策略。

[1] NASROLLAHZADEH M, SAJADI S M, SAJJADI M, et al. Chapter 1 - an introduction to nanotechnology [M]// NASROLLAHZADEH M, SAJADI S M, SAJJADI M, et al. Interface science and technology. Elsevier. 2019: 1-27.
[2] LONG Y-Z, LI M-M, GU C, et al. Recent advances in synthesis, physical properties and applications of conducting polymer nanotubes and nanofibers[J]. Progress in Polymer Science, 2011, 36(10): 1415-1442.
[3] BHADRA S, KHASTGIR D, SINGHA N K, et al. Progress in preparation, processing and applications of polyaniline[J]. Progress in Polymer Science, 2009, 34(8): 783-810.
[4] BAKER C O, HUANG X, NELSON W, et al. Polyaniline nanofibers: Broadening applications for conducting polymers[J]. Chemical Society Reviews, 2017, 46(5): 1510-1525.
[5] ZHANG Y, RUTLEDGE G C. Electrical conductivity of electrospun polyaniline and polyaniline-blend fibers and mats[J]. Macromolecules, 2012, 45(10): 4238-4246.
[6] STEJSKAL J, TRCHOVá M, BOBER P, et al. Conducting polymers: Polyaniline[M]. Encyclopedia of polymer science and technology. 2015: 1-44.
[7] WANG Y. Preparation and application of polyaniline nanofibers: An overview[J]. Polymer International, 2018, 67(6): 650-669.
[8] WANG X-X, YU G-F, ZHANG J, et al. Conductive polymer ultrafine fibers via electrospinning: Preparation, physical properties and applications[J]. Progress in Materials Science, 2021, 115: 100704.
[9] GENIèS E M, BOYLE A, LAPKOWSKI M, et al. Polyaniline: A historical survey[J]. Synthetic Metals, 1990, 36(2): 139-182.
[10] LIN C-W, XUE S, JI C, et al. Conducting polyaniline for antifouling ultrafiltration membranes: Solutions and challenges[J]. Nano Letters, 2021, 21(9): 3699-3707.
[11] LUTHRA V, SINGH R, GUPTA S K, et al. Mechanism of dc conduction in polyaniline doped with sulfuric acid[J]. Current Applied Physics, 2003, 3(2): 219-222.
[12] WATANABE A, MORI K, MIKUNI M, et al. Comparative study of redox reactions of polyaniline films in aqueous and nonaqueous solutions[J]. Macromolecules, 2002, 22(8): 3323-3327.
[13] BHADRA S, CHATTOPADHYAY S, SINGHA N K, et al. Improvement of conductivity of electrochemically synthesized polyaniline[J]. Journal of Applied Polymer Science, 2008, 108(1): 57-64.
[14] BHADRA S, SINGHA N K, CHATTOPADHYAY S, et al. Effect of different reaction parameters on the conductivity and dielectric properties of polyaniline synthesized electrochemically and modeling of conductivity against reaction parameters through regression analysis[J]. Journal of Polymer Science Part B: Polymer Physics, 2007, 45(15): 2046-2059.
[15] HEME H N, ALIF M S N, RAHAT S M S M, et al. Recent progress in polyaniline composites for high capacity energy storage: A review[J]. Journal of Energy Storage, 2021, 42: 103018.
[16] LU Q, ZHAO Q, ZHANG H, et al. Water dispersed conducting polyaniline nanofibers for high-capacity rechargeable lithium–oxygen battery[J]. ACS Macro Letters, 2013, 2(2): 92-95.
[17] LUO H, KANETI Y V, AI Y, et al. Nanoarchitectured porous conducting polymers: From controlled synthesis to advanced applications[J]. Advanced Materials, 2021, 33(29): 2007318.
[18] LYUTOV V, TSAKOVA V. Polysulfonate-doped polyanilines—oxidation of ascorbic acid and dopamine in neutral solution[J]. Journal of Solid State Electrochemistry, 2020, 24(11): 3113-3123.
[19] BLáHA M, BOUŠA M, VALEŠ V, et al. Two-dimensional cvd-graphene/polyaniline supercapacitors: Synthesis strategy and electrochemical operation[J]. ACS Applied Materials & Interfaces, 2021, 13(29): 34686-34695.
[20] NARAYANASAMY S, JAYAPRAKASH J. Application of carbon-polymer based composite electrodes for microbial fuel cells[J]. Reviews in Environmental Science and Bio/Technology, 2020, 19(3): 595-620.
[21] DAVID S, NICOLAU Y F, MELIS F, et al. Molecular weight of polyaniline synthesized by oxidation of aniline with ammonium persulfate and with ferric chloride[J]. Synthetic Metals, 1995, 69(1): 125-126.
[22] ADAMS P N, LAUGHLIN P J, MONKMAN A P. Synthesis of high molecular weight polyaniline at low temperatures[J]. Synthetic Metals, 1996, 76(1): 157-160.
[23] TERLEMEZYAN N G. Conducting polymers prepared by oxidative polymerization: Polyaniline[J]. Progress in Polymer Science, 1998, 23(8):1443-1484.
[24] GOSPODINOVA N, TERLEMEZYAN L. Conducting polymers prepared by oxidative polymerization: Polyaniline[J]. Progress in Polymer Science, 1998, 23(8): 1443-1484.
[25] STEJSKAL J, PROKEŠ J, TRCHOVá M. Reprotonation of polyaniline: A route to various conducting polymer materials[J]. Reactive and Functional Polymers, 2008, 68(9): 1355-1361.
[26] HEEGER A J, KIVELSON S, SCHRIEFFER J R, et al. Solitons in conducting polymers[J]. Reviews of Modern Physics, 1988, 60(3): 781-850.
[27] MACDIARMID A G, CHIANG J C, RICHTER A F, et al. Polyaniline: Synthesis and characterization of the emeraldine oxidation state by elemental analysis[J]. Synthetic Metals, 1987, 18: 285.
[28] ŠEDĚNKOVá I, PROKEŠ J, TRCHOVá M, et al. Conformational transition in polyaniline films – spectroscopic and conductivity studies of ageing[J]. Polymer Degradation and Stability, 2008, 93(2): 428-435.
[29] STEJSKAL J, PROKES J, TRCHOVA M. Reprotonated polyanilines: The stability of conductivity at elevated temperature[J]. Polymer Degradation and Stability, 2014, 102(APR.): 67-73.
[30] HUANG X A, KOCAEFE D, KOCAEFE Y, et al. Study of the degradation behavior of heat-treated jack pine (pinus banksiana) under artificial sunlight irradiation[J]. Polymer Degradation and Stability, 2012, 97(7): 1197-1214.
[31] BAVATHARANI C, MUTHUSANKAR E, WABAIDUR S M, et al. Electrospinning technique for production of polyaniline nanocomposites/nanofibres for multi-functional applications: A review[J]. Synthetic Metals, 2021, 271: 116609.
[32] KIM B H, PARK D H, JOO J, et al. Synthesis, characteristics, and field emission of doped and de-doped polypyrrole, polyaniline, poly(3,4-ethylenedioxythiophene) nanotubes and nanowires[J]. Synthetic Metals, 2005, 150(3): 279-284.
[33] LI X, WAN M, LI X, et al. The role of DNA in pani–DNA hybrid: Template and dopant[J]. Polymer, 2009, 50(19): 4529-4534.
[34] CALLEGARI V, GENCE L, MELINTE S, et al. Electrochemically template-grown multi-segmented gold-conducting polymer nanowires with tunable electronic behavior[J]. Chemistry of Materials, 2009, 21(18): 4241-4247.
[35] HUANG J, KANER R B. A general chemical route to polyaniline nanofibers[J]. Journal of the American Chemical Society, 2004, 126(3): 851-855.
[36] WAN M. A template-free method towards conducting polymer nanostructures[J]. Advanced Materials, 2008, 20(15): 2926-2932.
[37] CHIAM Y S, MOHAMAD AHAD I Z, WADI HARUN S, et al. Effects of the dopant ratio on polyaniline coated fiber bragg grating for ph detection[J]. Synthetic Metals, 2016, 211: 132-141.
[38] SIMOTWO S K, DELRE C, KALRA V. Supercapacitor electrodes based on high-purity electrospun polyaniline and polyaniline–carbon nanotube nanofibers[J]. ACS Applied Materials & Interfaces, 2016, 8(33): 21261-21269.
[39] CHAUDHARI S, SHARMA Y, ARCHANA P S, et al. Electrospun polyaniline nanofibers web electrodes for supercapacitors[J]. Journal of Applied Polymer Science, 2013, 129(4): 1660-1668.
[40] SHIN M K, KIM Y J, KIM S I, et al. Enhanced conductivity of aligned pani/peo/mwnt nanofibers by electrospinning[J]. Sensors and Actuators B: Chemical, 2008, 134(1): 122-126.
[41] YU Q-Z, SHI M-M, DENG M, et al. Morphology and conductivity of polyaniline sub-micron fibers prepared by electrospinning[J]. Materials Science and Engineering: B, 2008, 150(1): 70-76.
[42] SRINIVASAN S S, RATNADURAI R, NIEMANN M U, et al. Reversible hydrogen storage in electrospun polyaniline fibers[J]. International Journal of Hydrogen Energy, 2010, 35(1): 225-230.
[43] BABU V J, MURTHY D V B, SUBRAMANIAN V, et al. Microwave hall mobility and electrical properties of electrospun polymer nanofibers[J]. Journal of Applied Physics, 2011, 109(7): 074306.
[44] LIN Q, LI Y, YANG M. Polyaniline nanofiber humidity sensor prepared by electrospinning[J]. Sensors and Actuators B: Chemical, 2012, 161(1): 967-972.
[45] MACDIARMID A G. “Synthetic metals”: A novel role for organic polymers[J]. Current Applied Physics, 2001, 1(4): 269-279.
[46] TANG C C, HUANG R, LONG Y Z, et al. Synthesis, structural and gas sensing properties of nano-branched coaxial polyaniline fibers by electrospinning[J]. Advanced Materials Research, 2012, 562-564: 308-311.
[47] KIRISTI M, OKSUZ A U, OKSUZ L, et al. Electrospun chitosan/pedot nanofibers[J]. Materials Science and Engineering: C, 2013, 33(7): 3845-3850.
[48] LI X-Q, LIU W-W, LIU S-P, et al. In situ polymerization of aniline in electrospun microfibers[J]. Chinese Chemical Letters, 2014, 25(1): 83-86.
[49] SARVI A, CHIMELLO V, SILVA A B, et al. Coaxial electrospun nanofibers of poly(vinylidene fluoride)/polyaniline filled with multi-walled carbon nanotubes[J]. Polymer Composites, 2014, 35(6): 1198-1203.
[50] BAI C, WANG Y, FAN Z, et al. One-step preparation of gel-electrolyte-friendly fiber-shaped aerogel current collector for solid-state fiber-shaped supercapacitors with large capacity[J]. Journal of Power Sources, 2022, 521: 230971.
[51] JI S, LI Y, YANG M. Gas sensing properties of a composite composed of electrospun poly(methyl methacrylate) nanofibers and in situ polymerized polyaniline[J]. Sensors and Actuators B: Chemical, 2008, 133(2): 644-649.
[52] LI X, RAFIE A, SMOLIN Y Y, et al. Engineering conformal nanoporous polyaniline via oxidative chemical vapor deposition and its potential application in supercapacitors[J]. Chemical Engineering Science, 2019, 194: 156-164.
[53] KOSIŃSKI S, RYKOWSKA I, GONSIOR M, et al. Ionic liquids as antistatic additives for polymer composites – a review[J]. Polymer Testing, 2022, 112: 107649.
[54] ZHU A, WANG H, SUN S, et al. The synthesis and antistatic, anticorrosive properties of polyaniline composite coating[J]. Progress in Organic Coatings, 2018, 122: 270-279.
[55] 姜宇, 陈卓明, 辛斌杰, 等. 聚苯胺基导电功能性织物研究进展[J]. 当代化工研究, 2019, 27(04): 58-64.
[56] 吴连锋, 刘艳明, 王贤明, 等. 抗静电涂料研究概述[J]. 涂料工业, 2016, 46(08): 75-81.
[57] MA X, LI Y, SHEN B, et al. Carbon composite networks with ultrathin skin layers of graphene film for exceptional electromagnetic interference shielding[J]. ACS Applied Materials & Interfaces, 2018, 10(44): 38255-38263.
[58] SUDHA J D, SIVAKALA S, PRASANTH R, et al. Development of electromagnetic shielding materials from the conductive blends of polyaniline and polyaniline-clay nanocomposite-eva: Preparation and properties[J]. Composites Science and Technology, 2009, 69(3): 358-364.
[59] CHUNG D D L. Electromagnetic interference shielding effectiveness of carbon materials[J]. Carbon, 2001, 39(2): 279-285.
[60] THOMASSIN J-M, JéRôME C, PARDOEN T, et al. Polymer/carbon based composites as electromagnetic interference (emi) shielding materials[J]. Materials Science and Engineering: R: Reports, 2013, 74(7): 211-232.
[61] SAINI P, ARORA M, GUPTA G, et al. High permittivity polyaniline–barium titanate nanocomposites with excellent electromagnetic interference shielding response[J]. Nanoscale, 2013, 5(10): 4330-4336.
[62] SONG Q, YE F, YIN X, et al. Carbon nanotube–multilayered graphene edge plane core–shell hybrid foams for ultrahigh-performance electromagnetic-interference shielding[J]. Advanced Materials, 2017, 29(31): 1701583.
[63] SANKARAN S, DESHMUKH K, AHAMED M B, et al. Recent advances in electromagnetic interference shielding properties of metal and carbon filler reinforced flexible polymer composites: A review[J]. Composites Part A: Applied Science and Manufacturing, 2018, 114: 49-71.
[64] LEE J, LIU Y, LIU Y, et al. Ultrahigh electromagnetic interference shielding performance of lightweight, flexible, and highly conductive copper-clad carbon fiber nonwoven fabrics[J]. Journal of Materials Chemistry C, 2017, 5(31): 7853-7861.
[65] JING X, WANG Y, ZHANG B. Electrical conductivity and electromagnetic interference shielding of polyaniline/polyacrylate composite coatings[J]. Journal of Applied Polymer Science, 2005, 98(5): 2149-2156.
[66] ACHARYA S, ALEGAONKAR P, DATAR S. Effect of formation of heterostructure of sral4fe8o19/rgo/pvdf on the microwave absorption properties of the composite[J]. Chemical Engineering Journal, 2019, 374: 144-154.
[67] PASTORE R, DELFINI A, MICHELI D, et al. Carbon foam electromagnetic mm-wave absorption in reverberation chamber[J]. Carbon, 2019, 144: 63-71.
[68] WANG Y, CHENG X-D, SONG W-L, et al. Hydro-sensitive sandwich structures for self-tunable smart electromagnetic shielding[J]. Chemical Engineering Journal, 2018, 344: 342-352.
[69] GUO H, CHEN Y, LI Y, et al. Electrospun fibrous materials and their applications for electromagnetic interference shielding: A review[J]. Composites Part A: Applied Science and Manufacturing, 2021, 143: 106309.
[70] LAI H, LI W, XU L, et al. Scalable fabrication of highly crosslinked conductive nanofibrous films and their applications in energy storage and electromagnetic interference shielding[J]. Chemical Engineering Journal, 2020, 400: 125322.
[71] ZHANG Z, WANG G, GU W, et al. A breathable and flexible fiber cloth based on cellulose/polyaniline cellular membrane for microwave shielding and absorbing applications[J]. Journal of Colloid and Interface Science, 2022, 605: 193-203.
[72] KONG W, YI S, SUN W, et al. Polyaniline-decorated carbon fibers for enhanced mechanical and electromagnetic interference shielding performances of epoxy composites[J]. Materials & Design, 2022, 217: 110658.
[73] CHEN R, WAN Y, WU W, et al. A lotus effect-inspired flexible and breathable membrane with hierarchical electrospinning micro/nanofibers and zno nanowires[J]. Materials & Design, 2019, 162: 246-248.
[74] STEJSKAL J, HAJNá M, KAŠPáRKOVá V, et al. Purification of a conducting polymer, polyaniline, for biomedical applications[J]. Synthetic Metals, 2014, 195: 286-293.
[75] STEJSKAL J, GILBERT R G. Polyaniline. Preparation of a conducting polymer(iupac technical report)[J]. Pure and Applied Chemistry, 2002, 74(5): 857-867.
[76] MATTES B R, WANG H L, YANG D, et al. Formation of conductive polyaniline fibers derived from highly concentrated emeraldine base solutions[J]. Synthetic Metals, 1997, 84(1): 45-49.
[77] 王新月, 王华洁, 李建三, 等. 不同酸掺杂聚苯胺防污添加剂的制备及其在防污涂料中的应用[J]. 电镀与涂饰, 2020, 39(06): 323-328.
[78] 吕尤. 导电聚苯胺纤维的制备与改性[D]; 深圳: 哈尔滨工业大学材料系 2019.
[79] CHEN Z, JIANG Y, XIN B, et al. Electrochemical analysis of conducting reduced graphene oxide/polyaniline/polyvinyl alcohol nanofibers as supercapacitor electrodes[J]. Journal of Materials Science: Materials in Electronics, 2020, 31(8): 5958-5965.
[80] PAPKOV D, ZOU Y, ANDALIB M N, et al. Simultaneously strong and tough ultrafine continuous nanofibers[J]. ACS Nano, 2013, 7(4): 3324-3331.
[81] ZHOU C, REN Y, HAN J, et al. Chiral polyaniline hollow nanotwists toward efficient enantioselective separation of amino acids[J]. ACS Nano, 2019, 13(3): 3534-3544.
[82] ZHANG Y, PAN T, YANG Z. Flexible polyethylene terephthalate/polyaniline composite paper with bending durability and effective electromagnetic shielding performance[J]. Chemical Engineering Journal, 2020, 389: 124433.
[83] LIU L, DENG H, TANG X, et al. Specific electromagnetic radiation in the wireless signal range increases wakefulness in mice[J]. Proceedings of the National Academy of Sciences, 2021, 118(31): e2105838118.
[84] LI D-Y, LIU L-X, WANG Q-W, et al. Functional polyaniline/mxene/cotton fabrics with acid/alkali-responsive and tunable electromagnetic interference shielding performances[J]. ACS Applied Materials & Interfaces, 2022, 14(10): 12703-12712.
[85] ZHANG Y, FANG X-X, WEN B-Y. Asymmetric ni/pvc films for high-performance electromagnetic interference shielding[J]. Chinese Journal of Polymer Science, 2015, 33(6): 899-907.
[86] GOPAKUMAR D A, PAI A R, POTTATHARA Y B, et al. Cellulose nanofiber-based polyaniline flexible papers as sustainable microwave absorbers in the x-band[J]. ACS Applied Materials & Interfaces, 2018, 10(23): 20032-20043.
[87] MARINS J A, SOARES B G, FRAGA M, et al. Self-supported bacterial cellulose polyaniline conducting membrane as electromagnetic interference shielding material: Effect of the oxidizing agent[J]. Cellulose, 2014, 21(3): 1409-1418.
[88] AVADHANAM V, THANASAMY D, KIRAN MATHAD J, et al. Single walled carbon nano tube -polyaniline core-shell/polyurethane polymer composite for electromagnetic interference shielding[J]. Polymer Composites, 2018, 39(11): 4104-4114.
[89] KHASIM S. Polyaniline-graphene nanoplatelet composite films with improved conductivity for high performance x-band microwave shielding applications[J]. Results in Physics, 2019, 12: 1073-1081.
[90] JELMY E J, RAMAKRISHNAN S, KOTHURKAR N K. Emi shielding and microwave absorption behavior of au-mwcnt/polyaniline nanocomposites[J]. Polymers for Advanced Technologies, 2016, 27(9): 1246-1257.
[91] ISMAIL M M, RAFEEQ S N, SULAIMAN J M A, et al. Electromagnetic interference shielding and microwave absorption properties of cobalt ferrite cofe2o4/polyaniline composite[J]. Applied Physics A, 2018, 124(5): 380.
[92] KUMAR S, ARTI, KUMAR P, et al. Steady microwave absorption behavior of two-dimensional metal carbide mxene and polyaniline composite in x-band[J]. Journal of Magnetism and Magnetic Materials, 2019, 488: 165364.
[93] BORA P J, LAKHANI G, RAMAMURTHY P C, et al. Outstanding electromagnetic interference shielding effectiveness of polyvinylbutyral–polyaniline nanocomposite film[J]. RSC Advances, 2016, 6(82): 79058-79065.
[94] ZHANG C, LV Q, LIU Y, et al. Rational design and fabrication of lightweight porous polyimide composites containing polyaniline modified graphene oxide and multiwalled carbon nanotube hybrid fillers for heat-resistant electromagnetic interference shielding[J]. Polymer, 2021, 224: 123742.
[95] PAN T, ZHANG Y, WANG C, et al. Mulberry-like polyaniline-based flexible composite fabrics with effective electromagnetic shielding capability[J]. Composites Science and Technology, 2020, 188: 107991.
[96] JOON S, KUMAR R, SINGH A P, et al. Fabrication and microwave shielding properties of free standing polyaniline-carbon fiber thin sheets[J]. Materials Chemistry and Physics, 2015, 160: 87-95.
[97] ZHANG M, LING H, DING S, et al. Synthesis of cf@pani hybrid nanocomposites decorated with fe3o4 nanoparticles towards excellent lightweight microwave absorber[J]. Carbon, 2021, 174: 248-259.
[98] VYAS M K, CHANDRA A. Synergistic effect of conducting and insulating fillers in polymer nanocomposite films for attenuation of x-band[J]. Journal of Materials Science, 2019, 54(2): 1304-1325.