This research looks at ways of tailoring and improving the stiffness of polypyrrole hydrogels for use as flexible supercapacitor electrodes. Molecules providing additional cross-linking between polypyrrole chains are added post-polymerisation but before gelation, and are found to increase gel stiffness by up to 600%, with the degree of change dependent on reactant type and proportion. It was also found that addition of phytic acid led to an increase in pseudocapacitive behaviour of the hydrogel, and thus a maximum specific capacitance of 217.07 F·g−1 could be achieved. This is an increase of 140% compared to pristine polypyrrole hydrogels produced by this method.
A González, E Goikolea, J A Barrena, R Mysyk. Review on supercapacitors: Technologies and material. Renewable & Sustainable Energy Reviews, 2016, 58: 1189–1206 https://doi.org/10.1016/j.rser.2015.12.249
2
I Shown, A Ganguly, L C Chen, K H Chen. Conducting polymer-based flexible supercapacitor. Energy Science & Engineering, 2015, 3(1): 2–26 https://doi.org/10.1002/ese3.50
3
G Wang, L Zhang, J Zhang. A review of electrode materials for electrochemical supercapacitors. Chemical Society Reviews, 2012, 41(2): 797–828 https://doi.org/10.1039/C1CS15060J
4
Y Shi, G Yu. Designing hierarchically nanostructured conductive polymer gels for electrochemical energy storage and conversion. Chemistry of Materials, 2016, 28(8): 2466–2477 https://doi.org/10.1021/acs.chemmater.5b04879
5
J Stejskal, M Trchovä, P Bober, Z Moràvkovà, D Kopecký, M Vrňata, J Prokeš, M Varga, E Watzlovà. Polypyrrole salts and bases: Superior conductivity of nanotubes and their stability towards the loss of conductivity by deprotonation. RSC Advances, 2016, 6(91): 88382–88391 https://doi.org/10.1039/C6RA19461C
6
X Zhang, J Zhang, W Song, Z Lu. Controllable synthesis of conducting polypyrrole nanostructures. Journal of Physical Chemistry B, 2006, 110(3): 1158–1165 https://doi.org/10.1021/jp054335k
7
A Kaynak. Electrical conductivity of polypyrrole films at a temperature range of 70 K to 350 K. Materials Research Bulletin, 1998, 33(1): 81–88 https://doi.org/10.1016/S0025-5408(97)00195-5
J U Otaigbe. The processing, structure and properties of elastomeric fibres. Handbook of Textile Fibre Structure. Volume 1: Fundamentals and Manufactured Polymer Fibres. Cambridge: Elsevier, Woodhead Publishing, 2009, 1–528
H Kang, K Geckeler. Enhanced electrical conductivity of polypyrrole prepared by chemical oxidative polymerization: Effect of the preparation technique and polymer additive. Polymer, 2000, 41(18): 6931–6934 https://doi.org/10.1016/S0032-3861(00)00116-6
12
L Pan, A Chortos, G Yu, Y Wang, S Isaacson, R Allen, Y Shi, R Dauskardt, Z Bao. An ultra-sensitive resistive pressure sensor based on hollow-sphere microstructure induced elasticity in conducting polymer film. Nature Communications, 2014, 5(1): 1–8 https://doi.org/10.1038/ncomms4002
13
Y Shi, L Pan, B Liu, Y Wang, Y Cui, Z Bao, G Yu. Nanostructured conductive polypyrrole hydrogels as high-performance, flexible supercapacitor electrodes. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2014, 2(17): 6086–6091 https://doi.org/10.1039/C4TA00484A
14
M Rajesh, J C Raj, B C Kim, B B Cho, M Ko, K H Yu. Supercapacitive studies on electropolymerized natural organic phosphate doped polypyrrole thin films. Electrochimica Acta, 2016, 220: 373–383 https://doi.org/10.1016/j.electacta.2016.10.118
15
H Zhou, T Ni, X Qing, X Yue, G Li, Y Lu. One-step construction of graphene-polypyrrole hydrogels and their superior electrochemical performance. RSC Advances, 2013, 4(8): 4134–4139 https://doi.org/10.1039/C3RA44647F
16
H Bai, K Sheng, P Zhang, C Li, G Shi. Graphene oxide/conducting polymer composite hydrogels. Journal of Materials Chemistry, 2011, 21(46): 18653–18658 https://doi.org/10.1039/c1jm13918e
17
Y Lu, W He, T Cao, H Guo, Y Zhang, Q Li, Z Shao, Y Cui, X Zhang. Elastic, conductive, polymeric hydrogels and sponges. Scientific Reports, 2014, 4: 1–8
18
X Zhou, T Li, J Wang, F Chen, D Zhou, Q Liu, L Zhang, J Shena, X Zhou. Shape morphing of anisotropy-encoded tough hydrogels enabled by asymmetrically-induced swelling and site-specific mechanical strengthening. Journal of Materials Chemistry. B, Materials for Biology and Medicine, 2018, 29(29): 4731–4737 https://doi.org/10.1039/C8TB01372A
19
X Zhou, T Li, J Wang, F Chen, D Zhou, Q Liu, B Li, J Cheng, X Zhou, B Zheng. Mechanochemical regulated origami with tough hydrogels by ion transfer printing. ACS Applied Materials & Interfaces, 2018, 10(10): 9077–9084 https://doi.org/10.1021/acsami.8b01610
20
T Li, J Wang, L Zhang, J Yang, M Yang, D Zhu, X Zhou, S Handschuh-Wang, Y Liua, X Zhou. “Freezing”, morphing, and folding of stretchy tough hydrogels. Journal of Materials Chemistry. B, Materials for Biology and Medicine, 2017, 29(29): 5726–5732 https://doi.org/10.1039/C7TB01265A
21
T Dai, X Qing, H Zhou, C Shen, J Wang, Y Lu. Mechanically strong conducting hydrogels with special double network structure. Synthetic Metals, 2010, 160(7-8): 791–796 https://doi.org/10.1016/j.synthmet.2010.01.024
22
J L Bredas, J C Scott, K Yakushi, G B Street. Polarons and bipolarons in polypyrrole: Evolution of the band structure and optical spectrum upon doping. Physical Review. B, 1984, 30(2): 1023–1025 https://doi.org/10.1103/PhysRevB.30.1023
23
Y Wang, Y Shi, L Pan, Y Ding, Y Zhao, Y Li, Y Shi, G Yu. Dopant-enabled supramolecular approach for controlled synthesis of nanostructured conductive polymer hydrogels. Nano Letters, 2015, 15(11): 7736–7741 https://doi.org/10.1021/acs.nanolett.5b03891
K G Neoh, T T Young, E T Kang, K L Tan. Structural and mechanical degradation of polypyrrole films due to aqueous media and heat treatment and the subsequent redoping characteristics. Journal of Applied Polymer Science, 1997, 64(3): 519–526 https://doi.org/10.1002/(SICI)1097-4628(19970418)64:3<519::AID-APP8>3.0.CO;2-N
26
Q Xie, S Kuwabata, H Yoneyama. EQCM studies on polypyrrole in aqueous solutions. Journal of Electroanalytical Chemistry, 1997, 420(1-2): 219–225 https://doi.org/10.1016/S0022-0728(96)04777-8
27
A G MacDiarmid, R J Mammone, R B Kaner, S J Porter, R Pethig, A J Heeger, D R Rosseinsky. The concept of ‘doping’ of conducting polymers: The role of reduction potentials. Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, 1985, 314(1528): 3–15 https://doi.org/10.1098/rsta.1985.0004
28
A Diaz, J Crowley, J Bargon, G Gardini, J Torrance. Electrooxidation of aromatic oligomers and conducting polymers. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, 1981, 121: 355–361 https://doi.org/10.1016/S0022-0728(81)80592-X