Abstract
Cellulose/poly(vinyl alcohol) (PVA) composite gels are prepared as separators for quasi-solid-state electrical double-layer capacitors (EDLCs) by a simple freeze-thawing method. Fourier-transform infrared spectroscopy, scanning electron microscopy and mechanical testing machine are used to characterize the structure and morphology. Compared with the PVA gel, the as-prepared composite gels show improved network structure and enhanced mechanical properties. The cyclic voltammetric curves, galvanostatic charge/discharge curves, electrochemical impedance spectroscopy and cycling performance of EDLCs with these composite gels are also evaluated. It is found that the EDLC with the optimum composite gel can work in a voltage window of 0–1.8 V and display a specific capacitance of 125.1 F g−1 (based on active carbon on one electrode) at a current density of 1 A g−1. Furthermore, it also has an excellent cycling stability with capacitance retention of ~ 88% after 1500 cycles. These results suggest that the composite gels can serve as a class of promising separators for EDLCs.
Graphical abstract
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Abitbol T, Johnstone T, Quinn TM, Gray DG (2011) Reinforcement with cellulose nanocrystals of poly(vinyl alcohol) hydrogels prepared by cyclic freezing and thawing. Soft Matter 7:2373. https://doi.org/10.1039/c0sm01172j
Anothumakkool B, Torris ATA, Bhange SN, Badiger MV, Kurungot S (2014) Electrodeposited polyethylenedioxythiophene with infiltrated gel electrolyte interface: a close contest of an all-solid-state supercapacitor with its liquid-state counterpart. Nanoscale 6:5944–5952. https://doi.org/10.1039/c4nr00659c
Castro C et al (2014) In situ production of nanocomposites of poly(vinyl alcohol) and cellulose nanofibrils from gluconacetobacter bacteria: effect of chemical crosslinking. Cellulose 21:1745–1756
Chang C, Lue A, Zhang L (2008) Effects of crosslinking methods on structure and properties of cellulose/PVA hydrogels. Macromol Chem Phys 209:1266–1273. https://doi.org/10.1002/macp.200800161
Di Fabio A, Giorgi A, Mastragostino M, Soavi F (2001) Carbon-poly(3-methylthiophene) hybrid supercapacitors. J Electrochem Soc 148:A845. https://doi.org/10.1149/1.1380254
Gamby J, Taberna PL, Simon P, Fauvarque JF, Chesneau M (2001) Studies and characterisations of various activated carbons used for carbon/carbon supercapacitors. J Power Sources 101:109–116
Gao Q, Demarconnay L, Raymundo-Piñero E, Béguin F (2012) Exploring the large voltage range of carbon/carbon supercapacitors in aqueous lithium sulfate electrolyte. Energy Environ Sci 5:9611. https://doi.org/10.1039/c2ee22284a
Hai T, Sugimoto R (2018) Surface functionalization of cellulose with poly(3-hexylthiophene) via novel oxidative polymerization. Carbohydr Polym 179:221
He F, He X, Yang W, Zhang X, Zhou L (2018) In-situ synthesis and structural characterization of cellulose-silica aerogels by one-step impregnation. J Non-Cryst Solids 488:36–43
Huang C-W, Wu C-A, Hou S-S, Kuo P-L, Hsieh C-T, Teng H (2012) Gel electrolyte derived from poly(ethylene glycol) blending poly(acrylonitrile) applicable to roll-to-roll assembly of electric double layer capacitors. Adv Funct Mater 22:4677–4685. https://doi.org/10.1002/adfm.201201342
Huang H, Luo G, Xu L, Lei C, Tang Y, Tang S, Du Y (2015) NH3 assisted photoreduction and N-doping of graphene oxide for high performance electrode materials in supercapacitors. Nanoscale 7:2060–2068. https://doi.org/10.1039/c4nr05776g
Jiang M, Zhu J, Chen C, Lu Y, Ge Y, Zhang X (2016) Poly(vinyl alcohol) borate gel polymer electrolytes prepared by electrodeposition and their application in electrochemical supercapacitors. ACS Appl Mater Interfaces 8:3473–3481
Lee J-K, Lee Y-J, Chae W-S, Sung Y-M (2006) Enhanced ionic conductivity in PEO-LiClO4 hybrid electrolytes by structural modification. J Electroceram 17:941–944. https://doi.org/10.1007/s10832-006-7672-7
Li L, Wu Z, Yuan S, Zhang X-B (2014) Advances and challenges for flexible energy storage and conversion devices and systems. Energy Environ Sci 7:2101. https://doi.org/10.1039/c4ee00318g
Liang Y et al (2018) Surface-modified cellulose nanocrystals for biobased epoxy nanocomposites. Polymer 134:155–162
Liu D, Sun X, Tian H, Maiti S, Ma Z (2013) Effects of cellulose nanofibrils on the structure and properties on PVA nanocomposites. Cellulose 20:2981–2989
Liu X, Wu D, Wang H, Wang Q (2014) Self-recovering tough gel electrolyte with adjustable supercapacitor performance. Adv Mater 26:4370–4375. https://doi.org/10.1002/adma.201400240
Liu Y et al (2018) Understanding of carbon-based supercapacitors ageing mechanisms by electrochemical and analytical methods. J Power Sources 366:123–130
Lu J, Wang T, Drzal LT (2008) Preparation and properties of microfibrillated cellulose polyvinyl alcohol composite materials. Compos A Appl Sci Manuf 39:738–746. https://doi.org/10.1016/j.compositesa.2008.02.003
Luo J-Y, Liu J-L, He P, Xia Y-Y (2008) A novel LiTi2(PO4)3/MnO2 hybrid supercapacitor in lithium sulfate aqueous electrolyte. Electrochim Acta 53:8128–8133. https://doi.org/10.1016/j.electacta.2008.05.080
Ma G, Li J, Sun K, Peng H, Mu J, Lei Z (2014) High performance solid-state supercapacitor with PVA–KOH–K3[Fe(CN)6] gel polymer as electrolyte and separator. J Power Sources 256:281–287. https://doi.org/10.1016/j.jpowsour.2014.01.062
Moon WG, Kim GP, Lee M, Song HD, Yi J (2015) A biodegradable gel electrolyte for use in high-performance flexible supercapacitors. ACS Appl Mater Interfaces 7:3503–3511. https://doi.org/10.1021/am5070987
Na R et al (2016) A novel poly(ethylene glycol)-grafted poly(arylene ether ketone) blend micro-porous polymer electrolyte for solid-state electric double layer capacitors formed by incorporating a chitosan-based LiClO4gel electrolyte. J Mater Chem A 4:18116–18127. https://doi.org/10.1039/c6ta07846j
Niu Z et al (2013) Highly stretchable, integrated supercapacitors based on single-walled carbon nanotube films with continuous reticulate architecture. Adv Mater 25:1058–1064. https://doi.org/10.1002/adma.201204003
Trapa PE et al (2005) Rubbery graft copolymer electrolytes for solid-state, thin-film lithium batteries. J Electrochem Soc 152:A1. https://doi.org/10.1149/1.1824032
Wang G, Lu X, Ling Y, Zhai T, Wang H, Tong Y, Li Y (2012) LiCl/PVA gel electrolyte stabilizes vanadium oxide nanowire electrodes for pseudocapacitors. ACS Nano 6:10296–10302. https://doi.org/10.1021/nn304178b
Wang W, Liang T, Bai H, Dong W, Liu X (2018) All cellulose composites based on cellulose diacetate and nanofibrillated cellulose prepared by alkali treatment. Carbohydr Polym 179:297–304
Wessells CD, Peddada SV, McDowell MT, Huggins RA, Cui Y (2012) The effect of insertion species on nanostructured open framework hexacyanoferrate battery electrodes. J Electrochem Soc 159:A98. https://doi.org/10.1149/2.060202jes
Wu S, Li F, Wang H, Fu L, Zhang B, Li G (2010) Effects of poly (vinyl alcohol) (PVA) content on preparation of novel thiol-functionalized mesoporous PVA/SiO 2 composite nanofiber membranes and their application for adsorption of heavy metal ions from aqueous solution. Polymer 51:6203–6211
Yang Z, Deng J, Chen X, Ren J, Peng H (2013) A highly stretchable, fiber-shaped supercapacitor. Angew Chem 52:13453–13457. https://doi.org/10.1002/anie.201307619
Yang L, Hu J, Lei G, Liu H (2014) Ionic liquid-gelled polyvinylidene fluoride/polyvinyl acetate polymer electrolyte for solid supercapacitor. Chem Eng J 258:320–326. https://doi.org/10.1016/j.cej.2014.05.149
Zhang X, Wang L, Peng J, Cao P, Cai X, Li J, Zhai M (2015) A flexible ionic liquid gelled PVA-Li2SO4 polymer electrolyte for semi-solid-state supercapacitors. Adv Mater Interfaces 2:1500267. https://doi.org/10.1002/admi.201500267
Zheng JP (1999) Ruthenium oxide-carbon composite electrodes for electrochemical capacitors. Electrochem Solid State Lett 2:359–361
Zhou M, Zhang H, Qiao Y, Li CM, Lu Z (2018) A flexible sandwich-structured supercapacitor with poly(vinyl alcohol)/H3PO4-soaked cotton fabric as solid electrolyte, separator and supporting layer. Cellulose 25:3459–3469. https://doi.org/10.1007/s10570-018-1786-3
Acknowledgments
This work was supported by the National Natural Science Foundation of China (NSFC) (51503161) and Hubei Provincial Natural Science Foundation of China (2018CFB267).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Ji, Y., Liang, N., Xu, J. et al. Cellulose and poly(vinyl alcohol) composite gels as separators for quasi-solid-state electric double layer capacitors. Cellulose 26, 1055–1065 (2019). https://doi.org/10.1007/s10570-018-2123-6
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-018-2123-6