纤维素纳米纤丝-还原氧化石墨烯/聚苯胺气凝胶柔性电极复合材料的制备与性能
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摘要
利用高长径比的纤维素纳米纤丝(CNF)与片层结构的氧化石墨烯(GO)形成的CNF-GO复合水凝胶经抗坏血酸还原制备出CNF-还原氧化石墨烯(rGO)复合水凝胶材料。通过冷冻干燥法得到CNF-rGO复合气凝胶,并进一步通过苯胺单体在CNF-rGO复合气凝胶的孔道内原位聚合制备出CNF-rGO/聚苯胺(PANI)气凝胶柔性电极复合材料。研究了不同苯胺、CNF和GO的质量比对CNF-rGO/PANI气凝胶柔性电极复合材料的结构形貌和电化学性能的影响。结果表明,苯胺原位聚合后所得CNF-rGO/PANI复合气凝胶仍具有紧密的三维多孔网络结构。与rGO/PANI气凝胶电极复合材料相比,CNF-rGO/PANI气凝胶电极复合材料具有更理想的电容行为。当CNF与GO质量比为60∶40,PANI添加量为0.1mol时,CNF-rGO/PANI气凝胶电极复合材料比电容可达85.9F·g-1,且其电化学性能几乎不受弯曲程度的影响,展现出了良好的柔韧性和电化学性能。
The cellulose nanofiber-reduced graphene oxide(CNF-rGO)composite hydrogel was prepared by ascorbic acid reduction of CNF-graphene oxide(GO)composite hydrogel which was obtained from CNF with high aspect ratio and GO with nanosheet.By freeze-drying method,CNF-rGO composite aerogel was obtained.By the in situ polymerization of aniline monomer,CNF-rGO/polyaniline(PANI)composite aerogels as flexible electrode materials was prepared.The effects of different dosage mass ratio of aniline,CNF and rGO on the morphology,structure and electrochemical properties of CNF-rGO/PANI aerogels electrode composites were studied.The results show that the CNF-rGO/PANI composite aerogels still have relatively close 3 Dnetwork structure after in situ polymerization of aniline.Compared with rGO/PANI aerogel eletrode composites,the CNF-rGO/PANI aerogel eletrode composites have more excellent capacitance behavior.When the mass ratio of CNF and GO is 60∶40 and the amount of PANI is0.1 mol,the specific capacitance of the CNF-rGO/PANI aerogel electrode composites is 85.9 F·g-1,and its electrochemical properties are hardly affected by bending degree.So,the CNF-rGO/PANI aerogel eletrode composites show good electrochemical performance and excellent flexibility.
The cellulose nanofiber-reduced graphene oxide(CNF-rGO)composite hydrogel was prepared by ascorbic acid reduction of CNF-graphene oxide(GO)composite hydrogel which was obtained from CNF with high aspect ratio and GO with nanosheet.By freeze-drying method,CNF-rGO composite aerogel was obtained.By the in situ polymerization of aniline monomer,CNF-rGO/polyaniline(PANI)composite aerogels as flexible electrode materials was prepared.The effects of different dosage mass ratio of aniline,CNF and rGO on the morphology,structure and electrochemical properties of CNF-rGO/PANI aerogels electrode composites were studied.The results show that the CNF-rGO/PANI composite aerogels still have relatively close 3 Dnetwork structure after in situ polymerization of aniline.Compared with rGO/PANI aerogel eletrode composites,the CNF-rGO/PANI aerogel eletrode composites have more excellent capacitance behavior.When the mass ratio of CNF and GO is 60∶40 and the amount of PANI is0.1 mol,the specific capacitance of the CNF-rGO/PANI aerogel electrode composites is 85.9 F·g-1,and its electrochemical properties are hardly affected by bending degree.So,the CNF-rGO/PANI aerogel eletrode composites show good electrochemical performance and excellent flexibility.
引文
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[25]HUMMERS W S,OFFEMAN R E.Preparation of graphitic oxide[J].Journal of the American Chemical Society,1958,80(6):1339.
[2]ZHANG X Y,ZHANG H Z,LIN Z Q,et al.Recent advances and challenges of stretchable supercapacitors based on carbon materials[J].Science China Materials,2016,59(6):475-494.
[3]ZHOU H C,LONG J R,YAGHI O M.Introduction to metal-organic frameworks[J].Chemical Reviews,2012,112:673-674.
[4]NOGI M,KARAKAWA M,KOMODA N,et al.Transparent conductive nanofiber paper for foldable solar cells[J].Scientific Reports,2015,5:17254.
[5]MA L N,LIU R,NIU H J,et al.Freestanding conductive film based on polypyrrole/bacterial cellulose/graphene paper for flexible supercapacitor:Large areal mass exhibits excellent areal capacitance[J].Electrochimica Acta,2016,222:429-437.
[6]潘媛媛,杨旖旎,滕佑超,等.纳米纤维素/碳纳米管/纳米银线柔性电极的制备[J].包装工程,2018,39(7):80-85.PAN Y Y,YANG Y N,TENG Y C,et al.Preparation of flexible cellulose nanofibers/carbon nanotubes/silver nanowires composite electrode[J].Packaing Engineering,2018,39(7):80-85(in Chinese).
[7]JIA J,SUN X,LIN X,et al.Exceptional electrical conductivity and fracture resistance of 3Dinterconnected graphene foam/epoxy composites[J].ACS Nano,2014,8(6):5774-5783.
[8]苏中淮,陶国良,吴海平,等.银纳米线-聚对苯二甲酸乙二醇酯透明导电胶膜[J].复合材料学报,2013,30(5):55-60.SU Z H,TAO G L,WU H P,et al.Silver nanowires-polyethylene terephthalate conduvtive film[J].Acta Materiae Compositae Sinica,2013,30(5):55-60(in Chinese).
[9]XIONG Z Y,LIAO C L,HAN W H,et al.Mechanically tough large-area hierarchical porous graphene films for highperformance flexible supercapacitor applications[J].Advanced Materials,2015,27(30):4469-4475.
[10]NIU Z Q,DONG H B,ZHU B W,et al.Highly stretchable,integrated supercapacitors based on single-walled carbon nanotube films with continuous reticulate architecture[J].Advanced Materials,2013,25(7):1058-1064.
[11]CONG H P,REN X C,WANG P,et al.Flexible graphenepolyaniline composite paper for high-performance supercapacitor[J].Energy&Environmental Science,2013,6(4):1185-1191.
[12]MALHO J M,LAAKSONEN P I,WATHER A,et al.Facile method for stiff,tough,and strong nanocomposites by direct exfoliation of multilayered graphene into native nano cellulose matrix[J].Biomacromolecules,2012,13(4):1093-1099.
[13]WANG G K,SUN X,LU F Y,et al.Flexible pillared graphene-paper electrodes for high-performance electrochemical supercapacitors[J].Small,2012,8(3):452-459.
[14]WU Q,XV Y X,YAO Z Y,et al.Supercapacitors based on flexible graphene/polyaniline nanofiber composite films[J].ACS Nano,2010,4(4):1963-1970.
[15]MAITI U N,LIM J,LEE K E,et al.Three-dimensional shape engineered,interfacial gelation of reduced graphene oxide for high rate,large capacity supercapacitors[J].Advanced Mater,2014,26(4):615-619.
[16]SUMBOJA A,FOO C Y,WANG X,et al.Large areal mass,flexible and free-standing reduced graphene oxide/manganese dioxide paper for asymmetric supercapacitor device[J].Advanced Materials,2013,25(20):2809-2815.
[17]YANG C,LI D G.Flexible and foldable supercapacitor electrodes from the porous 3Dnetwork of cellulose nanofibers,carbon nanotubes and polyaniline[J].Materials Letters,2015,155:78-81.
[18]LIU Q Z,JING S S,WANG S,et al.Flexible nanocomposites with ultrahigh specific areal capacitance and tunable properties based on a cellulose derived nanofiber-carbon sheet framework coated with polyaniline[J].Journal of Materials Chemistry A,2016,4(34):13352-13362.
[19]韩景泉,王绍霖,岳一莹,等.纳米纤维素-聚吡咯/天然橡胶柔性导电弹性体的制备与性能[J].复合材料学报,2018,35(10):2612-2623.HAN J Q,WANG S L,YUE Y Y,et al.Preparation and characterization of cellulose nanofibers-polypyrrole/natural rubber flexible conductive elastomer[J].Acta Materiae Compositae Sinica,2018,35(10):2612-2623(in Chinese).
[20]韩景泉,王慧祥,岳一莹,等.纤维素纳米纤丝-碳纳米管/聚乙烯醇硼酸盐复合导电水凝胶[J].复合材料学报,2017,34(10):2312-2320.HAN J Q,WANG H X,YUE Y Y,et al.Cellulose nanofiber-carbon nanotube/polyvinyl alcohol-borax hybrid conductive hydrogel[J].Acta Materiae Compositae Sinica,2017,34(10):2312-2320(in Chinese).
[21]YANG C,CHEN C C,PAN Y Y,et al.Flexible highly specific capacitance aerogel electrodes based on cellulose nanofibers,carbon nanotubes and polyaniline[J].Electrochimica Act,2015,182:264-271.
[22]XV S M,YU W J,YAO X L,et al.Nanocellulose-assisted dispersion of graphene to fabricate poly(vinylalcohol)/graphene nanocomposite for humidity sensing[J].Composites Science and Technology,2016,131:67-76.
[23]MA L N,LIU R,NIU H J,et al.Flexible and freestanding supercapacitor electrodes based on nitrogen-doped carbon networks/graphene/bacterial cellulose with ultrahigh areal capacitance[J].ACS Applied Materials&Interface,2016,8(49):33608-33618.
[24]周昌兵,徐阳,刘馨月,等.剑麻纤维素纳米纤的制备及表征[J].高分子材料科学与工程,2017,33(10):130-134.ZHOU C B,XV Y,LIU X Y,et al.Fabrication and characterization of nanofibrillated cellulose from sisal fiber[J].Polymeric Materials Science and Engineering,2017,33(10):130-134(in Chinese).
[25]HUMMERS W S,OFFEMAN R E.Preparation of graphitic oxide[J].Journal of the American Chemical Society,1958,80(6):1339.