CN108335921B - Polypyrrole nanotube/graphene nanosheet composite material, and preparation and application thereof - Google Patents
Polypyrrole nanotube/graphene nanosheet composite material, and preparation and application thereof Download PDFInfo
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- CN108335921B CN108335921B CN201810060771.8A CN201810060771A CN108335921B CN 108335921 B CN108335921 B CN 108335921B CN 201810060771 A CN201810060771 A CN 201810060771A CN 108335921 B CN108335921 B CN 108335921B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 176
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 146
- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 122
- 239000002071 nanotube Substances 0.000 title claims abstract description 106
- 239000002135 nanosheet Substances 0.000 title claims abstract description 92
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- 238000004146 energy storage Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims description 24
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- 239000000047 product Substances 0.000 claims description 21
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- 238000000576 coating method Methods 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000005917 acylation reaction Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 claims description 5
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- BGRWYRAHAFMIBJ-UHFFFAOYSA-N diisopropylcarbodiimide Natural products CC(C)NC(=O)NC(C)C BGRWYRAHAFMIBJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007784 solid electrolyte Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 4
- 229940012189 methyl orange Drugs 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 claims description 3
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 3
- 229930003268 Vitamin C Natural products 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- 229940071870 hydroiodic acid Drugs 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 235000019154 vitamin C Nutrition 0.000 claims description 3
- 239000011718 vitamin C Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-Lutidine Substances CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims 1
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 claims 1
- 239000002086 nanomaterial Substances 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 4
- 230000001681 protective effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- 239000003990 capacitor Substances 0.000 description 10
- 239000000376 reactant Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 7
- 229920001940 conductive polymer Polymers 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
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- 239000006185 dispersion Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
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- 239000011241 protective layer Substances 0.000 description 3
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002055 nanoplate Substances 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to the field of energy storage nano materials, and particularly relates to a polypyrrole nanotube/graphene nanosheet composite material, a preparation method and application thereof, wherein a shell layer formed by graphene nanosheets is coated on the outer surface of a polypyrrole nanotube, the size of each graphene nanosheet is 5-30 nm, the graphene nanosheets and the polypyrrole nanotube are connected through amido bonds, the carbon content of the amido bonds in the composite material is not higher than 6.7% of the total carbon ratio, and the polypyrrole nanotube is partially or completely coated by the corresponding graphene shell layer. The composite material is connected with the polypyrrole nanotube and the graphene nanosheet through chemical covalent bonds, the polypyrrole nanotube is completely wrapped by the controllable graphene shell layer by adjusting the mass ratio of the polypyrrole nanotube to the graphene nanosheet, the composite material is applied to an all-solid-state flexible supercapacitor, the conductivity is increased, the capacitance capacity is optimized and improved, and meanwhile, the composite material serves as a protective shell layer to enhance the charge-discharge cycle stability.
Description
Technical Field
The invention belongs to the field of energy storage nano materials, and particularly relates to a polypyrrole nanotube/graphene nanosheet composite material, and a preparation method and application thereof.
Background
With the continuous increase of the demand of sustainable and clean energy, the important role of the electrochemical energy storage system in the fields of green power grids, portable electronic equipment, electric automobiles and the like is increasingly prominent. The super capacitor has the advantages of high power density, high charging and discharging speed, long service life and the like, and has gained much attention, wearable electronic products are rapidly developed in recent years, all-solid-state flexible super capacitors are highly favored, and the development of electrode materials with excellent electrochemical capacitance performance and high cycle stability is a key content and an important challenge.
The conductive polymer (such as polypyrrole, polyaniline and polythiophene) has low cost, good physical and chemical properties and excellent electrochemical capacitance performance, and is an ideal electrode material of a super capacitor. To further improve specific surface and expansion properties, various conductive polymer nanostructures such as nanotubes, nanospheres, nanowires, etc. and composites thereof are designed, prepared and used as electrode materials. However, the conductive polymer of the nanostructure has poor cycle stability, is easily dedoped in an insulating state, has high contact resistance, and has structural stability damaged in the charge and discharge volume expansion/contraction process. The compounding of the conductive polymer and the carbon nano material (such as carbon nano tube/wire, fullerene and graphene) is an effective way for improving the conductivity and the charge-discharge cycle stability of the conductive polymer, particularly the graphene has the characteristics of good conductivity, low permeability, high hardness and the like, and is an electrode material with potential. For example, chinese patent CN1026227768A discloses a nanocomposite prepared by in-situ polymerization of graphene oxide and polypyrrole and applied to a supercapacitor electrode, and a rapid preparation method thereof. In chinese patent CN105140045A, pyrrole is adsorbed on a graphene nanosheet by a molecular adsorption method, and an electrode material of a graphene polypyrrole pseudocapacitive supercapacitor is obtained after a polymerization reaction.
The compounding strategy of the conductive polypyrrole and the graphene mainly comprises the modes of physical compounding, chemical covalent bond bonding, polypyrrole nanostructure coating by a graphene layer and the like under the van der waals force or electrostatic adsorption effect. In which a conductive polymer nanostructure is coated with a stable thin shell (e.g., Nafion film, TiO)2Carbon material) can effectively delay the structural damage caused by volume expansion/contraction in the cyclic charge-discharge process, and greatly prolong the service life. For example, the graphene shell layer can serve as an electron transfer channel to improve conductivity, and also serves as a protective layer to alleviate structural damage of internal active materials and improve cycle stability. However, the polypyrrole nano-structure coated with the carbon material generally prepared in the prior art adopts a complete coating mode, and the shell layer is completely coated, so that the contact between the inner core and electrolyte ions is hindered to a certain extent, and the capacitance capacity is influenced.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a polypyrrole nanotube/graphene nanosheet composite material with a core/shell structure, a preparation method and application thereof, which fully combine the characteristics and requirements of the polypyrrole/graphene composite material used as a capacitor electrode material, redesign the initial size, the mass ratio, the morphology and the final coating structure of the polypyrrole nanotube and the graphene nanosheet, and correspondingly obtain the polypyrrole nanotube/graphene nanosheet composite material with the core/shell structure and the controllable graphene shell coating degree.
In order to achieve the above object, according to one aspect of the present invention, there is provided a polypyrrole nanotube/graphene nanoplatelet composite, in which graphene nanoplatelets form shell layers coated on the outer surface of a polypyrrole nanotube, the size of each graphene nanoplatelet is 5 to 30nm, the graphene nanoplatelets and the polypyrrole nanotube are connected by amide bonds, the carbon content of the amide bonds in the composite is not higher than 6.7%, and the polypyrrole nanotube is partially or completely coated by the corresponding graphene shell layers.
Preferably, the amide bond carbon accounts for 4-6% of the total carbon in the composite material.
According to another aspect of the present invention, there is provided a method for preparing a polypyrrole/graphene composite material, comprising the steps of:
(1) mixing and dispersing a polypyrrole nanotube and a graphene nanosheet in a solvent according to a mass ratio of 10: 1-1: 10, adding a catalyst, and carrying out an acylation reaction to obtain an acylation reaction product; the graphene nanosheet contains carboxyl, and the size of the graphene nanosheet is 5-30 nm;
(2) cleaning the acylation reaction product obtained in the step (1), removing a solvent, a catalyst and unreacted graphene nanosheets, drying, dispersing in deionized water, adding a reducing agent, and removing oxygen-containing groups on a graphene shell layer in the reaction product to obtain a reduced product;
(3) and (3) drying the product obtained after reduction in the step (2) after washing to obtain the polypyrrole nanotube/graphene nanosheet composite material with the core/shell structure.
Preferably, the preparation method of the polypyrrole nanotube comprises the following steps: mixing ferric trichloride and methyl orange in a solvent according to a molar ratio of 5: 1-20: 1, stirring for 30-120 minutes at 10-30 ℃, dropwise adding 20-200 mu L of pyrrole monomer, stirring for 6-24 hours at 10-30 ℃, cleaning, filtering and drying the obtained product to obtain the polypyrrole nanotube.
Preferably, the preparation method of the graphene nanoplatelets comprises the following steps: adding carbon black powder into nitric acid with the concentration of 4-12M, heating and refluxing for 12-72 hours, performing ultrasonic treatment and centrifugation to obtain supernatant, and heating at 150-250 ℃ for 6-24 hours to obtain the graphene nanosheet.
Preferably, the polypyrrole nanotubes and the graphene nanosheets are mixed according to a mass ratio of 5: 1-1: 1.
Preferably, the solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran or chloroform.
Preferably, the catalyst is selected from the group consisting of Dicyclohexylcarbodiimide (DCC), Diisopropylcarbodiimide (DIC), 1- (3-dimethylaminopropyl) -3-Ethylcarbodiimide (EDCI), 4-N, N-Dimethylpyridine (DMAP), and 1-hydroxybenzotriazole (HOBt).
Preferably, the acylation reaction temperature is 20-30 ℃, and the reaction time is 6-48 hours.
Preferably, the drying temperature is 25-80 ℃, and the drying time is 6-24 hours.
Preferably, the reducing agent is selected from hydrazine hydrate, sodium borohydride, vitamin C or hydroiodic acid.
According to another aspect of the invention, there is provided a use of the composite material for the preparation of an energy storage electrode active material.
According to another aspect of the invention, an all-solid-state flexible supercapacitor is characterized by comprising a flexible current collector, an electrode active material and a solid electrolyte, wherein the electrode active material is the polypyrrole nanotube/graphene nanosheet composite material.
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
(1) the invention provides a polypyrrole nanotube/graphene nanosheet composite material with a core/shell structure and controllable graphene shell coating degree, wherein the graphene nanosheets are in keyed joint coating on the outer surface of the polypyrrole nanotube, carboxyl groups of the graphene nanosheets are connected with amino groups of the polypyrrole nanotube through amido bonds, and the polypyrrole nanotube is partially or completely coated by the controllable graphene shell by adjusting the mass ratio of the graphene nanosheets to the amino groups of the polypyrrole nanotube.
(2) The invention provides a preparation method of a polypyrrole nanotube/graphene nanosheet composite material with a core/shell structure and controllable graphene shell coating degree, wherein the polypyrrole nanotube/graphene nanosheet composite material is prepared by mixing and reacting a carboxyl-containing graphene nanosheet and a polypyrrole nanotube with the size of 5-30 nm according to different mass ratios, and controlling the total amount of the shell graphene nanosheet by adjusting the mass ratio of the polypyrrole nanotube to the graphene nanosheet, so that the polypyrrole nanotube is partially and completely coated by the graphene shell, and the polypyrrole nanotube/graphene nanosheet composite material with different coating degrees is obtained.
(3) According to the method, the polypyrrole nanotube is coated by the graphene nanosheets with specific size ranges, and the polypyrrole nanotube is partially to completely coated by the controllable graphene shell layers by adjusting the mass ratio of the polypyrrole nanotube to the graphene nanosheets. The graphene shell layer not only serves as a protective layer of the polypyrrole nanotube core, but also can improve conductivity. More importantly, the partial coating of the controllable shell layer also optimizes the capacitance capacity of the controllable shell layer. The invention finds that the complete wrapping of the graphene shell layer can limit partial electrochemical behaviors of the core conductive polypyrrole, such as an ion doping/de-doping process in a charging and discharging process, so that the capacitance is reduced, and partial wrapping to a certain degree can overcome the defects and obtain higher electrical performance. Therefore, the polypyrrole nanotube/graphene nanosheet composite with the core/shell structure, which is prepared by the method, is used as an electrode active material of the super capacitor, and has high capacitance capacity and stable charge-discharge cycle characteristics.
(4) According to the method, the polypyrrole is coated by the graphene nanosheets with the size of 5-30 nm, so that the total amount of the shell graphene nanosheets is controllable, and partial coating becomes possible.
Drawings
Fig. 1 is a schematic diagram of a preparation process of a polypyrrole nanotube/graphene nanoplatelet composite according to an embodiment of the present invention;
FIG. 2 is a ratio of amido bond carbons to total carbons of polypyrrole nanotube/graphene nanoplate composites prepared under the condition of different mass ratios of reactants (graphene nanoplate GNFs: polypyrrole nanotubes PNTs) and corresponding Transmission Electron Microscope (TEM) photographs in an embodiment of the present invention;
FIG. 3 is a graph of capacitance of polypyrrole nanotube/graphene nanoplatelet composites prepared with different mass ratios of reactants (graphene nanoplatelets GNFs: polypyrrole nanotubes PNTs) according to an embodiment of the present invention;
fig. 4 is a cyclic voltammetry curve of an all-solid-state flexible supercapacitor assembled according to an embodiment of the invention in different bending states and an application example.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a preparation method of a polypyrrole/graphene composite material, which is characterized by comprising the following steps:
(1) mixing and dispersing a polypyrrole nanotube and a graphene nanosheet in a solvent according to a mass ratio of 10: 1-1: 10, adding a catalyst, and carrying out an acylation reaction to obtain an acylation reaction product; the graphene nanosheet is a carboxyl-containing graphene nanosheet with the size of 5-30 nm;
(2) cleaning the acylation reaction product obtained in the step (1), removing a solvent, a catalyst and unreacted graphene nanosheets, drying, dispersing in deionized water, adding a reducing agent to remove residual oxygen-containing groups on a graphene shell layer in the reaction product, and improving the conductivity of the composite material to obtain a reduced product;
(3) and (3) washing and drying the reduced product obtained in the step (2) to obtain the polypyrrole nanotube/graphene nanosheet composite material.
The specific preparation method of the polypyrrole nanotube comprises the following steps: mixing ferric trichloride and methyl orange in a solvent according to a molar ratio of 5: 1-20: 1, stirring for 30-120 minutes at 10-30 ℃, dropwise adding 20-200 mu L of pyrrole monomer, stirring for 6-24 hours at 10-30 ℃, cleaning, filtering and drying the obtained product, specifically, cleaning with 200-1000 mL of deionized water/ethanol mixed solution, filtering, placing in a drying box, and drying for 6-24 hours at 25-80 ℃ to obtain the polypyrrole nanotube.
The specific preparation method of the graphene nanosheet comprises the following steps: adding 0.1-1.0 g of carbon black powder into 50-250 mL of 4-12M concentrated nitric acid, heating and refluxing for 12-72 hours, performing ultrasonic treatment and centrifugation to obtain supernatant, and heating at 150-250 ℃ for 6-24 hours to obtain the graphene nanosheet.
The specific preparation method of the polypyrrole/graphene composite comprises the following steps: mixing the polypyrrole nanotubes and the graphene nanosheets according to different mass ratios of 10: 1-1: 10, ultrasonically dispersing the polypyrrole nanotubes and the graphene nanosheets in a certain amount of solvent, wherein the solvent can be N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, trichloromethane or the like, adding a trace amount of catalyst, and the catalyst can be Dicyclohexylcarbodiimide (DCC), Diisopropylcarbodiimide (DIC), 1- (3-dimethylaminopropyl) -3-Ethylcarbodiimide (EDCI), 4-N, N-Dimethylpyridine (DMAP), 1-hydroxybenzotriazole (HOBt) or a combination thereof, and stirring and reacting for 6-48 hours at 10-30 ℃. And ultrasonically cleaning the obtained product by using a solvent and deionized water, placing the product in a drying box, and drying the product for 6-24 hours at the temperature of 25-80 ℃. And (2) ultrasonically dispersing a certain amount of dried product in a solvent again, adding a reducing agent such as hydrazine hydrate, sodium borohydride, vitamin C or hydroiodic acid and the like, stirring and reacting for 2-12 hours at 10-30 ℃, washing the product with the solvent and deionized water, and drying for 6-24 hours at 25-80 ℃ to obtain the polypyrrole nanotube/graphene nanosheet composite.
The invention provides a polypyrrole nanotube/graphene nanosheet composite material with a core/shell structure, wherein the coating degree of the polypyrrole nanotube/graphene nanosheet composite material is controllable, the graphene nanosheet is in key joint coating on the outer surface of the polypyrrole nanotube, the graphene nanosheet is connected with the polypyrrole nanotube through an amido bond, the size of the graphene nanosheet is 5-30 nm, and the polypyrrole nanotube is partially or completely coated by a controllable graphene shell layer by adjusting the mass ratio of the graphene nanosheet to the polypyrrole nanotube. And (3) describing the coating degree of the polypyrrole nanotube by the graphene shell layer by combining a Transmission Electron Microscope (TEM) picture and analyzing a carbon C spectrum result by X-ray photoelectron spectroscopy (XPS) according to the change of the proportion of amido bond carbon in the compound to the total carbon, wherein the proportion of the amido bond carbon in the compound to the total carbon is 0-6.7%, and the polypyrrole nanotube is completely coated by the corresponding graphene shell layer. The total carbon comprises three parts of the carbon content of the graphene nanosheets, the carbon content of the polypyrrole nanotubes and the carbon content of amide bonds. The composite material can be used as an electrode active material to further assemble an all-solid-state flexible supercapacitor. When the polypyrrole nanotubes and the graphene nanosheets are synthesized according to the mass ratio of 5: 1-1: 1, the amido bond carbon in the composite material accounts for 4% -6% of the total carbon ratio, the prepared graphene shell partially covers the polypyrrole nanotubes, and the capacitance capacity is optimal.
The invention also provides an all-solid-state flexible supercapacitor, which comprises the following components: flexible current collector, electrode active material, solid state electrolyte. The flexible current collector can be aluminum foil, copper foil, carbon cloth and the like, the electrode active material is the polypyrrole nanotube/graphene nanosheet composite, and the solid electrolyte can be polyvinyl alcohol (PVA)/H2SO4PVA/LiCl, or PVA/H3PO4And (4) preparing gel.
The specific steps for assembling the all-solid-state flexible supercapacitor are as follows:
step A: an electrode active material dispersion liquid was prepared. And ultrasonically dispersing the polypyrrole nanotube/graphene nanosheet compound and an additive into a solvent according to a mass ratio of 100: 1-500: 1, wherein the additive can be selected from Nafion, polyvinylidene fluoride, tetrafluoroethylene and the like, the additive has the function of increasing the cohesiveness of an electrode active material and the binding force with a current collector, and the solvent can be selected from deionized water, ethanol, acetone and the like.
And B: and preparing the electrode of the super capacitor. And D, respectively dripping a certain amount of the electrode active material dispersion liquid prepared in the step A on two flexible current collectors, and drying at 25-80 ℃ for later use.
And C: an electrolyte gel is prepared. 0.5 to 5g of PVA and a certain amount of electrolyte (H)2SO4LiCl, or H3PO4Etc.) in deionized water, heating and stirring vigorously to obtain a clear gel for later use.
Step D: and assembling the super capacitor. And D, filling the electrolyte gel prepared in the step C between the two electrodes prepared in the step B to serve as a solid electrolyte and a diaphragm, drying at 25-80 ℃, and packaging with a Parafilm film to obtain the all-solid-state flexible supercapacitor.
Generally, the polypyrrole nano-structure coated by the shell layer prepared in the prior art is completely coated, and the completely coated shell layer can limit partial electrochemical behaviors of the conductive polypyrrole of the core, such as an ion doping/dedoping process in a charging and discharging process, so that capacitance is reduced. Compared with the prior art, the invention has the advantages that: the polypyrrole nanotube and the graphene nanosheet with a specific size range are connected through a chemical covalent bond, and the polypyrrole nanotube is partially to completely coated by the controllable graphene shell layer by adjusting the mass ratio of the polypyrrole nanotube to the graphene nanosheet. The graphene shell layer not only serves as a protective layer of the polypyrrole nanotube core, but also can improve conductivity. Meanwhile, the invention discovers that the complete wrapping of the graphene shell layer can limit partial electrochemical behaviors of the core conductive polypyrrole, such as an ion doping/de-doping process in a charging and discharging process, so that the capacitance is reduced, the partial wrapping to a certain degree can overcome the defects, the higher electrical property is obtained, and the capacitance capacity is optimized by the partial wrapping of the controllable shell layer. Therefore, the polypyrrole nanotube/graphene nanosheet composite with the controllable coating degree, which is prepared by the method, is used as an electrode active material of the super capacitor, and has high capacitance capacity and stable charge-discharge cycle characteristic.
The following are examples:
examples
Step one, preparing polypyrrole nanotubes. 1.5mmol of ferric chloride (FeCl)3·6H2O) is added into 30mL of 5mM methyl orange water solution, stirred for 30 minutes at the room temperature of 25 ℃, 105 mu L of pyrrole monomer is dripped, stirred for 12 hours at the room temperature of 25 ℃, 500mL of deionized water/ethanol mixed solution is used for cleaning the obtained black product, the black product is filtered and placed in a drying box, and the black polypyrrole nanotube is obtained after drying for 24 hours at the temperature of 60 ℃.
And step two, preparing the graphene nanosheet. Adding 0.4g of carbon black powder (Vulcan XC-72R, particle size of 30nm, Cabot Corporation) into 100mL of 6M concentrated nitric acid, heating to 130 ℃, refluxing for 48 hours, centrifuging (3000rcf), taking the upper layer of red brown clear liquid, carrying out ultrasonic treatment for 1 hour, centrifuging again (5000rcf), taking the upper layer of clear liquid, and heating at 200 ℃ for 12 hours to obtain the brown graphene nanosheet.
And step three, preparing the polypyrrole nanotube/graphene nanosheet composite. Respectively mixing and ultrasonically dispersing 9mg of polypyrrole nanotubes and 1mg of graphene nano sheets (in a mass ratio of 9:1), 9mg of polypyrrole nanotubes and 3mg of graphene nano sheets (in a mass ratio of 3:1), 9mg of polypyrrole nanotubes and 9mg of graphene nano sheets (in a mass ratio of 1:1), 3mg of polypyrrole nanotubes and 9mg of graphene nano sheets (in a mass ratio of 1:3) and 1mg of polypyrrole nanotubes and 9mg of graphene nano sheets (in a mass ratio of 1:9) in 30mL of N, N-Dimethylformamide (DMF), adding 1mg of 4-N, N-Dimethylpyridine (DMAP) and 10mg of Dicyclohexylcarbodiimide (DCC), stirring and reacting at 25 ℃ for 24 hours, sequentially ultrasonically cleaning the product with DMF and deionized water, placing the product in a drying box, and drying the product at 60 ℃ for 12 hours. And ultrasonically dispersing the dried product into deionized water again, adding a reducing agent hydrazine hydrate, stirring and reacting for 6 hours at the room temperature of 25 ℃, washing with the deionized water, and drying for 12 hours at the temperature of 60 ℃ to obtain the polypyrrole nanotube/graphene nanosheet composite. The synthetic scheme is shown in figure 1.
Other conditions are unchanged, the mass ratio of the graphene nanosheets to the polypyrrole nanotubes is only changed, coating in different degrees is achieved, the carbon C spectrum result of X-ray photoelectron spectroscopy (XPS) is combined with a Transmission Electron Microscope (TEM) picture, the coating degree of the polypyrrole nanotubes by the graphene shell is described according to the change of the total carbon ratio of amido bond carbon in the composite, the composite is used as an electrode active material, the capacitance capacity of the composite is tested, and the results are listed in Table 1.
TABLE 1 variation of the total carbon ratio of amido bond carbons in the composite material composite prepared by different mass ratios of graphene nanoplatelets and polypyrrole nanotubes and corresponding capacitance capacity
FIG. 2 is a Transmission Electron Microscope (TEM) photograph showing the ratio of amido bond carbon to total carbon of polypyrrole nanotube/graphene nanosheet composites prepared under different mass ratios of reactants (graphene nanosheet: polypyrrole nanotube) according to an embodiment of the present invention; FIG. 3 is the capacitance capacity of polypyrrole nanotube/graphene nanoplatelet composites prepared under the condition of different mass ratios of reactants (graphene nanoplatelets: polypyrrole nanotubes) according to the embodiment of the present invention, and as can be seen from the combination of Table 1, FIG. 2 and FIG. 3, when the mass ratio of the reactants (graphene nanoplatelets/polypyrrole nanotubes) is increased from 0:1 to 3:1, the proportion of amide bond carbon to total carbon (C) in the resulting composite is increased from 0:1 to 3:1 (C)N-C＝O/Ctotal) Gradually increasing from 0% to 6.7% to show that the total amount of the polypyrrole nanotube surface shell layer graphene nanosheets gradually increases, and when the mass ratio of the reactants is further increased to 9:1, CN-C＝O/CtotalThe value is kept unchanged, the total amount of the shell graphene nanosheets reaches saturation, and the polypyrrole nanotube is completely coated by the graphene shell. The corresponding TEM photo also shows that when the mass ratio of reactants is 1:9, the surface of the polypyrrole nanotube is partially coated with the graphene nanosheet, but a complete shell layer is not formed, and a completely coated layer is gradually formed along with the increase of the mass ratio of the reactantsA complete graphene shell layer. As can be seen from fig. 3, the capacitance capacity of the polypyrrole nanotube/graphene nanosheet composite is higher than that of a pure polypyrrole nanotube or graphene nanosheet, and when the mass ratio of the reactants (graphene nanosheet/polypyrrole nanotube) is increased from 0:1 to 1:3, the capacitance capacity of the obtained composite is gradually increased, and the mass ratio of the reactants is further increased, so that the capacitance capacity of the composite is reduced. Therefore, in this example, when the mass ratio of the reactants (graphene nanoplatelets/polypyrrole nanotubes) is 1:3, the ratio of amide bond carbons to total carbons (C) of the resulting composite isN-C＝O/Ctotal) 4.7 percent, is the polypyrrole nanotube which is not completely coated by the graphene nano-sheet, and has optimal capacitance capacity.
And step four, assembling the all-solid-state flexible super capacitor. And dispersing 10mg of the polypyrrole nanotube/graphene nanosheet composite with the optimal capacitance capacity in 0.98mL of ethanol, adding 20 mu L of Nafion 117 solution, and performing ultrasonic dispersion to obtain an electrode active material dispersion liquid. According to 3mg cm-2The electrode active material dispersion liquid is respectively coated on two pieces of aluminum foils in a dripping way to prepare electrodes, and the electrodes are dried for standby at 50 ℃. 2g of PVA and 4.25g of LiCl are mixed and dissolved in 20mL of deionized water, and the mixture is heated at 95 ℃ and stirred vigorously to obtain a clear gel for later use. And filling PVA/LiCl electrolyte gel between the two prepared electrodes to serve as a solid electrolyte and a diaphragm, drying at 50 ℃, and finally packaging by using a Parafilm film to prepare the all-solid-state flexible supercapacitor. Fig. 4 is a cyclic voltammetry curve and an application example of the fully solid flexible supercapacitor assembled according to the embodiment of the invention under different bending states, and it can be seen that the capacitor still shows good capacitance performance under the bending state.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of a polypyrrole/graphene composite material is characterized by comprising the following steps:
(1) mixing and dispersing a polypyrrole nanotube and a graphene nanosheet in a solvent according to a mass ratio of 10: 1-1: 10, adding a catalyst, and carrying out an acylation reaction to obtain an acylation reaction product; the graphene nanosheet contains carboxyl, and the size of the graphene nanosheet is 5-30 nm;
(2) cleaning the acylation reaction product obtained in the step (1), removing a solvent, a catalyst and unreacted graphene nanosheets, drying, dispersing in deionized water, adding a reducing agent, and removing oxygen-containing groups on a graphene shell layer in the reaction product to obtain a reduced product;
(3) washing and drying the reduced product in the step (2) to obtain a polypyrrole nanotube/graphene nanosheet composite material with a core/shell structure;
in the prepared composite material, a shell layer formed by graphene nanosheets is coated on the outer surface of a polypyrrole nanotube, wherein the size of the graphene nanosheets is 5-30 nm, the graphene nanosheets and the polypyrrole nanotube are connected through amido bonds, the carbon content of the amido bonds in the composite material is lower than 6.7% of the total carbon ratio, and the polypyrrole nanotube is partially coated by the graphene shell layer;
coating polypyrrole by using a graphene nanosheet with the size of 5-30 nm, so that the total amount of the shell layer graphene nanosheets is controllable; and obtaining the polypyrrole nanotube/graphene nanosheet composite material with different coating degrees by adjusting the mass ratio of the polypyrrole nanotube to the graphene nanosheet.
2. The method of claim 1, wherein the polypyrrole nanotubes are prepared by a method comprising: mixing ferric trichloride and methyl orange in a solvent according to a molar ratio of 5: 1-20: 1, stirring for 30-120 minutes at 10-30 ℃, dropwise adding 20-200 mu L of pyrrole monomer, stirring for 6-24 hours at 10-30 ℃, cleaning, filtering and drying the obtained product to obtain the polypyrrole nanotube.
3. The preparation method according to claim 1, wherein the preparation method of the graphene nanoplatelets is: adding carbon black powder into nitric acid with the concentration of 4-12M, heating and refluxing for 12-72 hours, performing ultrasonic treatment and centrifugation to obtain supernatant, and heating at 150-250 ℃ for 6-24 hours to obtain the graphene nanosheet.
4. The preparation method according to claim 1, wherein the polypyrrole nanotubes and the graphene nanoplatelets are mixed in a mass ratio of 5:1 to 1: 1.
5. The method of claim 1, wherein the catalyst is selected from the group consisting of dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, 4-N, N-lutidine, and 1-hydroxybenzotriazole.
6. The method according to claim 1, wherein the acylation reaction temperature in the step (1) is 20 to 30 ℃ and the reaction time is 6 to 48 hours.
7. The method according to claim 1, wherein the reducing agent in the step (2) is selected from hydrazine hydrate, sodium borohydride, vitamin C, and hydroiodic acid.
8. The method of claim 1, wherein the composite material is produced with amide bond carbons at a total carbon ratio of between 4% and 6%.
9. Use of a composite material prepared by the preparation method according to any one of claims 1 to 8 for preparing an energy storage electrode active material.
10. An all-solid-state flexible supercapacitor, which comprises a flexible current collector, an electrode active material and a solid electrolyte, wherein the electrode active material is a composite material prepared by the preparation method according to any one of claims 1 to 8.
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