CN108570229B - A kind of graphene nanobelt-polyaniline nanobelt composite material and preparation method thereof - Google Patents
A kind of graphene nanobelt-polyaniline nanobelt composite material and preparation method thereof Download PDFInfo
- Publication number
- CN108570229B CN108570229B CN201810435311.9A CN201810435311A CN108570229B CN 108570229 B CN108570229 B CN 108570229B CN 201810435311 A CN201810435311 A CN 201810435311A CN 108570229 B CN108570229 B CN 108570229B
- Authority
- CN
- China
- Prior art keywords
- nanoribbon
- graphene
- polyaniline
- nanobelt
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 259
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 229
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 133
- 239000002131 composite material Substances 0.000 title claims abstract description 115
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000002127 nanobelt Substances 0.000 title claims description 84
- 239000002074 nanoribbon Substances 0.000 claims abstract description 156
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000017 hydrogel Substances 0.000 claims abstract description 31
- 230000014759 maintenance of location Effects 0.000 claims abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 239000004964 aerogel Substances 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims description 64
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 60
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 50
- 238000001035 drying Methods 0.000 claims description 45
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 30
- 239000006185 dispersion Substances 0.000 claims description 27
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 23
- 239000002041 carbon nanotube Substances 0.000 claims description 22
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 22
- 238000004108 freeze drying Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 21
- 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 20
- 238000001816 cooling Methods 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 239000012286 potassium permanganate Substances 0.000 claims description 17
- 239000002244 precipitate Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000002114 nanocomposite Substances 0.000 claims description 15
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 12
- 238000000352 supercritical drying Methods 0.000 claims description 12
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 10
- 229930003268 Vitamin C Natural products 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 235000019154 vitamin C Nutrition 0.000 claims description 10
- 239000011718 vitamin C Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004472 Lysine Substances 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 7
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 7
- 229940068041 phytic acid Drugs 0.000 claims description 7
- 239000000467 phytic acid Substances 0.000 claims description 7
- 235000002949 phytic acid Nutrition 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 125000005227 alkyl sulfonate group Chemical group 0.000 claims description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical group I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 6
- 229940071870 hydroiodic acid Drugs 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 4
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 1
- 239000004567 concrete Substances 0.000 claims 1
- -1 ethoxy compound Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000005452 bending Methods 0.000 abstract description 26
- 238000000034 method Methods 0.000 abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 238000002791 soaking Methods 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 description 16
- 239000002086 nanomaterial Substances 0.000 description 14
- 230000001590 oxidative effect Effects 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000005457 ice water Substances 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000002109 single walled nanotube Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 description 2
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical group 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 235000018977 lysine Nutrition 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VCWJPGQFVGJLQJ-UHFFFAOYSA-N methyl octadecanoate;sodium Chemical compound [Na].CCCCCCCCCCCCCCCCCC(=O)OC VCWJPGQFVGJLQJ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000006250 one-dimensional material Substances 0.000 description 1
- 238000012946 outsourcing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
技术领域technical field
本发明属于纳米复合材料制备领域,涉及一种石墨烯纳米带-聚苯胺纳米带复合材料及其制备方法。The invention belongs to the field of nanocomposite material preparation, and relates to a graphene nanobelt-polyaniline nanobelt compound material and a preparation method thereof.
背景技术Background technique
石墨烯基纳米复合材料结合了石墨烯材料优异的电子/离子输运性能、力学性能以及活性纳米材料的电化学等性质,在锂电池、超级电容器等领域拥有广阔的应用价值和市场前景。过去的十几年里,石墨烯基纳米复合材料在储能材料、器件及技术方面的研究已经取得了令人瞩目的进展。然而,随着科技发展以及物质文化需求的提高,人们对储能材料提出了更高的要求,如高储量、轻薄化、柔性和可穿戴等。Graphene-based nanocomposites combine the excellent electron/ion transport properties, mechanical properties, and electrochemical properties of active nanomaterials, and have broad application value and market prospects in lithium batteries, supercapacitors, and other fields. In the past ten years, the research of graphene-based nanocomposites in energy storage materials, devices and technologies has made remarkable progress. However, with the development of science and technology and the improvement of material and cultural needs, people have put forward higher requirements for energy storage materials, such as high reserves, thinness, flexibility and wearability.
目前石墨烯基纳米复合材料主要通过以下两类方法制备:1)氧化石墨烯溶液与另外一种纳米材料共混,然后通过共水热、共沉积或原位聚合等方法形成复合材料,经过化学试剂或气氛还原等方式还原后得到石墨烯基纳米复合材料,所形成的复合结构一般为如图1所示的“填充”式,即纳米颗粒、纳米球或者纳米棒原位生长后填充在石墨烯片层的表面或者石墨烯片层之间;2)通过氧化石墨烯水热、模板浸渍等方法先形成网络结构,然后通过电化学沉积、水热等方法使得另外一种纳米材料包裹在石墨烯的骨架网络表面上,最后经过还原后所形成的复合结构称为如图2所示的“包覆”式。At present, graphene-based nanocomposites are mainly prepared by the following two methods: 1) The graphene oxide solution is blended with another nanomaterial, and then the composite material is formed by co-hydrothermal, co-deposition or in-situ polymerization. Graphene-based nanocomposites are obtained after reduction by means of reagents or atmosphere reduction, and the formed composite structure is generally a "filling" formula as shown in Figure 1, that is, nanoparticles, nanospheres or nanorods are grown in situ and then filled with graphite. The surface of the graphene sheet or between the graphene sheets; 2) The network structure is first formed by graphene oxide hydrothermal, template impregnation, etc., and then another nanomaterial is wrapped in graphite by electrochemical deposition, hydrothermal and other methods. On the surface of the alkene skeleton network, the composite structure formed after the final reduction is called the "coated" formula as shown in Figure 2.
以上两种方法简单、通用,但总结起来依然存在问题。首先,方法1)中石墨烯片层极易堆叠,纳米材料极易团聚,导致纳米材料的浪费,以及纳米材料性能的下降。方法2)虽然可以有效避免形成复合材料时石墨烯片层的堆叠,但由于具有非常大的孔隙结构,导致材料单位体积的储能密度较低。此外,两种方法都存在的致命问题是,不管纳米材料填充在孔隙还是包覆在网络表面,都基本呈现纳米颗粒形式,当材料遭受外界的弯折变形时,尤其是多次弯折变形时,“填充”式结构中纳米颗粒容易发生团聚、移位,而“包覆”式结构中纳米颗粒极易从网络表面剥落,从而导致整体材料性能的下降。The above two methods are simple and general, but there are still problems in summary. First, in method 1), the graphene sheets are very easy to stack, and the nanomaterials are very easy to agglomerate, which leads to the waste of nanomaterials and the decline of the performance of nanomaterials. Although method 2) can effectively avoid the stacking of graphene sheets when forming the composite material, due to the very large pore structure, the energy storage density per unit volume of the material is low. In addition, the fatal problem of both methods is that no matter whether the nanomaterials are filled in the pores or coated on the surface of the network, they are basically in the form of nanoparticles. When the material is subjected to external bending deformation, especially when it is repeatedly bent , the nanoparticles in the "filled" structure are prone to agglomeration and displacement, while the nanoparticles in the "encapsulated" structure are easily exfoliated from the network surface, resulting in a decrease in the overall material properties.
因此,开发一种能够有效避免因弯折变形而引发材料性能明显下降的石墨烯基纳米复合材料极具现实意义。Therefore, it is of great practical significance to develop a graphene-based nanocomposite that can effectively avoid the obvious degradation of material properties caused by bending deformation.
发明内容SUMMARY OF THE INVENTION
本发明所要解决的技术问题是克服现有技术复合材料抗弯折变形性能不佳,易引发性能下降的缺陷,提供一种能够有效避免因弯折变形而引发材料性能明显下降的石墨烯基纳米复合材料及其制备方法。The technical problem to be solved by the present invention is to overcome the defects of poor bending deformation resistance and easy performance degradation of composite materials in the prior art, and to provide a graphene-based nanomaterial that can effectively avoid the obvious decline in material performance caused by bending deformation. Composite materials and methods of making the same.
为实现上述目的,本发明采用如下技术方案:To achieve the above object, the present invention adopts the following technical solutions:
一种石墨烯纳米带-聚苯胺纳米带复合材料,所述石墨烯纳米带-聚苯胺纳米带复合材料为石墨烯纳米带与聚苯胺纳米带形成的具有网络互穿结构的复合气凝胶;所述石墨烯纳米带-聚苯胺纳米带复合材料在弯折1000次后,比电容保留率为96%以上。现有技术中的石墨烯-聚苯胺纳米颗粒复合材料在弯折400次后就由于纳米颗粒的团聚、石墨烯与聚苯胺失联等原因导致整体复合材料的性能明显下降,在弯折1000次后纳米复合材料的比电容下降至开始的60%左右,所述石墨烯纳米带-聚苯胺纳米带复合材料在电流密度为0.25A/g的条件下,比电容为600~700F/g,而现有的“填充式”及“包覆式”石墨烯-聚苯胺纳米颗粒复合材料的比电容仅为300~450F/g。现有技术无法同时兼顾比电容大及抗弯折性能好。A graphene nanoribbon-polyaniline nanoribbon composite material, wherein the graphene nanoribbon-polyaniline nanoribbon composite material is a composite aerogel with a network interpenetrating structure formed by graphene nanoribbons and polyaniline nanoribbons; After the graphene nanobelt-polyaniline nanobelt composite material is bent 1000 times, the specific capacitance retention rate is more than 96%. The graphene-polyaniline nanoparticle composite material in the prior art has a significant decrease in the performance of the overall composite material due to the agglomeration of nanoparticles and the loss of connection between graphene and polyaniline after being bent 400 times. After the specific capacitance of the nanocomposite decreased to about 60% of the initial value, the graphene nanoribbon-polyaniline nanoribbon composite material had a specific capacitance of 600-700F/g under the condition of a current density of 0.25A/g, while The specific capacitance of the existing "filled" and "wrapped" graphene-polyaniline nanoparticle composite materials is only 300-450 F/g. The prior art cannot take into account the large specific capacitance and the good bending resistance at the same time.
如上所述的一种石墨烯纳米带-聚苯胺纳米带复合材料,所述石墨烯纳米带-聚苯胺纳米带复合材料的电导率为100~1000S/m,由于其多孔结构使得电解质溶液离子快捷有效地传输;由于石墨烯纳米带的三维贯通,显示出优异的导电性;两类二维纳米材料发生缠结产生双网络互穿结构等协同效应,从而具有更加优异的机械性能,可回复的压缩应变为10~30%。A graphene nanoribbon-polyaniline nanoribbon composite material as described above, the electrical conductivity of the graphene nanoribbon-polyaniline nanoribbon composite material is 100-1000 S/m, and due to its porous structure, the electrolyte solution is ionically fast Effectively transport; due to the three-dimensional penetration of graphene nanoribbons, it shows excellent electrical conductivity; two types of two-dimensional nanomaterials are entangled to produce synergistic effects such as double network interpenetrating structures, resulting in more excellent mechanical properties, recoverable The compressive strain is 10 to 30%.
如上所述的一种石墨烯纳米带-聚苯胺纳米带复合材料,所述石墨烯纳米带的宽度为200nm~1μm,长度为3~20μm,厚度为5~50nm;所述聚苯胺纳米带的宽度为50~1000nm,长度为10~20μm,厚度为10~100nm。A graphene nanoribbon-polyaniline nanoribbon composite material as described above, wherein the graphene nanoribbon has a width of 200 nm to 1 μm, a length of 3 to 20 μm, and a thickness of 5 to 50 nm; The width is 50 to 1000 nm, the length is 10 to 20 μm, and the thickness is 10 to 100 nm.
本发明还提供一种如上所述的一种石墨烯纳米带-聚苯胺纳米带复合材料的方法,将氧化石墨烯纳米带水凝胶先后在混合液I和混合液II中浸泡处理得到氧化石墨烯纳米带-聚苯胺纳米带复合材料,再经还原得到石墨烯纳米带-聚苯胺纳米带复合材料;The present invention also provides a graphene nanoribbon-polyaniline nanoribbon composite material method as described above, wherein the graphene oxide nanoribbon hydrogel is successively soaked in mixed solution I and mixed solution II to obtain graphite oxide A graphene nanobelt-polyaniline nanobelt composite material, and then the graphene nanobelt-polyaniline nanobelt composite material is obtained by reduction;
所述混合液I主要由樟脑磺酸、水和苯胺组成,所述混合液II主要由过硫酸铵、水与樟脑磺酸或植酸组成。The mixed solution I is mainly composed of camphorsulfonic acid, water and aniline, and the mixed solution II is mainly composed of ammonium persulfate, water, camphorsulfonic acid or phytic acid.
作为优选的技术方案:As the preferred technical solution:
如上所述的方法,其步骤如下:As described above, the steps are as follows:
(1)将碳纳米管均匀分散在浓硫酸后,保持一定的搅拌速度依次加入磷酸、高锰酸钾,再缓慢升温至60~80℃,待温度稳定后,保温2~3h,分离产物即得氧化石墨烯纳米带;温度过低,氧化反应不进行,碳纳米管剪不开;温度过高,反应太剧烈,导致纳米带产生很多缺陷;升温过快,反应速率过大,导致氧化石墨烯纳米带的尺寸非常不均匀;升温过慢,导致整个周期太长,且纳米带尺寸会比较小。(1) After uniformly dispersing the carbon nanotubes in concentrated sulfuric acid, keep a certain stirring speed and add phosphoric acid and potassium permanganate in turn, and then slowly heat up to 60-80°C. Graphene oxide nanobelts are obtained; if the temperature is too low, the oxidation reaction does not proceed, and the carbon nanotubes cannot be cut; if the temperature is too high, the reaction is too violent, resulting in many defects in the nanobelts; if the temperature is too fast, the reaction rate is too large, resulting in graphite oxide The size of the ene nanoribbons is very non-uniform; the heating is too slow, resulting in too long the overall period, and the nanoribbons will be smaller in size.
(2)将氧化石墨烯纳米带均匀分散在水中后加入表面活性剂,制得氧化石墨烯纳米带稳定分散液;加入表面活性剂的作用有两:(1)更有利于氧化石墨烯纳米带的均匀分散;(2)表面活性剂分散在溶液中为后期聚苯胺生长为纳米带起到诱导作用,也就是软模板作用。(2) After the graphene oxide nanobelts are uniformly dispersed in water, a surfactant is added to obtain a stable dispersion liquid of graphene oxide nanobelts; the effect of adding a surfactant has two functions: (1) It is more conducive to the graphene oxide nanobelts (2) The surfactant is dispersed in the solution to induce the growth of polyaniline into nanobelts in the later stage, that is, the function of soft template.
(3)氧化石墨烯纳米带稳定分散液在120~160℃下水热反应12~36h,获得氧化石墨烯纳米带水凝胶;水热反应温度低于120℃时,由于氧化石墨烯纳米带表面还存在着较多含氧基团,有较强的负电性和亲水性,阻碍了氧化石墨烯纳米带的凝聚作用,从而不能形成稳定的三维结构;当温度从120℃升高到160℃时,含氧官能团逐渐被去除,氧化石墨烯纳米带的还原程度增加,静电和亲水作用力减弱,带带之间开始相互交织自组装在一起形成了较稳定的三维结构;但随着水热温度的进一步升高,氧化石墨烯纳米带的还原程度也相应的增加,凝聚作用力增强,带带之间堆叠紧密,团聚变得严重,网状孔径变小。当水热反应时间较短时,在压力和温度作用下,带带之间静电与氢键的作用未能完全形成,不能获得稳定的网络结构。(3) The stable dispersion of graphene oxide nanoribbons is hydrothermally reacted at 120-160 °C for 12-36 h to obtain graphene oxide nanoribbon hydrogel; There are also many oxygen-containing groups, which have strong negative charge and hydrophilicity, which hinder the cohesion of graphene oxide nanobelts, so that a stable three-dimensional structure cannot be formed; when the temperature increases from 120 °C to 160 °C When the oxygen-containing functional groups are gradually removed, the reduction degree of the graphene oxide nanoribbons increases, the electrostatic and hydrophilic forces weaken, and the ribbons begin to interweave and self-assemble together to form a relatively stable three-dimensional structure; With the further increase of the thermal temperature, the reduction degree of the graphene oxide nanoribbons also increases correspondingly, the cohesion force increases, the ribbons are stacked tightly, the agglomeration becomes serious, and the mesh pore size becomes smaller. When the hydrothermal reaction time is short, under the action of pressure and temperature, the electrostatic and hydrogen bonds between the bands are not fully formed, and a stable network structure cannot be obtained.
(4)樟脑磺酸溶解在水中后加入苯胺配制成均匀的混合液I,再将氧化石墨烯纳米带水凝胶在室温条件即15~25℃下浸入混合液I中8~24h;室温条件下苯胺的渗透速率适中,温度过高会破坏凝胶网络结构,温度过低导致苯胺渗透率太低;浸泡8~24h苯胺即可在表面活性剂的作用下充分渗透进氧化石墨烯纳米带水凝胶中的多孔结构空间中,浸泡时间过短无法实现上述效果,浸泡时间过长浪费了时间成本。(4) After dissolving camphorsulfonic acid in water, adding aniline to prepare a uniform mixed solution I, and then immersing the graphene oxide nanobelt hydrogel in the mixed solution I at room temperature, that is, 15-25 °C for 8-24 hours; room temperature conditions The permeation rate of lower aniline is moderate. If the temperature is too high, the gel network structure will be damaged. If the temperature is too low, the permeability of aniline will be too low. Soak aniline for 8-24 hours to fully penetrate into the graphene oxide nanobelt water under the action of surfactant. In the porous structure space in the gel, if the soaking time is too short, the above effect cannot be achieved, and the soaking time is too long, which wastes time and cost.
(5)樟脑磺酸或植酸溶解在水中后加入过硫酸铵配制成均匀的混合液II,将步骤(4)处理得到的氧化石墨烯纳米带水凝胶浸泡在混合液II中在0~4℃下聚合6~48h后,洗涤干燥即得氧化石墨烯纳米带-聚苯胺纳米带复合材料;低温(0~4℃)聚合有利于聚苯胺纳米带的形成,过高的温度导致反应过快从而导致聚苯胺纳米棒或者纳米颗粒的形成。聚合时间过短聚苯胺纳米带聚合不充分,聚合时间过长会使形成的分子链在氧化环境中氧化降解,从而降低其电导率。此处的樟脑磺酸提供酸性环境,使苯胺具有良好的溶解性,同时提高其电导率;过硫酸铵为氧化剂,使苯胺能够在低温下发生氧化聚合。(5) after dissolving camphorsulfonic acid or phytic acid in water, add ammonium persulfate to prepare a uniform mixed solution II, and soak the graphene oxide nanobelt hydrogel obtained in step (4) in the mixed solution II at 0 ~ After 6-48 hours of polymerization at 4°C, the graphene oxide nanoribbon-polyaniline nanoribbon composite material is obtained by washing and drying; low temperature (0-4°C) polymerization is conducive to the formation of polyaniline nanoribbons, and excessively high temperature leads to overreaction This leads to the formation of polyaniline nanorods or nanoparticles. If the polymerization time is too short, the polyaniline nanobelt will not be fully polymerized, and if the polymerization time is too long, the formed molecular chain will be oxidatively degraded in an oxidative environment, thereby reducing its electrical conductivity. The camphorsulfonic acid here provides an acidic environment, which makes aniline have good solubility and improves its electrical conductivity at the same time; ammonium persulfate is an oxidant, which enables aniline to undergo oxidative polymerization at low temperature.
(6)将氧化石墨烯纳米带-聚苯胺纳米带复合材料浸渍在还原剂中在80~100℃下反应4~12h,洗涤干燥后即得石墨烯纳米带-聚苯胺纳米带复合材料。这种还原处理方法可在低于100℃的较低温度下实现,在去除氧化石墨烯纳米带含氧官能团的同时,反应产物以液相的形式析出,产生的毛细作用力提高了石墨烯纳米带之间的结合力,因此还原后得到的石墨烯纳米带在导电性、力学强度和柔韧性等方面都有了显著的提高。(6) The graphene oxide nanoribbon-polyaniline nanoribbon composite material is dipped in a reducing agent and reacted at 80-100° C. for 4-12 hours, and the graphene nanoribbon-polyaniline nanoribbon composite material is obtained after washing and drying. This reduction treatment method can be achieved at a lower temperature below 100 °C. While removing the oxygen-containing functional groups of the graphene oxide nanobelts, the reaction products are precipitated in the form of liquid phase, and the generated capillary force improves the graphene nanobelt. Therefore, the graphene nanoribbons obtained after reduction have significant improvements in electrical conductivity, mechanical strength, and flexibility.
如上所述的方法,步骤(1)中,所述碳纳米管、浓硫酸、磷酸及高锰酸钾的质量比为15~25:6~10:1:75~125;所述浓硫酸的质量浓度为95~98%;所述磷酸的质量浓度为85%;所述一定的搅拌速度为200~500rpm;所述缓慢升温的升温速率为5~10℃/min;所述分离产物为依次进行冷却静置、清洗、离心处理。在该氧化剂/碳纳米管质量比的条件下制备氧化石墨烯纳米带时,随着反应时间的增加,氧化石墨烯纳米带的氧化程度会增加,直到达到饱和。而在低氧化剂/碳纳米管质量比条件下,随着反应时间的增加,氧化剂逐渐消耗,但当氧化剂被消耗完全或浓度很低时,在强酸条件下,生成的氧化石墨烯纳米带表面的含氧基团又逐渐被还原。In the above method, in step (1), the mass ratio of the carbon nanotubes, concentrated sulfuric acid, phosphoric acid and potassium permanganate is 15~25:6~10:1:75~125; The mass concentration is 95 to 98%; the mass concentration of the phosphoric acid is 85%; the certain stirring speed is 200 to 500 rpm; Perform cooling, standing, washing, and centrifugation. When graphene oxide nanoribbons are prepared under the condition of this oxidant/carbon nanotube mass ratio, with the increase of reaction time, the oxidation degree of graphene oxide nanoribbons will increase until it reaches saturation. Under the condition of low oxidant/carbon nanotube mass ratio, the oxidant is gradually consumed with the increase of reaction time, but when the oxidant is completely consumed or the concentration is very low, under strong acid conditions, the surface of the generated graphene oxide nanoribbons The oxygen-containing groups are gradually reduced again.
如上所述的方法,所述冷却静置是指冷却到室温后,倒入含过氧化氢的冰水中静置12~24h,过氧化氢除了冷却作用外还可除去多余的高锰酸钾;所述清洗为使用稀盐酸对冷却静置所得沉淀物进行多次清洗;所述离心是指使用离心机将清洗后的沉淀物离心2~4次,离心机转速为8000~10000rpm。In the above-mentioned method, the cooling and standing means that after cooling to room temperature, pouring into ice water containing hydrogen peroxide and standing for 12-24 hours, the hydrogen peroxide can also remove excess potassium permanganate in addition to the cooling effect; The washing is to use dilute hydrochloric acid to wash the precipitate obtained by cooling and standing for multiple times; the centrifugation refers to centrifuging the
如上所述的方法,步骤(2)中,所述表面活性剂为十二烷基苯磺酸钠、仲烷基磺酸钠或脂肪酸甲酯乙氧基化合物,所述氧化石墨烯纳米带稳定分散液中表面活性剂的浓度为30~80mg/mL;所述氧化石墨烯纳米带稳定分散液中氧化石墨烯纳米带的浓度为4~10mg/mL;步骤(4)中,所述樟脑磺酸与苯胺的质量比为2~4:1;所述混合液I中苯胺的浓度为5~25mg/mL。混合液I中酸浓度(2~4:1)有利于生成结构规整和较高电导率的聚苯胺;酸浓度较低时,聚苯胺形成的同时,伴随着吩嗪类物质和苯胺齐聚物的生成,产物呈现聚集结构,其电导率也较低。In the above method, in step (2), the surfactant is sodium dodecyl benzene sulfonate, sodium secondary alkyl sulfonate or fatty acid methyl ester ethoxylate, and the graphene oxide nanobelt is stable The concentration of the surfactant in the dispersion is 30-80 mg/mL; the concentration of the graphene oxide nanobelts in the stable dispersion of graphene oxide nanobelts is 4-10 mg/mL; in step (4), the camphorsulfonic acid The mass ratio of acid to aniline is 2-4:1; the concentration of aniline in the mixed solution I is 5-25 mg/mL. The acid concentration (2~4:1) in the mixed solution I is conducive to the formation of polyaniline with regular structure and higher electrical conductivity; when the acid concentration is low, the polyaniline is formed, accompanied by phenazine substances and aniline oligomers. The formation of , the product presents an aggregated structure, and its electrical conductivity is also low.
如上所述的方法,步骤(5)中,所述樟脑磺酸或植酸与过硫酸铵的质量比为4~8:1;所述混合液II中过硫酸铵的浓度为8~50mg/mL;所述浸泡是指氧化石墨烯纳米带水凝胶完全浸没于混合液II中;步骤(6)中,所述还原剂为氢碘酸、维生素C、赖氨酸或者维生素C与赖氨酸的混合溶液,所述还原剂与氧化石墨烯纳米带的质量比为3:1。聚合过程中,该氧化剂用量与酸浓度有利于生成结构规整和较高电导率的聚苯胺;而在氧化剂用量较高和酸浓度较低时,聚苯胺形成的同时,伴随着吩嗪类物质和苯胺齐聚物的生成,产物呈现聚集结构,其电导率也较低。The above method, in step (5), the mass ratio of the camphorsulfonic acid or phytic acid and ammonium persulfate is 4~8:1; the concentration of ammonium persulfate in the mixed solution II is 8~50mg/ The immersion means that the graphene oxide nanobelt hydrogel is completely immersed in the mixed solution II; in step (6), the reducing agent is hydroiodic acid, vitamin C, lysine or vitamin C and lysine The mixed solution of acid, the mass ratio of the reducing agent to the graphene oxide nanobelt is 3:1. In the polymerization process, the amount of the oxidant and the concentration of the acid are conducive to the formation of polyaniline with regular structure and higher conductivity; when the amount of the oxidant is high and the acid concentration is low, the polyaniline is formed, accompanied by phenazine substances and The formation of aniline oligomers presents aggregated structures with low electrical conductivity.
如上所述的方法,步骤(5)和步骤(6)中的洗涤为用去离子水与乙醇交替洗涤5~6次,直至洗涤溶液变为无色;步骤(5)和步骤(6)中的干燥为冷冻干燥或超临界干燥。In the above method, the washing in steps (5) and (6) is to alternately wash with deionized water and ethanol for 5 to 6 times, until the washing solution becomes colorless; in steps (5) and (6) The drying is freeze drying or supercritical drying.
如上所述的方法,所述冷冻干燥的干燥温度为-30~-40℃,干燥时间12h~48h;所述超临界干燥的干燥温度为30~40℃,干燥压力为8~10MPa,干燥时间为4h~10h。In the above method, the drying temperature of the freeze-drying is -30~-40℃, and the drying time is 12h~48h; the drying temperature of the supercritical drying is 30~40℃, the drying pressure is 8~10MPa, and the drying time is 12h~48h. For 4h ~ 10h.
发明机理:Invention Mechanism:
由于现有石墨烯基纳米复合材料结构的限制,本发明通过制备纳米带改变材料结构克服这一问题。Due to the limitation of the existing graphene-based nanocomposite material structure, the present invention overcomes this problem by preparing nanoribbons to change the material structure.
与纳米颗粒、纳米片等纳米结构相比,纳米带具有的优势有:1)宽度大,增加了材料间单点的接触面积以及材料间接触的几率,更有利于电子和离子传输网络的建立;2)厚度薄,离子可以从厚度方向进入活性材料,保证了与线状纳米材料相近的扩散距离;并且由于边缘效应反应活性位点更多;3)具有优异的柔性,可以形成良好的柔性网络结构,在遭受弯折变形时,容易通过自身形态的调整保持整体材料的柔性、可弯折性。Compared with nanostructures such as nanoparticles and nanosheets, nanoribbons have the following advantages: 1) The width is large, which increases the contact area of a single point between materials and the probability of contact between materials, which is more conducive to the establishment of electron and ion transport networks. 2) The thickness is thin, ions can enter the active material from the thickness direction, ensuring a similar diffusion distance to the linear nanomaterial; and due to the edge effect, there are more reactive sites; 3) It has excellent flexibility and can form a good flexibility When the network structure is subjected to bending deformation, it is easy to maintain the flexibility and bendability of the overall material through the adjustment of its own shape.
聚苯胺是一类典型的导电聚合物,这类聚合物主链上具有共轭体系,可以通过掺杂而导电,具有成本低、掺杂态电导率高、高存储容量和孔隙率、电压窗口宽、可逆性好及电化学活性可调节等诸多优点。另外,聚苯胺还具有很宽的可调的电容量范围,可用于制备高电导率、高性能的超级电容器电极材料。但是,导电聚合物由于其导电性较差,电子转移速度慢等因素制约着在超级电容器中充分的使用。因此,将聚苯胺与其它高导电性的碳材料复合具有重要意义。Polyaniline is a typical class of conductive polymers. This type of polymer has a conjugated system on the main chain, which can conduct electricity through doping. It has low cost, high doped state conductivity, high storage capacity and porosity, and voltage window. It has many advantages, such as wide width, good reversibility and tunable electrochemical activity. In addition, polyaniline also has a wide tunable capacitance range, which can be used to prepare high-conductivity, high-performance supercapacitor electrode materials. However, conductive polymers are restricted from being fully used in supercapacitors due to their poor conductivity and slow electron transfer speed. Therefore, it is of great significance to composite polyaniline with other highly conductive carbon materials.
本发明构筑如图3所示的石墨烯纳米带与聚苯胺纳米带的网络互穿式结构,该纳米复合材料将具有以下优点:1)具有三维连通的孔道,有利于电解质离子的快速、全面渗透,从而提高了有效活性位点;2)纳米带具有非常小的厚度,降低了离子扩散距离,从而提高了材料利用率;3)纳米材料与石墨烯纳米带相互贯穿/缠绕,形成了一个导电网络,从而保障了电子的快速输运;4)在外界弯应力作用下,纳米带形成的互穿网络由于其柔性以及相互滑移等方式,具有更优异的抗弯折性。The present invention constructs a network interpenetrating structure of graphene nanoribbons and polyaniline nanoribbons as shown in FIG. 3 , and the nanocomposite material will have the following advantages: 1) It has three-dimensional connected pores, which is conducive to the rapid and comprehensive operation of electrolyte ions. 2) The nanobelt has a very small thickness, which reduces the ion diffusion distance, thereby improving the material utilization rate; 3) The nanomaterial and the graphene nanoribbon penetrate/entangle with each other, forming a 4) Under the action of external bending stress, the interpenetrating network formed by nanoribbons has better bending resistance due to its flexibility and mutual slippage.
有益效果:Beneficial effects:
(1)本发明的一种石墨烯纳米带-聚苯胺纳米带复合材料的制备方法,制备过程简单,易于操作,设计巧妙,极具推广价值;(1) The preparation method of a graphene nanoribbon-polyaniline nanoribbon composite material of the present invention has the advantages of simple preparation process, easy operation, ingenious design, and great promotion value;
(2)本发明的一种石墨烯纳米带-聚苯胺纳米带复合材料,以石墨烯纳米带为基底,石墨烯纳米带独特的长径比与边缘结构赋予了其高的比表面积,同时石墨烯纳米带具有优异的导电性,其片层结构使得电催化过程中电子以及离子可以快捷有效地传输;通过水热方法实现了准一维材料与二维材料的复合,使得两者的优势得以充分发挥,从而构建了具有优异性能的复合材料;(2) A graphene nanoribbon-polyaniline nanoribbon composite material of the present invention is based on graphene nanoribbons, and the unique aspect ratio and edge structure of graphene nanoribbons endow it with a high specific surface area, while graphite The alkene nanoribbons have excellent electrical conductivity, and their lamellar structure enables electrons and ions to be transported quickly and efficiently in the electrocatalytic process; the composite of quasi-one-dimensional materials and two-dimensional materials is realized by a hydrothermal method, so that the advantages of both can be realized. Give full play to the construction of composite materials with excellent properties;
(3)本发明的一种石墨烯纳米带-聚苯胺纳米带复合材料,可用作高性能超级电容器电极材料以及锂离子电池、太阳能电池等新型能源的理想电极材料,极具应用前景。(3) A graphene nanoribbon-polyaniline nanoribbon composite material of the present invention can be used as a high-performance supercapacitor electrode material and an ideal electrode material for new energy sources such as lithium ion batteries and solar cells, and has great application prospects.
附图说明Description of drawings
图1为“填充式”复合结构石墨烯基纳米复合材料的结构示意图;Fig. 1 is the structural representation of "filled type" composite structure graphene-based nanocomposite;
图2为“包覆式”复合结构石墨烯基纳米复合材料的结构示意图;Fig. 2 is the structural representation of "wrapped" composite structure graphene-based nanocomposite;
图3为本发明的石墨烯纳米带-聚苯胺纳米带复合材料结构示意图;3 is a schematic structural diagram of a graphene nanoribbon-polyaniline nanoribbon composite material of the present invention;
图4为对石墨烯/聚苯胺纳米复合材料进行弯折测试的示意图;Fig. 4 is the schematic diagram of bending test on graphene/polyaniline nanocomposite;
图5为弯折对石墨烯/聚苯胺纳米复合材料比电容的影响对比图(A为本发明的石墨烯纳米带-聚苯胺纳米带复合材料,B为石墨烯/聚苯胺纳米颗粒);Fig. 5 is a comparative diagram of the effect of bending on the specific capacitance of graphene/polyaniline nanocomposite materials (A is the graphene nanoribbon-polyaniline nanoribbon composite material of the present invention, and B is graphene/polyaniline nanoparticle);
其中,1-石墨烯,2-填充纳米材料,3-外包纳米材料,4-石墨烯骨架,5-聚苯胺纳米带,6-石墨烯纳米带。Among them, 1-graphene, 2-filled nanomaterials, 3-outsourcing nanomaterials, 4-graphene skeleton, 5-polyaniline nanobelts, 6-graphene nanobelts.
具体实施方式Detailed ways
下面结合具体实施方式,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。The present invention will be further described below in conjunction with specific embodiments. It should be understood that these examples are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.
实施例1Example 1
一种石墨烯纳米带-聚苯胺纳米带复合材料的制备方法,其制备步骤如下:A preparation method of graphene nanobelt-polyaniline nanobelt composite material, the preparation steps are as follows:
(1)先将碳纳米管均匀分散在浓硫酸后,保持300rpm的搅拌速度依次加入磷酸、高锰酸钾,再以5℃/min的升温速率缓慢升温至70℃,待温度稳定后,保温2h,接着经冷却到室温后,倒入含过氧化氢的冰水中静置12h,然后使用稀盐酸对冷却静置所得沉淀物进行多次清洗,最后将清洗后的沉淀物离心2次后即得氧化石墨烯纳米带,其中碳纳米管、浓硫酸、磷酸及高锰酸钾的质量比为15:6:1:75,浓硫酸的质量浓度为98%,磷酸的质量浓度为85%,离心机转速为9000rpm;(1) After uniformly dispersing the carbon nanotubes in the concentrated sulfuric acid, add phosphoric acid and potassium permanganate in turn at a stirring speed of 300 rpm, and then slowly heat up to 70 °C at a heating rate of 5 °C/min. After the temperature is stable, keep warm After cooling to room temperature for 2 hours, pour it into ice water containing hydrogen peroxide and let stand for 12 hours, then use dilute hydrochloric acid to wash the precipitate obtained by cooling and standing for several times, and finally centrifuge the washed precipitate for 2 times. Graphene oxide nanobelts are obtained, wherein the mass ratio of carbon nanotubes, concentrated sulfuric acid, phosphoric acid and potassium permanganate is 15:6:1:75, the mass concentration of concentrated sulfuric acid is 98%, and the mass concentration of phosphoric acid is 85%, The speed of the centrifuge is 9000rpm;
(2)将氧化石墨烯纳米带均匀分散在水中后加入十二烷基苯磺酸钠,制得氧化石墨烯纳米带稳定分散液,其中氧化石墨烯纳米带稳定分散液中氧化石墨烯纳米带的浓度为4mg/mL,十二烷基苯磺酸钠的浓度为50mg/mL;(2) adding sodium dodecyl benzene sulfonate after uniformly dispersing the graphene oxide nanoribbons in water to obtain a stable dispersion liquid of graphene oxide nanoribbons, wherein the graphene oxide nanoribbons in the stable dispersion liquid of graphene oxide nanoribbons The concentration of sodium dodecylbenzene sulfonate is 4mg/mL, and the concentration of sodium dodecylbenzenesulfonate is 50mg/mL;
(3)氧化石墨烯纳米带稳定分散液在120℃下水热反应14h,获得氧化石墨烯纳米带水凝胶;(3) The stable dispersion of graphene oxide nanoribbons is hydrothermally reacted at 120 °C for 14 h to obtain a graphene oxide nanoribbon hydrogel;
(4)樟脑磺酸溶解在水中后加入苯胺配制成均匀的混合液I,再将氧化石墨烯纳米带水凝胶在20℃下浸入混合液I中16h,其中樟脑磺酸与苯胺的质量比为3:1,混合液I中苯胺的浓度为15mg/mL;(4) After dissolving camphorsulfonic acid in water, add aniline to prepare a uniform mixed solution I, and then immerse the graphene oxide nanobelt hydrogel in the mixed solution I at 20°C for 16 h, wherein the mass ratio of camphorsulfonic acid to aniline It is 3:1, and the concentration of aniline in the mixed solution I is 15mg/mL;
(5)樟脑磺酸溶解在水中后加入过硫酸铵配制成均匀的混合液II,将步骤(4)处理得到的氧化石墨烯纳米带水凝胶完全浸没于混合液II中在2℃下聚合24h后,用去离子水与乙醇交替洗涤6次,直至洗涤溶液变为无色后,经冷冻干燥后即得氧化石墨烯纳米带-聚苯胺纳米带复合材料,其中樟脑磺酸与过硫酸铵的质量比为5:1,混合液II中过硫酸铵的浓度为20mg/mL,冷冻干燥的干燥温度为-35℃,干燥时间40h;(5) After the camphorsulfonic acid is dissolved in water, ammonium persulfate is added to prepare a uniform mixed solution II, and the graphene oxide nanoribbon hydrogel obtained by the treatment in step (4) is completely immersed in the mixed solution II and polymerized at 2° C. After 24 hours, alternately washed 6 times with deionized water and ethanol, until the washing solution became colorless, and obtained the graphene oxide nanobelt-polyaniline nanobelt composite material after freeze-drying, wherein camphorsulfonic acid and ammonium persulfate The mass ratio of ammonium persulfate is 5:1, the concentration of ammonium persulfate in mixed solution II is 20mg/mL, the drying temperature of freeze-drying is -35°C, and the drying time is 40h;
(6)先将氧化石墨烯纳米带-聚苯胺纳米复合材料浸渍在氢碘酸中在90℃下反应8h,然后用去离子水与乙醇交替洗涤6次,直至洗涤溶液变为无色后,经冷冻干燥后即得石墨烯纳米带-聚苯胺纳米带复合材料,其中氢碘酸与氧化石墨烯纳米带的质量比为3:1,冷冻干燥的干燥温度为-35℃,干燥时间30h。(6) First, the graphene oxide nanoribbon-polyaniline nanocomposite was immersed in hydroiodic acid and reacted at 90 °C for 8 h, and then washed with deionized water and ethanol alternately for 6 times until the washing solution became colorless, The graphene nanoribbon-polyaniline nanoribbon composite material is obtained after freeze-drying, wherein the mass ratio of hydroiodic acid and graphene oxide nanoribbon is 3:1, the drying temperature of freeze-drying is -35°C, and the drying time is 30h.
最终制得的石墨烯纳米带-聚苯胺纳米带复合材料为石墨烯纳米带与聚苯胺纳米带形成的具有网络互穿结构的复合气凝胶,石墨烯纳米带的宽度为600nm,长度为12μm,厚度为45nm,聚苯胺纳米带的宽度为500nm,长度为15μm,厚度为50nm,制得的石墨烯纳米带-聚苯胺纳米带复合材料的电导率为900S/m,可回复的压缩应变为28%,在电流密度为0.25A/g的条件下比电容为700F/g。The graphene nanoribbon-polyaniline nanoribbon composite material finally prepared is a composite aerogel with a network interpenetrating structure formed by graphene nanoribbons and polyaniline nanoribbons. The width of the graphene nanoribbons is 600 nm and the length is 12 μm. , the thickness is 45 nm, the width of the polyaniline nanoribbon is 500 nm, the length is 15 μm, and the thickness is 50 nm. 28%, and the specific capacitance is 700F/g at a current density of 0.25A/g.
通过电化学工作站利用循环伏安法测试获得材料的比电容(F/g),按照图4所示方法弯折多次后(将样品用夹具固定在基底上,按虚线弯折150°),重新测试材料的比电容,表征弯折对石墨烯纳米带/聚苯胺纳米带复合材料的比电容性能的影响,测得石墨烯纳米带-聚苯胺纳米带复合材料的比电容保留率为96%。The specific capacitance (F/g) of the material was obtained by cyclic voltammetry in an electrochemical workstation, and after bending it several times according to the method shown in Figure 4 (fix the sample on the substrate with a clamp, and bend it by 150° according to the dotted line), The specific capacitance of the material was re-tested to characterize the effect of bending on the specific capacitance properties of the graphene nanoribbon/polyaniline nanoribbon composite, and the specific capacitance retention rate of the graphene nanoribbon-polyaniline nanoribbon composite was measured to be 96% .
对比例1Comparative Example 1
一种石墨烯-聚苯胺纳米颗粒复合材料的制备方法,通过氧化石墨烯溶液与苯胺原位聚合制备了“填充”式石墨烯-聚苯胺纳米颗粒复合材料。对制得的石墨烯-聚苯胺纳米颗粒复合材料进行与实施例1相同的弯折测试,实施例1制得的石墨烯纳米带-聚苯胺纳米带复合材料和对比例1制得的石墨烯-聚苯胺纳米颗粒复合材料进行弯折测试时比电容变化曲线如图5所示,图中A为本发明的石墨烯纳米带-聚苯胺纳米带复合材料,B为石墨烯-聚苯胺纳米颗粒复合材料,由图5可知,弯折1000次后,本发明石墨烯纳米带-聚苯胺纳米带复合材料的比电容保留率依然在96%左右;而对于石墨烯/聚苯胺纳米颗粒复合材料在弯折400次后就由于聚苯胺纳米颗粒的团聚、聚苯胺与石墨烯两相分离等原因导致整体复合材料的性能明显下降,在弯折1000次后纳米复合材料的比电容下降至开始的60%左右,在电流密度为0.25A/g的条件下比电容为330F/g。本发明制备的石墨烯纳米带-聚苯胺纳米带复合材料具有优异的抗弯折变形性能,其相比于现有技术取得了显著的进步。A method for preparing a graphene-polyaniline nanoparticle composite material. A "filled" graphene-polyaniline nanoparticle composite material is prepared by in-situ polymerization of a graphene oxide solution and aniline. The obtained graphene-polyaniline nanoparticle composite material is subjected to the same bending test as in Example 1, the graphene nanoribbon-polyaniline nanoribbon composite material obtained in Example 1 and the graphene obtained in Comparative Example 1 The specific capacitance change curve when the polyaniline nanoparticle composite material is subjected to a bending test is shown in Figure 5. In the figure, A is the graphene nanoribbon-polyaniline nanoribbon composite material of the present invention, and B is the graphene-polyaniline nanoparticle The composite material, as can be seen from Figure 5, after 1000 times of bending, the specific capacitance retention rate of the graphene nanoribbon-polyaniline nanoribbon composite material of the present invention is still about 96%; After 400 times of bending, the performance of the overall composite material decreased significantly due to the agglomeration of polyaniline nanoparticles and the two-phase separation of polyaniline and graphene. %, and the specific capacitance is 330F/g under the condition of a current density of 0.25A/g. The graphene nanoribbon-polyaniline nanoribbon composite material prepared by the invention has excellent bending deformation resistance, which has achieved remarkable progress compared with the prior art.
对比例2Comparative Example 2
一种碳纳米管-聚苯胺纳米带复合材料的制备方法,其制备步骤如下:A preparation method of carbon nanotube-polyaniline nanobelt composite material, the preparation steps are as follows:
(1)在水中加入十二烷基苯磺酸钠,其浓度为50mg/mL,然后加入单壁碳纳米管,经超声分散4h后制得碳纳米管稳定分散液,其中单壁碳纳米管的浓度为8mg/mL;(1) Add sodium dodecyl benzene sulfonate to water at a concentration of 50 mg/mL, then add single-walled carbon nanotubes, and ultrasonically disperse for 4 hours to obtain a stable dispersion of carbon nanotubes, in which the single-walled carbon nanotubes are dispersed. The concentration of 8mg/mL;
(2)将单壁碳纳米管溶液继续超声分散16h,获得单壁碳纳米管凝胶;(2) ultrasonically dispersing the single-walled carbon nanotube solution for 16 hours to obtain a single-walled carbon nanotube gel;
(3)樟脑磺酸溶解在水中后加入苯胺配制成均匀的混合液I,再将碳纳米管水凝胶在20℃下浸入混合液I中16h,其中樟脑磺酸与苯胺的质量比为3:1,混合液I中苯胺的浓度为15mg/mL;(3) After dissolving camphorsulfonic acid in water, add aniline to prepare a uniform mixed solution I, and then immerse the carbon nanotube hydrogel in the mixed solution I at 20°C for 16 hours, wherein the mass ratio of camphorsulfonic acid to aniline is 3 : 1, the concentration of aniline in
(4)樟脑磺酸溶解在水中后加入过硫酸铵配制成均匀的混合液II,将步骤(3)处理得到的碳纳米管水凝胶完全浸没于混合液II中在2℃下聚合24h后,用去离子水与乙醇交替洗涤6次,直至洗涤溶液变为无色后,经冷冻干燥后即得碳纳米管-聚苯胺纳米带复合材料,其中樟脑磺酸与过硫酸铵的质量比为5:1,混合液II中过硫酸铵的浓度为20mg/mL,冷冻干燥的干燥温度为-35℃,干燥时间40h。(4) After dissolving camphorsulfonic acid in water, adding ammonium persulfate to prepare a uniform mixed solution II, immersing the carbon nanotube hydrogel obtained in step (3) in the mixed solution II and polymerizing at 2°C for 24 hours , alternately wash 6 times with deionized water and ethanol, until the washing solution becomes colorless, after freeze-drying, the carbon nanotube-polyaniline nanobelt composite material is obtained, wherein the mass ratio of camphorsulfonic acid and ammonium persulfate is 5:1, the concentration of ammonium persulfate in mixed solution II is 20 mg/mL, the drying temperature of freeze-drying is -35°C, and the drying time is 40h.
最终制得的碳纳米管-聚苯胺纳米带复合材料中聚苯胺纳米带与碳纳米管形成网络互穿的结构,在电流密度为0.25A/g的条件下其比电容为450F/g,在弯折1000次后,比电容保留率为94%,与实施例1对比可以发现,两者抗弯折性能差不多,而其优异的抗弯折来源于网络互穿结构。但是,本发明中石墨烯纳米带-聚苯胺纳米带的比电容可以达到700F/g,远好于碳纳米管-聚苯胺纳米带复合材料,这是由于与碳纳米管相比,石墨烯纳米带的尺寸更大,其形成的网络结构中空间也更大,更有利于聚苯胺纳米带的生长,因此在复合材料中聚苯胺含量更高,导致最终的复合材料的比电容更高。In the finally prepared carbon nanotube-polyaniline nanobelt composite material, the polyaniline nanobelt and carbon nanotube form a network interpenetrating structure, and the specific capacitance is 450F/g under the condition of a current density of 0.25A/g. After 1000 times of bending, the specific capacitance retention rate is 94%. Compared with Example 1, it can be found that the bending resistance of the two is similar, and the excellent bending resistance is derived from the network interpenetrating structure. However, in the present invention, the specific capacitance of the graphene nanoribbon-polyaniline nanoribbon can reach 700 F/g, which is far better than that of the carbon nanotube-polyaniline nanoribbon composite material. The larger the size of the ribbon, the larger the space in the network structure formed by it, which is more favorable for the growth of PANI nanobelts, so the PANI content in the composite material is higher, resulting in a higher specific capacitance of the final composite material.
实施例2Example 2
一种石墨烯纳米带-聚苯胺纳米带复合材料的制备方法,其制备步骤如下:A preparation method of graphene nanobelt-polyaniline nanobelt composite material, the preparation steps are as follows:
(1)先将碳纳米管均匀分散在浓硫酸后,保持200rpm的搅拌速度依次加入磷酸、高锰酸钾,再以5℃/min的升温速率缓慢升温至60℃,待温度稳定后,保温2h,接着经冷却到室温后,倒入含过氧化氢的冰水中静置12h,然后使用稀盐酸对冷却静置所得沉淀物进行多次清洗,最后将清洗后的沉淀物离心2次后即得氧化石墨烯纳米带,其中碳纳米管、浓硫酸、磷酸及高锰酸钾的质量比为15:6:1:75,浓硫酸的质量浓度为95%,磷酸的质量浓度为85%,离心机转速为8000rpm;(1) After uniformly dispersing the carbon nanotubes in concentrated sulfuric acid, add phosphoric acid and potassium permanganate in turn at a stirring speed of 200 rpm, and then slowly heat up to 60 °C at a heating rate of 5 °C/min. After the temperature is stable, keep the temperature After cooling to room temperature for 2 hours, pour it into ice water containing hydrogen peroxide and let stand for 12 hours, then use dilute hydrochloric acid to wash the precipitate obtained by cooling and standing for several times, and finally centrifuge the washed precipitate for 2 times. Obtain graphene oxide nanobelt, wherein the mass ratio of carbon nanotubes, concentrated sulfuric acid, phosphoric acid and potassium permanganate is 15:6:1:75, the mass concentration of concentrated sulfuric acid is 95%, and the mass concentration of phosphoric acid is 85%, The speed of the centrifuge is 8000rpm;
(2)将氧化石墨烯纳米带均匀分散在水中后加入仲烷基磺酸钠,制得氧化石墨烯纳米带稳定分散液,其中氧化石墨烯纳米带稳定分散液中氧化石墨烯纳米带的浓度为4mg/mL,仲烷基磺酸钠的浓度为30mg/mL;(2) after the graphene oxide nanobelts are uniformly dispersed in water, sodium secondary alkyl sulfonate is added to obtain a stable dispersion liquid of graphene oxide nanobelts, wherein the concentration of graphene oxide nanobelts in the stable dispersion liquid of graphene oxide nanobelts is 4 mg/mL, and the concentration of sodium secondary alkyl sulfonate is 30 mg/mL;
(3)氧化石墨烯纳米带稳定分散液在120℃下水热反应12h,获得氧化石墨烯纳米带水凝胶;(3) The stable dispersion of graphene oxide nanoribbons is hydrothermally reacted at 120 °C for 12 h to obtain a graphene oxide nanoribbon hydrogel;
(4)樟脑磺酸溶解在水中后加入苯胺配制成均匀的混合液I,再将氧化石墨烯纳米带水凝胶在15℃下浸入混合液I中8h,其中樟脑磺酸与苯胺的质量比为2:1,混合液I中苯胺的浓度为5mg/mL;(4) After dissolving camphorsulfonic acid in water, add aniline to prepare a uniform mixed solution I, and then immerse the graphene oxide nanobelt hydrogel in the mixed solution I at 15°C for 8 h, wherein the mass ratio of camphorsulfonic acid to aniline It is 2:1, and the concentration of aniline in the mixed solution I is 5mg/mL;
(5)植酸溶解在水中后加入过硫酸铵配制成均匀的混合液II,将步骤(4)处理得到的氧化石墨烯纳米带水凝胶完全浸没于混合液II中在0℃下聚合6h后,用去离子水与乙醇交替洗涤6次,直至洗涤溶液变为无色后,经冷冻干燥后即得氧化石墨烯纳米带-聚苯胺纳米带复合材料,其中植酸与过硫酸铵的质量比为4:1,混合液II中过硫酸铵的浓度为8mg/mL,冷冻干燥的干燥温度为-30℃,干燥时间48h;(5) After phytic acid is dissolved in water, ammonium persulfate is added to prepare a uniform mixed solution II, and the graphene oxide nanoribbon hydrogel obtained in step (4) is completely immersed in the mixed solution II and polymerized at 0 °C for 6 h Then, alternately wash 6 times with deionized water and ethanol, until the washing solution becomes colorless, after freeze-drying, the graphene oxide nanobelt-polyaniline nanobelt composite material is obtained, wherein the quality of phytic acid and ammonium persulfate is The ratio is 4:1, the concentration of ammonium persulfate in mixed solution II is 8 mg/mL, the drying temperature of freeze-drying is -30°C, and the drying time is 48h;
(6)先将氧化石墨烯纳米带-聚苯胺纳米带复合材料浸渍在维生素C中在80℃下反应8h,然后用去离子水与乙醇交替洗涤6次,直至洗涤溶液变为无色后,经冷冻干燥后即得石墨烯纳米带-聚苯胺纳米带复合材料,其中维生素C与氧化石墨烯纳米带的质量比为3:1,冷冻干燥的干燥温度为-30℃,干燥时间48h。(6) First, the graphene oxide nanoribbon-polyaniline nanoribbon composite material was immersed in vitamin C and reacted at 80 °C for 8 h, and then washed with deionized water and ethanol alternately for 6 times until the washing solution became colorless, The graphene nanoribbon-polyaniline nanoribbon composite material is obtained after freeze-drying, wherein the mass ratio of vitamin C to the graphene oxide nanoribbon is 3:1, the drying temperature of freeze-drying is -30°C, and the drying time is 48h.
最终制得的石墨烯纳米带-聚苯胺纳米带复合材料为石墨烯纳米带与聚苯胺纳米带形成的具有网络互穿结构的复合气凝胶,石墨烯纳米带的宽度为200nm,长度为20μm,厚度为50nm,聚苯胺纳米带的宽度为1000nm,长度为20μm,厚度为100nm,制得的石墨烯纳米带-聚苯胺纳米带复合材料的电导率为100S/m,可回复的压缩应变为10%,在电流密度为0.25A/g的条件下其比电容为600F/g,石墨烯纳米带-聚苯胺纳米带复合材料在弯折1000次后,比电容保留率为96.2%。The graphene nanoribbon-polyaniline nanoribbon composite material finally prepared is a composite aerogel with a network interpenetrating structure formed by graphene nanoribbons and polyaniline nanoribbons. The width of the graphene nanoribbons is 200 nm and the length is 20 μm. , the thickness is 50 nm, the width of the polyaniline nanoribbon is 1000 nm, the length is 20 μm, and the thickness is 100 nm. 10%, its specific capacitance is 600F/g under the condition of current density of 0.25A/g, and the specific capacitance retention rate of graphene nanoribbon-polyaniline nanoribbon composite is 96.2% after bending 1000 times.
实施例3Example 3
一种石墨烯纳米带-聚苯胺纳米带复合材料的制备方法,其制备步骤如下:A preparation method of graphene nanobelt-polyaniline nanobelt composite material, the preparation steps are as follows:
(1)先将碳纳米管均匀分散在浓硫酸后,保持500rpm的搅拌速度依次加入磷酸、高锰酸钾,再以10℃/min的升温速率缓慢升温至80℃,待温度稳定后,保温3h,接着经冷却到室温后,倒入含过氧化氢的冰水中静置24h,然后使用稀盐酸对冷却静置所得沉淀物进行多次清洗,最后将清洗后的沉淀物离心4次后即得氧化石墨烯纳米带,其中碳纳米管、浓硫酸、磷酸及高锰酸钾的质量比为25:10:1:125,浓硫酸的质量浓度为98%,磷酸的质量浓度为85%,离心机转速为10000rpm;(1) After uniformly dispersing the carbon nanotubes in concentrated sulfuric acid, add phosphoric acid and potassium permanganate in turn at a stirring speed of 500 rpm, and then slowly heat up to 80 °C at a heating rate of 10 °C/min. After the temperature is stable, keep warm After cooling to room temperature for 3 hours, pour it into ice water containing hydrogen peroxide and let it stand for 24 hours, then use dilute hydrochloric acid to wash the precipitate obtained by cooling and standing for several times, and finally centrifuge the washed precipitate for 4 times. Graphene oxide nanobelts are obtained, wherein the mass ratio of carbon nanotubes, concentrated sulfuric acid, phosphoric acid and potassium permanganate is 25:10:1:125, the mass concentration of concentrated sulfuric acid is 98%, and the mass concentration of phosphoric acid is 85%, The speed of the centrifuge is 10000rpm;
(2)将氧化石墨烯纳米带均匀分散在水中后加入硬脂酸甲酯聚氧乙烯醚磺酸钠,制得氧化石墨烯纳米带稳定分散液,其中氧化石墨烯纳米带稳定分散液中氧化石墨烯纳米带的浓度为10mg/mL,硬脂酸甲酯聚氧乙烯醚磺酸钠的浓度为80mg/mL;(2) after the graphene oxide nanobelt is uniformly dispersed in water, sodium methyl stearate polyoxyethylene ether sulfonate is added to obtain a graphene oxide nanobelt stable dispersion, wherein the graphene oxide nanobelt stabilized dispersion is oxidized The concentration of graphene nanoribbon is 10mg/mL, and the concentration of methyl stearate polyoxyethylene ether sulfonate sodium is 80mg/mL;
(3)氧化石墨烯纳米带稳定分散液在160℃下水热反应36h,获得氧化石墨烯纳米带水凝胶;(3) The stable dispersion of graphene oxide nanoribbons is hydrothermally reacted at 160 °C for 36 h to obtain a graphene oxide nanoribbon hydrogel;
(4)樟脑磺酸溶解在水中后加入苯胺配制成均匀的混合液I,再将氧化石墨烯纳米带水凝胶在25℃下浸入混合液I中24h,其中樟脑磺酸与苯胺的质量比为4:1,混合液I中苯胺的浓度为25mg/mL;(4) After dissolving camphorsulfonic acid in water, add aniline to prepare a uniform mixed solution I, and then immerse the graphene oxide nanobelt hydrogel in the mixed solution I at 25°C for 24 hours, wherein the mass ratio of camphorsulfonic acid to aniline It is 4:1, and the concentration of aniline in mixed solution I is 25mg/mL;
(5)樟脑磺酸溶解在水中后加入过硫酸铵配制成均匀的混合液II,将步骤(4)处理得到的氧化石墨烯纳米带水凝胶完全浸没于混合液II中在4℃下聚合48h后,用去离子水与乙醇交替洗涤5次,直至洗涤溶液变为无色后,经冷冻干燥后即得氧化石墨烯纳米带-聚苯胺纳米带复合材料,其中樟脑磺酸与过硫酸铵的质量比为8:1,混合液II中过硫酸铵的浓度为50mg/mL,冷冻干燥的干燥温度为-40℃,干燥时间12h;(5) After the camphorsulfonic acid is dissolved in the water, ammonium persulfate is added to prepare a uniform mixed solution II, and the graphene oxide nanoribbon hydrogel obtained by the step (4) is completely immersed in the mixed solution II and polymerized at 4° C. After 48 hours, alternately wash with deionized water and ethanol for 5 times, until the washing solution becomes colorless, after freeze-drying, the graphene oxide nanobelt-polyaniline nanobelt composite material is obtained, wherein camphorsulfonic acid and ammonium persulfate The mass ratio of ammonium persulfate is 8:1, the concentration of ammonium persulfate in mixed solution II is 50 mg/mL, the drying temperature of freeze-drying is -40 °C, and the drying time is 12 h;
(6)先将氧化石墨烯纳米带-聚苯胺纳米带复合材料浸渍在赖氨酸中在100℃下反应12h,然后用去离子水与乙醇交替洗涤5次,直至洗涤溶液变为无色后,经冷冻干燥后即得石墨烯纳米带-聚苯胺纳米带复合材料,其中赖氨酸与氧化石墨烯纳米带的质量比为3:1,冷冻干燥的干燥温度为-40℃,干燥时间12h。(6) First, the graphene oxide nanoribbon-polyaniline nanoribbon composite material was immersed in lysine and reacted at 100 °C for 12 h, and then washed with deionized water and ethanol alternately for 5 times until the washing solution became colorless. , the graphene nanoribbon-polyaniline nanoribbon composite material is obtained after freeze-drying, wherein the mass ratio of lysine and graphene oxide nanoribbon is 3:1, the drying temperature of freeze-drying is -40°C, and the drying time is 12h .
最终制得的石墨烯纳米带-聚苯胺纳米带复合材料为石墨烯纳米带与聚苯胺纳米带形成的具有网络互穿结构的复合气凝胶,石墨烯纳米带的宽度为1μm,长度为3μm,厚度为5nm,聚苯胺纳米带的宽度为50nm,长度为10μm,厚度为10nm,制得的石墨烯纳米带-聚苯胺纳米带复合材料的电导率为120S/m,可回复的压缩应变为15%,在电流密度为0.25A/g的条件下其比电容为650F/g,石墨烯纳米带-聚苯胺纳米带复合材料在弯折1000次后,比电容保留率为96.5%。The graphene nanoribbon-polyaniline nanoribbon composite material finally prepared is a composite aerogel with a network interpenetrating structure formed by graphene nanoribbons and polyaniline nanoribbons. The width of the graphene nanoribbons is 1 μm and the length is 3 μm. , the thickness is 5 nm, the width of the polyaniline nanoribbon is 50 nm, the length is 10 μm, and the thickness is 10 nm. 15%, the specific capacitance is 650F/g under the condition of current density of 0.25A/g, and the specific capacitance retention rate of graphene nanoribbon-polyaniline nanoribbon composite is 96.5% after 1000 times of bending.
实施例4Example 4
一种石墨烯纳米带-聚苯胺纳米带复合材料的制备方法,其制备步骤如下:A preparation method of graphene nanobelt-polyaniline nanobelt composite material, the preparation steps are as follows:
(1)先将碳纳米管均匀分散在浓硫酸后,保持300rpm的搅拌速度依次加入磷酸、高锰酸钾,再以7℃/min的升温速率缓慢升温至65℃,待温度稳定后,保温2h,接着经冷却到室温后,倒入含过氧化氢的冰水中静置16h,然后使用稀盐酸对冷却静置所得沉淀物进行多次清洗,最后将清洗后的沉淀物离心3次后即得氧化石墨烯纳米带,其中碳纳米管、浓硫酸、磷酸及高锰酸钾的质量比为18:8:1:80,浓硫酸的质量浓度为96%,磷酸的质量浓度为85%,离心机转速为8500rpm;(1) After uniformly dispersing the carbon nanotubes in concentrated sulfuric acid, add phosphoric acid and potassium permanganate in turn at a stirring speed of 300 rpm, and then slowly heat up to 65 °C at a heating rate of 7 °C/min. After the temperature is stable, keep the temperature After cooling to room temperature for 2 hours, pour it into ice water containing hydrogen peroxide and let it stand for 16 hours, then use dilute hydrochloric acid to wash the precipitate obtained by cooling and standing for several times, and finally centrifuge the washed precipitate for 3 times. Graphene oxide nanobelts are obtained, wherein the mass ratio of carbon nanotubes, concentrated sulfuric acid, phosphoric acid and potassium permanganate is 18:8:1:80, the mass concentration of concentrated sulfuric acid is 96%, and the mass concentration of phosphoric acid is 85%, The speed of the centrifuge is 8500rpm;
(2)将氧化石墨烯纳米带均匀分散在水中后加入十二烷基苯磺酸钠,制得氧化石墨烯纳米带稳定分散液,其中氧化石墨烯纳米带稳定分散液中氧化石墨烯纳米带的浓度为5mg/mL,十二烷基苯磺酸钠的浓度为40mg/mL;(2) adding sodium dodecyl benzene sulfonate after uniformly dispersing the graphene oxide nanoribbons in water to obtain a stable dispersion liquid of graphene oxide nanoribbons, wherein the graphene oxide nanoribbons in the stable dispersion liquid of graphene oxide nanoribbons The concentration of sodium dodecylbenzenesulfonate is 5mg/mL, and the concentration of sodium dodecylbenzenesulfonate is 40mg/mL;
(3)氧化石墨烯纳米带稳定分散液在140℃下水热反应18h,获得氧化石墨烯纳米带水凝胶;(3) The stable dispersion of graphene oxide nanoribbons is hydrothermally reacted at 140 °C for 18 h to obtain a graphene oxide nanoribbon hydrogel;
(4)樟脑磺酸溶解在水中后加入苯胺配制成均匀的混合液I,再将氧化石墨烯纳米带水凝胶在20℃下浸入混合液I中20h,其中樟脑磺酸与苯胺的质量比为2:1,混合液I中苯胺的浓度为20mg/mL;(4) After dissolving camphorsulfonic acid in water, add aniline to prepare a uniform mixed solution I, and then immerse the graphene oxide nanobelt hydrogel in the mixed solution I at 20°C for 20 h, wherein the mass ratio of camphorsulfonic acid to aniline It is 2:1, and the concentration of aniline in the mixed solution I is 20mg/mL;
(5)樟脑磺酸溶解在水中后加入过硫酸铵配制成均匀的混合液II,将步骤(4)处理得到的氧化石墨烯纳米带水凝胶完全浸没于混合液II中在0℃下聚合8h后,用去离子水与乙醇交替洗涤6次,直至洗涤溶液变为无色后,经冷冻干燥后即得氧化石墨烯纳米带-聚苯胺纳米带复合材料,其中樟脑磺酸与过硫酸铵的质量比为6:1,混合液II中过硫酸铵的浓度为15mg/mL,冷冻干燥的干燥温度为-35℃,干燥时间20h;(5) After the camphorsulfonic acid is dissolved in water, ammonium persulfate is added to prepare a uniform mixed solution II, and the graphene oxide nanoribbon hydrogel obtained by the treatment in step (4) is completely immersed in the mixed solution II and polymerized at 0° C. After 8 hours, alternately washed with deionized water and ethanol for 6 times until the washing solution became colorless, and after freeze-drying, the graphene oxide nanobelt-polyaniline nanobelt composite material was obtained, wherein camphorsulfonic acid and ammonium persulfate The mass ratio of ammonium persulfate is 6:1, the concentration of ammonium persulfate in mixed solution II is 15mg/mL, the drying temperature of freeze-drying is -35℃, and the drying time is 20h;
(6)先将氧化石墨烯纳米带-聚苯胺纳米带复合材料浸渍在维生素C与赖氨酸的混合溶液(质量比1:1)中在90℃下反应6h,然后用去离子水与乙醇交替洗涤6次,直至洗涤溶液变为无色后,经冷冻干燥后即得石墨烯纳米带-聚苯胺纳米带复合材料,其中维生素C与赖氨酸的混合溶液与氧化石墨烯纳米带的质量比为3:1,冷冻干燥的干燥温度为-35℃,干燥时间20h。(6) First, the graphene oxide nanoribbon-polyaniline nanoribbon composite material was immersed in a mixed solution of vitamin C and lysine (mass ratio 1:1) for 6 h at 90 °C, and then deionized water and ethanol were used for the reaction. Alternately washed 6 times, until the washing solution becomes colorless, after freeze-drying, the graphene nanobelt-polyaniline nanobelt composite material is obtained, wherein the mixed solution of vitamin C and lysine and the quality of the graphene oxide nanobelt are obtained. The ratio is 3:1, the drying temperature of freeze-drying is -35°C, and the drying time is 20h.
最终制得的石墨烯纳米带-聚苯胺纳米带复合材料为石墨烯纳米带与聚苯胺纳米带形成的具有网络互穿结构的复合气凝胶,石墨烯纳米带的宽度为400nm,长度为10μm,厚度为20nm,聚苯胺纳米带的宽度为200nm,长度为15μm,厚度为30nm,制得的石墨烯纳米带-聚苯胺纳米带复合材料的电导率为400S/m,可回复的压缩应变为20%,在电流密度为0.25A/g的条件下其比电容为680F/g,石墨烯纳米带-聚苯胺纳米带复合材料在弯折1000次后,比电容保留率为97%。The graphene nanoribbon-polyaniline nanoribbon composite material finally prepared is a composite aerogel with a network interpenetrating structure formed by graphene nanoribbons and polyaniline nanoribbons. The width of the graphene nanoribbons is 400 nm and the length is 10 μm. , the thickness is 20 nm, the width of the polyaniline nanoribbon is 200 nm, the length is 15 μm, and the thickness is 30 nm. 20%, the specific capacitance is 680F/g under the condition of current density of 0.25A/g, and the specific capacitance retention rate of graphene nanoribbon-polyaniline nanoribbon composite is 97% after bending 1000 times.
实施例5Example 5
一种石墨烯纳米带-聚苯胺纳米带复合材料的制备方法,其制备步骤如下:A preparation method of graphene nanobelt-polyaniline nanobelt composite material, the preparation steps are as follows:
(1)先将碳纳米管均匀分散在浓硫酸后,保持400rpm的搅拌速度依次加入磷酸、高锰酸钾,再以10℃/min的升温速率缓慢升温至70℃,待温度稳定后,保温3h,接着经冷却到室温后,倒入含过氧化氢的冰水中静置20h,然后使用稀盐酸对冷却静置所得沉淀物进行多次清洗,最后将清洗后的沉淀物离心2次后即得氧化石墨烯纳米带,其中碳纳米管、浓硫酸、磷酸及高锰酸钾的质量比为20:10:1:120,浓硫酸的质量浓度为97%,磷酸的质量浓度为85%,离心机转速为9000rpm;(1) After uniformly dispersing the carbon nanotubes in concentrated sulfuric acid, add phosphoric acid and potassium permanganate in turn at a stirring speed of 400 rpm, and then slowly heat up to 70 °C at a heating rate of 10 °C/min. After the temperature is stable, keep the temperature After cooling to room temperature for 3 hours, pour it into ice water containing hydrogen peroxide and let it stand for 20 hours, then use dilute hydrochloric acid to wash the precipitate obtained by cooling and standing for several times, and finally centrifuge the washed precipitate for 2 times. Graphene oxide nanobelts are obtained, wherein the mass ratio of carbon nanotubes, concentrated sulfuric acid, phosphoric acid and potassium permanganate is 20:10:1:120, the mass concentration of concentrated sulfuric acid is 97%, and the mass concentration of phosphoric acid is 85%, The speed of the centrifuge is 9000rpm;
(2)将氧化石墨烯纳米带均匀分散在水中后加入十二烷基苯磺酸钠,制得氧化石墨烯纳米带稳定分散液,其中氧化石墨烯纳米带稳定分散液中氧化石墨烯纳米带的浓度为8mg/mL,十二烷基苯磺酸钠的浓度为60mg/mL;(2) adding sodium dodecyl benzene sulfonate after uniformly dispersing the graphene oxide nanoribbons in water to obtain a stable dispersion liquid of graphene oxide nanoribbons, wherein the graphene oxide nanoribbons in the stable dispersion liquid of graphene oxide nanoribbons The concentration of sodium dodecylbenzenesulfonate is 8mg/mL, and the concentration of sodium dodecylbenzenesulfonate is 60mg/mL;
(3)氧化石墨烯纳米带稳定分散液在150℃下水热反应25h,获得氧化石墨烯纳米带水凝胶;(3) The stable dispersion of graphene oxide nanoribbons is hydrothermally reacted at 150 °C for 25 h to obtain a graphene oxide nanoribbon hydrogel;
(4)樟脑磺酸溶解在水中后加入苯胺配制成均匀的混合液I,再将氧化石墨烯纳米带水凝胶在25℃下浸入混合液I中24h,其中樟脑磺酸与苯胺的质量比为4:1,混合液I中苯胺的浓度为20mg/mL;(4) After dissolving camphorsulfonic acid in water, add aniline to prepare a uniform mixed solution I, and then immerse the graphene oxide nanobelt hydrogel in the mixed solution I at 25°C for 24 hours, wherein the mass ratio of camphorsulfonic acid to aniline It is 4:1, and the concentration of aniline in mixed solution I is 20mg/mL;
(5)樟脑磺酸溶解在水中后加入过硫酸铵配制成均匀的混合液II,将步骤(4)处理得到的氧化石墨烯纳米带水凝胶完全浸没于混合液II中在0℃下聚合6h后,用去离子水与乙醇交替洗涤5次,直至洗涤溶液变为无色后,经超临界干燥后即得氧化石墨烯纳米带-聚苯胺纳米带复合材料,其中樟脑磺酸与过硫酸铵的质量比为7:1,混合液II中过硫酸铵的浓度为30mg/mL,超临界干燥的干燥温度为40℃,干燥压力为10MPa,干燥时间为10h;(5) After the camphorsulfonic acid is dissolved in water, ammonium persulfate is added to prepare a uniform mixed solution II, and the graphene oxide nanoribbon hydrogel obtained by the treatment in step (4) is completely immersed in the mixed solution II and polymerized at 0° C. After 6h, alternately wash with deionized water and ethanol for 5 times until the washing solution becomes colorless, and after supercritical drying, the graphene oxide nanobelt-polyaniline nanobelt composite material is obtained, wherein camphorsulfonic acid and persulfuric acid are obtained. The mass ratio of ammonium is 7:1, the concentration of ammonium persulfate in mixed solution II is 30mg/mL, the drying temperature of supercritical drying is 40°C, the drying pressure is 10MPa, and the drying time is 10h;
(6)先将氧化石墨烯纳米带-聚苯胺纳米带复合材料浸渍在氢碘酸中在80℃下反应10h,然后用去离子水与乙醇交替洗涤5次,直至洗涤溶液变为无色后,经超临界干燥后即得石墨烯纳米带-聚苯胺纳米带复合材料,其中氢碘酸与氧化石墨烯纳米带的质量比为3:1,超临界干燥的干燥温度为40℃,干燥压力为10MPa,干燥时间为10h。(6) First, the graphene oxide nanoribbon-polyaniline nanoribbon composite material was immersed in hydroiodic acid for 10 h at 80 °C, and then washed alternately with deionized water and ethanol for 5 times until the washing solution became colorless. , the graphene nanoribbon-polyaniline nanoribbon composite material is obtained after supercritical drying, wherein the mass ratio of hydroiodic acid and graphene oxide nanoribbon is 3:1, the drying temperature of supercritical drying is 40 ° C, and the drying pressure is 10MPa, and the drying time is 10h.
最终制得的石墨烯纳米带-聚苯胺纳米带复合材料为石墨烯纳米带与聚苯胺纳米带形成的具有网络互穿结构的复合气凝胶,石墨烯纳米带的宽度为800nm,长度为10μm,厚度为40nm,聚苯胺纳米带的宽度为700nm,长度为20μm,厚度为80nm,制得的石墨烯纳米带-聚苯胺纳米带复合材料的电导率为900S/m,可回复的压缩应变为25%,在电流密度为0.25A/g的条件下其比电容为640F/g,石墨烯纳米带-聚苯胺纳米带复合材料在弯折1000次后,比电容保留率为96.7%。The final graphene nanoribbon-polyaniline nanoribbon composite material is a composite aerogel with a network interpenetrating structure formed by graphene nanoribbons and polyaniline nanoribbons. The width of the graphene nanoribbons is 800 nm and the length is 10 μm. , the thickness is 40 nm, the width of the polyaniline nanoribbon is 700 nm, the length is 20 μm, and the thickness is 80 nm. 25%, the specific capacitance is 640F/g under the condition of current density of 0.25A/g, and the specific capacitance retention rate of graphene nanoribbon-polyaniline nanoribbon composite is 96.7% after 1000 times of bending.
实施例6Example 6
一种石墨烯纳米带-聚苯胺纳米带复合材料的制备方法,其制备步骤如下:A preparation method of graphene nanobelt-polyaniline nanobelt composite material, the preparation steps are as follows:
(1)先将碳纳米管均匀分散在浓硫酸后,保持500rpm的搅拌速度依次加入磷酸、高锰酸钾,再以8℃/min的升温速率缓慢升温至60℃,待温度稳定后,保温3h,接着经冷却到室温后,倒入含过氧化氢的冰水中静置20h,然后使用稀盐酸对冷却静置所得沉淀物进行多次清洗,最后将清洗后的沉淀物离心4次后即得氧化石墨烯纳米带,其中碳纳米管、浓硫酸、磷酸及高锰酸钾的质量比为25:6:1:100,浓硫酸的质量浓度为95%,磷酸的质量浓度为85%,离心机转速为9500rpm;(1) After uniformly dispersing the carbon nanotubes in concentrated sulfuric acid, add phosphoric acid and potassium permanganate in turn at a stirring speed of 500 rpm, and then slowly heat up to 60 °C at a heating rate of 8 °C/min. After the temperature is stable, keep warm After cooling to room temperature for 3 hours, pour it into ice water containing hydrogen peroxide and let it stand for 20 hours, then use dilute hydrochloric acid to wash the precipitate obtained by cooling and standing for several times, and finally centrifuge the washed precipitate for 4 times. Graphene oxide nanobelts are obtained, wherein the mass ratio of carbon nanotubes, concentrated sulfuric acid, phosphoric acid and potassium permanganate is 25:6:1:100, the mass concentration of concentrated sulfuric acid is 95%, and the mass concentration of phosphoric acid is 85%, The speed of the centrifuge is 9500rpm;
(2)将氧化石墨烯纳米带均匀分散在水中后加入仲烷基磺酸钠,制得氧化石墨烯纳米带稳定分散液,其中氧化石墨烯纳米带稳定分散液中氧化石墨烯纳米带的浓度为10mg/mL,仲烷基磺酸钠的浓度为50mg/mL;(2) after the graphene oxide nanobelts are uniformly dispersed in water, sodium secondary alkyl sulfonate is added to obtain a stable dispersion liquid of graphene oxide nanobelts, wherein the concentration of graphene oxide nanobelts in the stable dispersion liquid of graphene oxide nanobelts is 10mg/mL, and the concentration of sodium secondary alkyl sulfonate is 50mg/mL;
(3)氧化石墨烯纳米带稳定分散液在160℃下水热反应36h,获得氧化石墨烯纳米带水凝胶;(3) The stable dispersion of graphene oxide nanoribbons is hydrothermally reacted at 160 °C for 36 h to obtain a graphene oxide nanoribbon hydrogel;
(4)樟脑磺酸溶解在水中后加入苯胺配制成均匀的混合液I,再将氧化石墨烯纳米带水凝胶在20℃下浸入混合液I中20h,其中樟脑磺酸与苯胺的质量比为4:1,混合液I中苯胺的浓度为20mg/mL;(4) After dissolving camphorsulfonic acid in water, add aniline to prepare a uniform mixed solution I, and then immerse the graphene oxide nanobelt hydrogel in the mixed solution I at 20°C for 20 h, wherein the mass ratio of camphorsulfonic acid to aniline It is 4:1, and the concentration of aniline in mixed solution I is 20mg/mL;
(5)樟脑磺酸溶解在水中后加入过硫酸铵配制成均匀的混合液II,将步骤(4)处理得到的氧化石墨烯纳米带水凝胶完全浸没于混合液II中在3℃下聚合18h后,用去离子水与乙醇交替洗涤6次,直至洗涤溶液变为无色后,经超临界干燥后即得氧化石墨烯纳米带-聚苯胺纳米带复合材料,其中樟脑磺酸与过硫酸铵的质量比为5:1,混合液II中过硫酸铵的浓度为40mg/mL,超临界干燥的干燥温度为30℃,干燥压力为8MPa,干燥时间为4h;(5) After the camphorsulfonic acid is dissolved in the water, ammonium persulfate is added to prepare a uniform mixed solution II, and the graphene oxide nanoribbon hydrogel obtained by the treatment in step (4) is completely immersed in the mixed solution II and polymerized at 3° C. After 18 hours, alternately wash with deionized water and ethanol for 6 times, until the washing solution becomes colorless, and after supercritical drying, the graphene oxide nanobelt-polyaniline nanobelt composite material is obtained, wherein camphorsulfonic acid and persulfuric acid are obtained. The mass ratio of ammonium is 5:1, the concentration of ammonium persulfate in mixed solution II is 40mg/mL, the drying temperature of supercritical drying is 30°C, the drying pressure is 8MPa, and the drying time is 4h;
(6)先将氧化石墨烯纳米带-聚苯胺纳米带复合材料浸渍在维生素C中在85℃下反应10h,然后用去离子水与乙醇交替洗涤6次,直至洗涤溶液变为无色后,经超临界干燥后即得石墨烯纳米带-聚苯胺纳米带复合材料,其中维生素C与氧化石墨烯纳米带的质量比为3:1,超临界干燥的干燥温度为30℃,干燥压力为8MPa,干燥时间为4h。(6) First, the graphene oxide nanoribbon-polyaniline nanoribbon composite material was immersed in vitamin C and reacted at 85 °C for 10 h, and then washed with deionized water and ethanol alternately for 6 times until the washing solution became colorless, The graphene nanoribbon-polyaniline nanoribbon composite material is obtained after supercritical drying, wherein the mass ratio of vitamin C and graphene oxide nanoribbon is 3:1, the drying temperature of supercritical drying is 30 ° C, and the drying pressure is 8 MPa , the drying time is 4h.
最终制得的石墨烯纳米带-聚苯胺纳米带复合材料为石墨烯纳米带与聚苯胺纳米带形成的具有网络互穿结构的复合气凝胶,石墨烯纳米带的宽度为1μm,长度为20μm,厚度为40nm,聚苯胺纳米带的宽度为700nm,长度为15μm,厚度为80nm,制得的石墨烯纳米带-聚苯胺纳米带复合材料的电导率为950S/m,可回复的压缩应变为25%,在电流密度为0.25A/g的条件下其比电容为630F/g,石墨烯纳米带-聚苯胺纳米带复合材料在弯折1000次后,比电容保留率为97.2%。The graphene nanoribbon-polyaniline nanoribbon composite material finally prepared is a composite aerogel with a network interpenetrating structure formed by graphene nanoribbons and polyaniline nanoribbons. The width of the graphene nanoribbons is 1 μm and the length is 20 μm. , the thickness is 40 nm, the width of the polyaniline nanoribbon is 700 nm, the length is 15 μm, and the thickness is 80 nm. 25%, the specific capacitance is 630F/g under the condition of current density of 0.25A/g, and the specific capacitance retention rate of graphene nanoribbon-polyaniline nanoribbon composite is 97.2% after bending 1000 times.
Claims (9)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810435311.9A CN108570229B (en) | 2018-05-09 | 2018-05-09 | A kind of graphene nanobelt-polyaniline nanobelt composite material and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810435311.9A CN108570229B (en) | 2018-05-09 | 2018-05-09 | A kind of graphene nanobelt-polyaniline nanobelt composite material and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108570229A CN108570229A (en) | 2018-09-25 |
CN108570229B true CN108570229B (en) | 2020-08-14 |
Family
ID=63571940
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810435311.9A Active CN108570229B (en) | 2018-05-09 | 2018-05-09 | A kind of graphene nanobelt-polyaniline nanobelt composite material and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108570229B (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110534353B (en) * | 2019-09-19 | 2020-11-03 | 福州大学 | Preparation method and application of poly (3, 4-ethylenedioxythiophene) composite material |
CN111484644A (en) * | 2020-04-17 | 2020-08-04 | 东华理工大学 | Method for preparing, separating and enriching uranium from polyamidoxime/graphene nanoribbon composite aerogel |
CN114752075B (en) * | 2022-03-08 | 2024-03-22 | 武汉工程大学 | Preparation method of copper sulfide-graphene-polyaniline composite hydrogel |
CN114854046B (en) * | 2022-05-09 | 2025-01-24 | 南京林业大学 | A triple stimulus responsive double-layer hydrogel actuator and preparation method thereof |
CN115863062B (en) * | 2022-12-27 | 2023-07-28 | 武汉立承科技有限公司 | Graphene nanobelt/metal oxide nanobelt composite film and preparation and application thereof |
CN116396524B (en) * | 2023-03-28 | 2025-06-24 | 武汉工程大学 | Polyaniline composite silicon carbide nanowire aerogel and preparation method and application thereof |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW201012749A (en) * | 2008-08-19 | 2010-04-01 | Univ Rice William M | Methods for preparation of graphene nanoribbons from carbon nanotubes and compositions, thin films and devices derived therefrom |
CN104817075B (en) * | 2015-04-17 | 2021-04-13 | 重庆大学 | A kind of preparation method of highly dispersed graphene oxide nanobelt liquid |
CN106128802B (en) * | 2016-07-04 | 2018-01-26 | 上海电力学院 | A kind of preparation method for the electrode material of supercapacitor |
CN106046401B (en) * | 2016-07-07 | 2018-12-25 | 北京化工大学 | A kind of preparation method of graphene polyaniline aeroge thermoelectric material |
-
2018
- 2018-05-09 CN CN201810435311.9A patent/CN108570229B/en active Active
Also Published As
Publication number | Publication date |
---|---|
CN108570229A (en) | 2018-09-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108570229B (en) | A kind of graphene nanobelt-polyaniline nanobelt composite material and preparation method thereof | |
Luo et al. | Overview of MXene/conducting polymer composites for supercapacitors | |
Li et al. | 3D MXene architectures for efficient energy storage and conversion | |
Gao | Graphene and polymer composites for supercapacitor applications: a review | |
Simotwo et al. | Polyaniline-based electrodes: recent application in supercapacitors and next generation rechargeable batteries | |
Wang et al. | Polypyrrole composites with carbon materials for supercapacitors | |
CN107919233B (en) | A kind of high voltage flexible solid-state supercapacitor and preparation method thereof | |
CN104900856B (en) | A cathode composite material for lithium-sulfur batteries based on nano-sulfur and its preparation method | |
CN104466134B (en) | The preparation method of self-supporting graphene/carbon nano-tube hybrid foam support amino anthraquinones base polymer | |
Bilal et al. | Insight into capacitive performance of polyaniline/graphene oxide composites with ecofriendly binder | |
CN105885410B (en) | A kind of molybdenum sulfide/polypyrrole/polyaniline trielement composite material and its preparation method and application | |
CN104867702B (en) | A kind of preparation method of anthraquinone molecular non-covalent modification grapheme/electroconductive polymer composite | |
CN104272506A (en) | Sulfur-containing composite for lithium-sulfur battery, electrode material comprising said composite, and lithium-sulfur battery | |
Li et al. | Soft conducting polymer hydrogels in situ doped by sulfonated graphene quantum dots for enhanced electrochemical activity | |
CN106046369A (en) | Preparation of polyaniline-graphene layer-layer composite material assisted by supercritical method | |
Li et al. | Ordered multiphase polymer nanocomposites for high-performance solid-state supercapacitors | |
CN111668472A (en) | Silicon-based composite negative electrode material and preparation method thereof, and lithium ion battery | |
CN114956108A (en) | Novel two-dimensional transition metal boride, preparation method thereof and application of novel two-dimensional transition metal boride as energy storage electrode material | |
US20240339623A1 (en) | Conductive agent slurry for secondary battery electrode, secondary battery electrode including same, and secondary battery | |
CN112940643B (en) | A kind of double polymer gel material and its preparation method and application | |
Zhou et al. | Charge carrier related superior capacitance of the precisely size-controlled polypyrrole nanoparticles | |
CN110707324A (en) | Preparation of Conductive Binder and Its Application in Battery Electrodes | |
CN115472440B (en) | A graphene-based N, S doped electrode material and its preparation method | |
CN117766853A (en) | Preparation method and application of composite solid electrolyte based on topological porous nano-sheet regulation and control | |
CN110289176A (en) | A preparation method of polyaniline grafted reduced graphene oxide/multi-walled carbon nanotube composite material for electrochemical energy storage |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |