CN104119677A - Cobalt ferrite-graphene-polyaniline ternary nano composite material and preparation method thereof - Google Patents
Cobalt ferrite-graphene-polyaniline ternary nano composite material and preparation method thereof Download PDFInfo
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 94
- 239000010941 cobalt Substances 0.000 title claims abstract description 94
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000000463 material Substances 0.000 title claims abstract description 82
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 72
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 78
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 11
- 239000010439 graphite Substances 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 11
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 10
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 239000004160 Ammonium persulphate Substances 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 6
- 241000446313 Lamella Species 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims 1
- 239000003999 initiator Substances 0.000 abstract description 13
- 230000001105 regulatory effect Effects 0.000 abstract description 7
- 239000007772 electrode material Substances 0.000 abstract description 5
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 abstract 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 abstract 1
- 229910021641 deionized water Inorganic materials 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- 239000002131 composite material Substances 0.000 description 17
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 7
- 229910000314 transition metal oxide Inorganic materials 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000002322 conducting polymer Substances 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 gac Substances 0.000 description 3
- 241001251371 Betula chinensis Species 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910021392 nanocarbon Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
-
- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K2201/011—Nanostructured additives
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- 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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Abstract
The invention discloses a cobalt ferrite-graphene-polyaniline ternary nano composite material and a preparation method thereof. The ternary nano composite material consists of nano cobalt ferrite, graphene and polyaniline, wherein the nano cobalt ferrite is loaded on a graphene sheet layer; the polyaniline is coated on the surface of the whole sheet layer. The preparation method for the cobalt ferrite- graphene-polyaniline ternary nano composite material comprises the steps of ultrasonically dispersing graphite oxide into absolute ethyl alcohol to obtain graphene oxide liquor; stirring and dissolving ferric nitrate and cobalt ferrite in alcohol; mixing the liquor obtained in the two steps, stirring and regulating a pH value; transferring a reaction system obtained in the third step into an hydrothermal kettle for reacting, and washing obtained products; dispersing products obtained in the fourth step and an initiator in acid liquor; under a constant-temperature state, adding aniline into the system obtained in the fifth step; reacting the obtained system under the constant-temperature condition; filtering the products obtained in the seventh step by using a lot of deionized water and separating out the products obtained in the seventh step, and drying to obtain the cobalt ferrite-graphene-polyaniline ternary nano composite material. The cobalt ferrite-graphene-polyaniline ternary nano composite material disclosed by the invention has excellent electrochemical performance, and is widely applied to the fields of catalytic materials, electrode materials, and the like.
Description
Technical field
First the present invention passes through hydro-thermal reaction, nano-ferrous acid in load on graphene sheet layer, adopt again the method for in-situ oxidizing-polymerizing to prepare cobalt ferrite-Graphene-polyaniline ternary nano composite material, this cobalt ferrite-Graphene-polyaniline ternary nano composite material has excellent electrochemical activity, has good application prospect and economic benefit at aspects such as ultracapacitors.
Background technology
Day by day serious along with energy problem, it is more and more important that the research of high-performance electric chemistry energy storage device becomes.Wherein ultracapacitor is due to high energy density, and charge-discharge velocity is fast, long service life etc., and advantage especially receives publicity.
In general, ultracapacitor is divided into double layer capacitor and fake capacitance device.The electrode materials of double layer capacitor is mainly carbon material, such as gac, carbon fiber, carbon nanotube etc.Recently, two-dimensional nano carbon material Graphene is because unique constitutional features is widely used on ultracapacitor, but more difficult owing to preparing in a large number at present Graphene, in preparation process due to the effect of Van der Waals force, Graphene is easily piled up again, affects its chemical property.The electrode materials of fake capacitance device mainly comprises transition metal oxide and conducting polymer.Conducting polymer is due to low cost, and the performances such as higher specific conductivity are subject to extensive concern.The advantages such as polyaniline, as a kind of important conducting polymer, has preparation easy, and chemical property is controlled, and environmental stability is good.But polyaniline is exactly that its cyclical stability is bad as the shortcoming of super capacitor material maximum.Another fake capacitance device electrode materials is transition metal oxide, for example tricobalt tetroxide, ferric oxide, Manganse Dioxide etc.In general, transition metal oxide all has higher ratio electric capacity, but preparation cost is higher, and reversibility is bad.Nano-ferrous acid is a kind of metallic iron oxide compound with spinel structure.They have high electric property, high Curie temperature and excellent stability, have applied to widely the fields such as information storage, electricity device and pharmaceutical carrier.But the report on ultracapacitor lacks considerably less about cobalt ferrite.In sum, three kinds of main electrode materialss all have merits and demerits separately.Research shows, two kinds of electrode materialss are combined with each other and prepare nanometer combined electrode material and can address the above problem to a certain extent.For example, by Graphene and transition metal oxide, as Manganse Dioxide is combined with each other, prepare Manganse Dioxide-graphene nanocomposite material, improved than electric capacity and reversibility.(Lingjuan Deng, Gang Zhu, Jianfang Wang, Liping Kang, Zonghuai Liu, Zupei Yang and Zenglin Wang, Journal of Power Sources, 2011,196,10782.) by polyaniline and transition metal oxide, as Manganse Dioxide is combined with each other, prepare Manganse Dioxide-polyaniline nano-composite material, improved than electric capacity and cyclical stability.(Jaidev, Razzak Imran Jafri, Ashish Kumar Mishra and Sundara Ramaprabhu, Journal of Materials Chemistry, 2011,21,17601.) polyaniline and Graphene are combined with each other to have improved compare electric capacity.(Qiong Wu, Yuxi Xu, Zhiyi Yao, Anran Liu, and Gaoquan Shi, ACS Nano, 2010,4,1963.) nearest, design and preparation contain nano-carbon material as the ternary nano composite material of carbon nanotube, polyaniline and transition metal oxide, show very high ratio electric capacity and excellent cyclical stability.（Ye?Hou,?Yingwen?Cheng,?Tyler?Hobson?and?Jie?Liu,?Nano?Letter,?2010,?10,?2727;?Qiang?Li,?Jianhua?Liu,?Jianhua?Zou,?Anindarupa?Chunder,?Yiqing?Chen,?Lei?Zhai,?Journal?of?Power?Sources,?2011,?196,?565;?Guihua?Yu,?Liangbing?Hu,?Nian?Liu,?Huiliang?Wang,?Michael?Vosgueritchian,?Yuan?Yang,?Yi?Cui?and?Zhenan?Bao,?Nano?Letter,?2011,?11,?4438.）。
Summary of the invention
The object of the present invention is to provide a kind of cobalt ferrite-Graphene-polyaniline ternary nano composite material with excellent electrochemical activity and preparation method thereof.
The technical solution that realizes the object of the invention is: a kind of cobalt ferrite-Graphene-polyaniline ternary nano composite material, described nano composite material is made up of nano-ferrous acid, Graphene and polyaniline, nano-ferrous acid loads on graphene sheet layer, polyaniline-coated is on the surface of whole lamella, wherein the mass ratio of cobalt ferrite and Graphene is 1 ~ 40%, and polyaniline accounts for 50 ~ 90% of ternary nano composite material total mass.
A preparation method for cobalt ferrite-Graphene-polyaniline ternary nano composite material, comprises the following steps:
The first step, is dispersed in cobalt ferrite-graphene nanocomposite material and ammonium persulphate in acid solution;
Second step, under ice bath state, joins aniline in the system of the first step gained;
The 3rd step is reacted the system of gained under 0 ~ 25 DEG C of condition;
The 4th step, carries out filtering separation, dry rear cobalt ferrite-Graphene-polyaniline ternary nano composite material that obtains by the product of the 3rd step gained.
In cobalt ferrite-graphene nanocomposite material described in the first step, the mass ratio of cobalt ferrite and Graphene is 1 ~ 40%, and the concentration of described acid solution is 0.1 ~ 1 mol/L; Described acid is selected from the one in hydrochloric acid, sulfuric acid or phosphoric acid.
The mol ratio of the aniline described in second step and ammonium persulphate is 1:1 ~ 3, and the mass ratio of the cobalt ferrite-graphene nanocomposite material described in described aniline and the first step is 1:0.2 ~ 1:2.
Reaction times 6 ~ 20 h described in the 3rd step.
In cobalt ferrite-Graphene-polyaniline ternary nano composite material described in the 4th step, polyaniline accounts for 50 ~ 90% of ternary nano composite material total mass.
Cobalt ferrite-graphene nanocomposite material described in the first step is prepared by following steps:
The 1st step: graphite oxide is carried out in ethanol to ultrasonic dispersion and obtain graphene oxide solution;
The 2nd step, the stirring and dissolving in ethanol by iron nitrate and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES;
The 3rd step, mixes first two steps gained solution, stirs, and regulates pH value;
The 4th step, is transferred to the 3rd step gained reaction system in water heating kettle and reacts, products therefrom washing.
Wherein, the ultrasonic jitter time described in the 1st step is 30 ~ 120 min, and described graphite oxide adopts Hummer legal system standby; Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES described in the 2nd step and iron nitrate mol ratio are 1:2; Described in the 3rd step, the churning time of mixing solutions is 30 ~ 120min, pH=7 ~ 12; Hydrothermal temperature described in the 4th step is 120 ~ 240 DEG C, and the reaction times is 12 ~ 28 h.
Cobalt ferrite-Graphene of the present invention-polyaniline ternary nano composite material, compared with prior art, its advantage is: (1) the present invention prepares cobalt ferrite-graphene nanocomposite material by hydro-thermal reaction, then prepares cobalt ferrite-Graphene-polyaniline ternary nano composite material by in-situ oxidizing-polymerizing method; (2) cobalt ferrite-Graphene-polyaniline ternary nano composite material that the present invention prepares has excellent chemical property; (3) cobalt ferrite-Graphene-polyaniline ternary nano composite material that the present invention prepares has good application prospect and economic benefit in electric chemical super capacitor field.
Brief description of the drawings
Fig. 1 is the TEM figure of example 1 cobalt ferrite-Graphene-polyaniline ternary nano composite material.
Embodiment
The first step: graphite oxide is carried out in ethanol to ultrasonic dispersion 30 ~ 120 min, obtain graphene oxide solution;
Second step is 1:2 Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and iron nitrate stirring and dissolving in ethanol by mol ratio;
The 3rd step, mixes first two steps gained solution, stirs 30 ~ 120min, and regulating pH value is 7 ~ 12;
The 4th step, is transferred to the 3rd step gained reaction system in water heating kettle and reacts, and temperature of reaction is 120 ~ 240 DEG C, and the reaction times is 12 ~ 28 h, obtains cobalt ferrite-graphene composite material after washing, and wherein the mass ratio of cobalt ferrite and Graphene is 1 ~ 40%;
The 5th step, is dispersed in the cobalt ferrite-graphene composite material of the 4th step gained and initiator ammonium persulfate in the acid solution of 0.1 ~ 1 mol/L, and acid can be the one in hydrochloric acid, sulfuric acid or phosphoric acid;
The 6th step, under ice bath state, aniline is joined in the system of the 5th step gained, the mol ratio of the initiator ammonium persulfate adding in the aniline adding and the 5th step is 1:1 ~ 3, and the mass ratio of the cobalt ferrite-graphene nanocomposite material adding in the aniline adding and the 5th step is 1:0.2 ~ 1:2;
The 7th step is reacted the system of gained 6 ~ 20 h at 0 ~ 25 DEG C;
The 8th step, carries out filtering separation by the product of the 7th step gained, obtains cobalt ferrite-Graphene-polyaniline ternary nano composite material after dry, and the massfraction that wherein polyaniline accounts for total material is about 50 ~ 90%.
embodiment 1:cobalt ferrite-Graphene-polyaniline ternary nano composite material, the mass ratio of cobalt ferrite and Graphene is 1%, the massfraction that polyaniline accounts for total material is about 90% preparation method, comprises the following steps:
The first step: 3 mg graphite oxides are carried out to ultrasonic dispersion 30 min in ethanol, obtain graphene oxide solution;
Second step, the stirring and dissolving in ethanol by 0.1486 g Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and 0.4126 g iron nitrate (mol ratio is 1:2);
The 3rd step, mixes first two steps gained solution, stirs 60 min, and regulating pH value is 7;
The 4th step, is transferred to the 3rd step gained reaction system in water heating kettle and reacts, and temperature of reaction is 240 DEG C, and the reaction times is 12 h, obtains cobalt ferrite-graphene composite material, and wherein the mass ratio of cobalt ferrite and Graphene is 1%;
The 5th step, is dispersed in the cobalt ferrite-graphene composite material of the 4th step gained and initiator ammonium persulfate in the hydrochloric acid soln of 1 mol/L;
The 6th step, under ice bath state, 1.0 mL aniline are joined in the system of the 5th step gained, and the mol ratio of the initiator adding in the aniline adding and the 5th step is 1:3, and the mass ratio of the cobalt ferrite-graphene composite material adding in the aniline adding and the 5th step is 1:0.2;
The 7th step is reacted the system of gained 18 h at 0 DEG C;
The 8th step, carries out filtering separation by the product of the 7th step gained, obtains cobalt ferrite-Graphene-polyaniline ternary nano composite material after dry, and the massfraction that wherein polyaniline accounts for total material is about 90%, and its TEM figure is shown in Fig. 1.
embodiment 2:cobalt ferrite-Graphene-polyaniline ternary nano composite material, the mass ratio of cobalt ferrite and Graphene is 10%, the massfraction that polyaniline accounts for total material is about 70% preparation method, comprises the following steps:
The first step: 13 mg graphite oxides are carried out to ultrasonic dispersion 60 min in ethanol, obtain graphene oxide solution;
Second step, the stirring and dissolving in ethanol by 0.1486g Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and 0.4126g iron nitrate (mol ratio is 1:2);
The 3rd step, mixes first two steps gained solution, stirs 30min, and regulating pH value is 8;
The 4th step, is transferred to the 3rd step gained reaction system in water heating kettle and reacts, and temperature of reaction is 200 DEG C, and the reaction times is 16 h, obtains cobalt ferrite-graphene composite material, and wherein the mass ratio of cobalt ferrite and Graphene is 10%;
The 5th step, is dispersed in the cobalt ferrite-graphene composite material of the 4th step gained and initiator ammonium persulfate in the sulphuric acid soln of 0.9 mol/L;
The 6th step, under ice bath state, 0.5 mL aniline is joined in the system of the 5th step gained, and the mol ratio of the initiator adding in the aniline adding and the 5th step is 1:1, and the mass ratio of the cobalt ferrite-graphene composite material adding in the aniline adding and the 5th step is 1:0.6;
The 7th step is reacted the system of gained 15 h at 25 DEG C;
The 8th step, carries out filtering separation by the product of the 7th step gained, obtains cobalt ferrite-Graphene-polyaniline ternary nano composite material after dry, and the massfraction that wherein polyaniline accounts for total material is about 68.4%.
embodiment 3:cobalt ferrite-Graphene-polyaniline ternary nano composite material, the mass ratio of cobalt ferrite and Graphene is 20%, the massfraction that polyaniline accounts for total material is about 60% preparation method, comprises the following steps:
The first step: 40 mg graphite oxides are carried out to ultrasonic dispersion 90 min in ethanol, obtain graphene oxide solution;
Second step, the stirring and dissolving in ethanol by 0.1486g Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and 0.4126g iron nitrate (mol ratio is 1:2);
The 3rd step, mixes first two steps gained solution, stirs 120min, and regulating pH value is 10;
The 4th step, is transferred to the 3rd step gained reaction system in water heating kettle and reacts, and temperature of reaction is 180 DEG C, and the reaction times is 20 h, obtains cobalt ferrite-graphene composite material, and wherein the mass ratio of cobalt ferrite and Graphene is 20%;
The 5th step, is dispersed in the cobalt ferrite-graphene composite material of the 4th step gained and initiator ammonium persulfate in the phosphoric acid solution of 0.5 mol/L;
The 6th step, be under 0 ~ 4 DEG C of state in temperature, 0.7 mL aniline is joined in the system of the 5th step gained, and the mol ratio of the initiator adding in the aniline adding and the 5th step is 1:2, and the mass ratio of the cobalt ferrite-graphene composite material adding in the aniline adding and the 5th step is 1:1;
The 7th step is reacted the system of gained 10 h at 10 DEG C;
The 8th step, carries out filtering separation by the product of the 7th step gained, obtains cobalt ferrite-Graphene-polyaniline ternary nano composite material after dry, and the massfraction that wherein polyaniline accounts for total material is about 57.3%.
embodiment 4:cobalt ferrite-Graphene-polyaniline ternary nano composite material, the mass ratio of cobalt ferrite and Graphene is 30%, the massfraction that polyaniline accounts for total material is about 80% preparation method, comprises the following steps:
The first step: 60 mg graphite oxides are carried out to ultrasonic dispersion 100 min in ethanol, obtain graphene oxide solution;
Second step, the stirring and dissolving in ethanol by 0.1486g Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and 0.4126g iron nitrate (mol ratio is 1:2);
The 3rd step, mixes first two steps gained solution, stirs 90min, and regulating pH value is 11;
The 4th step, is transferred to the 3rd step gained reaction system in water heating kettle and reacts, and temperature of reaction is 150 DEG C, and the reaction times is 24 h, obtains cobalt ferrite-graphene composite material, and wherein the mass ratio of cobalt ferrite and Graphene is 30%;
The 5th step, is dispersed in the cobalt ferrite-graphene composite material of the 4th step gained and initiator ammonium persulfate in the hydrochloric acid soln of 0.3 mol/L;
The 6th step, be under 0 ~ 4 DEG C of state in temperature, 1.0 mL aniline are joined in the system of the 5th step gained, the mol ratio of the initiator adding in the aniline adding and the 5th step is 1:3, and the mass ratio of the cobalt ferrite-graphene composite material adding in the aniline adding and the 5th step is 1:1.4;
The 7th step is reacted the system of gained 20 h at 15 DEG C;
The 8th step, carries out filtering separation by the product of the 7th step gained, obtains cobalt ferrite-Graphene-polyaniline ternary nano composite material after dry, and the massfraction that wherein polyaniline accounts for total material is about 78.2%.
embodiment 5:cobalt ferrite-Graphene-polyaniline ternary nano composite material, the mass ratio of cobalt ferrite and Graphene is 40%, the massfraction that polyaniline accounts for total material is about 50% preparation method, comprises the following steps:
The first step: 80 mg graphite oxides are carried out to ultrasonic dispersion 120 min in ethanol, obtain graphene oxide solution;
Second step, the stirring and dissolving in ethanol by 0.1486g Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and 0.4126g iron nitrate (mol ratio is 1:2);
The 3rd step, mixes first two steps gained solution, stirs 100min, and regulating pH value is 12;
The 4th step, is transferred to the 3rd step gained reaction system in water heating kettle and reacts, and temperature of reaction is 120 DEG C, and the reaction times is 28 h, obtains cobalt ferrite-graphene composite material, and wherein the mass ratio of cobalt ferrite and Graphene is 40%;
The 5th step, is dispersed in the cobalt ferrite-graphene composite material of the 4th step gained and initiator ammonium persulfate in the phosphoric acid solution of 0.1 mol/L;
The 6th step, be under 0 ~ 4 DEG C of state in temperature, 0.3 mL aniline is joined in the system of the 5th step gained, the mol ratio of the initiator adding in the aniline adding and the 5th step is 1:1, and the mass ratio of the cobalt ferrite-graphene composite material adding in the aniline adding and the 5th step is 1:2;
The 7th step is reacted the system of gained 6 h at 20 DEG C;
The 8th step, carries out filtering separation by the product of the 7th step gained, obtains cobalt ferrite-Graphene-polyaniline ternary nano composite material after dry, and the massfraction that wherein polyaniline accounts for total material is about 50%.
performance test: the cobalt ferrite-Graphene of gained-polyaniline ternary nano composite material is prepared into electrode, in three-electrode system, carries out the performance test of electrochemistry cyclic voltammetric, by Equation for Calculating gained specific capacitance (
c) size, experimental result is shown in form 1.
。
As shown in Table 1, the cobalt ferrite-Graphene of gained-polyaniline ternary nano composite material, in different electrolyte solutions, particularly all has good accumulate performance in acid and alkaline electrolyte.
Claims (9)
1. cobalt ferrite-Graphene-polyaniline ternary nano composite material, it is characterized in that described nano composite material is made up of nano-ferrous acid, Graphene and polyaniline, nano-ferrous acid loads on graphene sheet layer, polyaniline-coated is on the surface of whole lamella, wherein the mass ratio of cobalt ferrite and Graphene is 1 ~ 40%, and polyaniline accounts for 50 ~ 90% of ternary nano composite material total mass.
2. cobalt ferrite-Graphene according to claim 1-polyaniline ternary nano composite material, the matrix material described in it is characterized in that is prepared by following steps:
The first step, is dispersed in cobalt ferrite-graphene nanocomposite material and ammonium persulphate in acid solution;
Second step, under ice bath state, joins aniline in the system of the first step gained;
The 3rd step is reacted the system of gained under 0 ~ 25 DEG C of condition;
The 4th step, carries out filtering separation, dry rear cobalt ferrite-Graphene-polyaniline ternary nano composite material that obtains by the product of the 3rd step gained.
3. cobalt ferrite-Graphene according to claim 2-polyaniline ternary nano composite material, it is characterized in that in the cobalt ferrite-graphene nanocomposite material described in the first step, the mass ratio of cobalt ferrite and Graphene is 1 ~ 40%, the concentration of described acid solution is 0.1 ~ 1 mol/L, and described acid is selected from the one in hydrochloric acid, sulfuric acid or phosphoric acid; The mol ratio of the aniline described in second step and ammonium persulphate is 1:1 ~ 3, and the mass ratio of the cobalt ferrite-graphene nanocomposite material described in described aniline and the first step is 1:0.2 ~ 1:2.
4. cobalt ferrite-Graphene according to claim 2-polyaniline ternary nano composite material, is characterized in that reaction times 6 ~ 20 h described in the 3rd step; In cobalt ferrite-Graphene-polyaniline ternary nano composite material described in the 4th step, polyaniline accounts for 50 ~ 90% of ternary nano composite material total mass.
5. a preparation method for cobalt ferrite-Graphene-polyaniline ternary nano composite material, is characterized in that comprising the following steps:
The first step, is dispersed in cobalt ferrite-graphene nanocomposite material and ammonium persulphate in acid solution;
Second step, under ice bath state, joins aniline in the system of the first step gained;
The 3rd step is reacted the system of gained under 0 ~ 25 DEG C of condition;
The 4th step, carries out filtering separation, dry rear cobalt ferrite-Graphene-polyaniline ternary nano composite material that obtains by the product of the 3rd step gained.
6. the preparation method of cobalt ferrite-Graphene according to claim 5-polyaniline ternary nano composite material, it is characterized in that in the cobalt ferrite-graphene nanocomposite material described in the first step, the mass ratio of cobalt ferrite and Graphene is 1 ~ 40%, the concentration of described acid solution is 0.1 ~ 1 mol/L, and described acid is selected from the one in hydrochloric acid, sulfuric acid or phosphoric acid; The mol ratio of the aniline described in second step and ammonium persulphate is 1:1 ~ 3, and the mass ratio of the cobalt ferrite-graphene nanocomposite material described in described aniline and the first step is 1:0.2 ~ 1:2.
7. the preparation method of cobalt ferrite-Graphene according to claim 5-polyaniline ternary nano composite material, is characterized in that reaction times 6 ~ 20 h described in the 3rd step; In cobalt ferrite-Graphene-polyaniline ternary nano composite material described in the 4th step, polyaniline accounts for 50 ~ 90% of ternary nano composite material total mass.
8. the preparation method of cobalt ferrite-Graphene according to claim 5-polyaniline ternary nano composite material, is characterized in that the cobalt ferrite-graphene nanocomposite material described in the first step prepared by following steps:
The 1st step: graphite oxide is carried out in ethanol to ultrasonic dispersion and obtain graphene oxide solution;
The 2nd step, the stirring and dissolving in ethanol by iron nitrate and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES;
The 3rd step, mixes first two steps gained solution, stirs, and regulates pH value;
The 4th step, is transferred to the 3rd step gained reaction system in water heating kettle and reacts, products therefrom washing.
9. the preparation method of cobalt ferrite-Graphene according to claim 8-polyaniline ternary nano composite material, is characterized in that the ultrasonic jitter time described in the 1st step is 30 ~ 120 min, and described graphite oxide adopts Hummer legal system standby; Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES described in the 2nd step and iron nitrate mol ratio are 1:2; Described in the 3rd step, the churning time of mixing solutions is 30 ~ 120min, pH=7 ~ 12; Hydrothermal temperature described in the 4th step is 120 ~ 240 DEG C, and the reaction times is 12 ~ 28 h.
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