CN111320197B - Cerium dioxide graphene composite material for supercapacitor and preparation method thereof - Google Patents
Cerium dioxide graphene composite material for supercapacitor and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 68
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title claims abstract description 45
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 54
- 239000011259 mixed solution Substances 0.000 claims abstract description 43
- 239000000243 solution Substances 0.000 claims abstract description 43
- 239000000725 suspension Substances 0.000 claims abstract description 38
- 238000001035 drying Methods 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 14
- 230000009471 action Effects 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 238000009210 therapy by ultrasound Methods 0.000 claims description 17
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 6
- 238000013461 design Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000008367 deionised water Substances 0.000 description 31
- 229910021641 deionized water Inorganic materials 0.000 description 31
- 239000002244 precipitate Substances 0.000 description 17
- 238000005406 washing Methods 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 235000019441 ethanol Nutrition 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 13
- 239000003990 capacitor Substances 0.000 description 7
- 238000002484 cyclic voltammetry Methods 0.000 description 4
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- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
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- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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- 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
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- 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
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Abstract
The invention discloses a cerium dioxide/graphene composite material for a supercapacitor and a preparation method thereof, and belongs to the technical field of chemical materials. The preparation method comprises the following steps of taking cerous nitrate hexahydrate and graphene oxide to perform hydrothermal reaction under the action of a silane coupling agent to prepare the composite material: 1) adding cerous nitrate hexahydrate into a silane coupling agent to obtain a solution A; 2) adding a silane coupling agent into cerous nitrate hexahydrate to obtain a suspension B; 3) mixing the solution A obtained in the step 1) and the suspension B obtained in the step 2) to obtain a mixed solution, pouring the mixed solution into graphene oxide, uniformly mixing, transferring the mixed solution into a hydrothermal reaction kettle, controlling the reaction temperature to be 120-180 ℃, reacting for 12-48 hours, cooling, post-treating and drying to obtain the composite material. The design method of the invention has the advantages of simple operation, less energy consumption, less pollution and strong repeatability operability.
Description
Technical Field
The invention relates to a composite material for a supercapacitor, belongs to the technical field of composite materials, and particularly relates to a cerium dioxide graphene composite material for a supercapacitor and a preparation method thereof.
Background
The super capacitor is a novel energy storage device between a traditional capacitor and a rechargeable battery, has the characteristics of high power density, long cycle life, wide working temperature limit, good stability, environmental friendliness and the like, and is concerned by people. In the existing carbon materials, activated carbon, graphene, carbon nanotubes, carbon fibers and the like can be used as one of the main materials of the supercapacitor. Among them, graphene having a two-dimensional honeycomb structure in which a single layer of carbon atoms is densely formed is considered to be an excellent supercapacitor carbon-based material due to its excellent electrochemical properties, excellent chemical and thermodynamic stabilities, and physical and mechanical properties.
The metal oxide with the nano structure is one of the main pseudo capacitor materials, has higher theoretical specific capacitance, can improve energy density while keeping high power capacity, and has excellent energy storage characteristicAnd (4) point. CeO (CeO)2The nano material has low cost and good electrochemical oxidation-reduction characteristics, and is a good super capacitor electrode candidate material.
Conventional CeO2The electrode preparation method of the nano material composite graphene supercapacitor material mainly adopts the CeO prepared by an oil bath method by taking graphene oxide as a matrix and cerium nitrate as a cerium source2a/rGO composite material. In the preparation process, toxic hydrazine hydrate is added, high-temperature annealing at 500 ℃ is required, the method is high in energy consumption, toxic and harmful substances are generated, and large-scale industrial production is limited.
The Chinese invention patent application (application publication number: CN102631913A, application publication date: 2012-08-15) discloses a preparation method of a graphene loaded cerium dioxide nano cubic composite, which comprises the following specific preparation processes: and (2) pouring ammonia water into the mixed solution of graphene oxide and cerous nitrate hexahydrate, controlling the reaction temperature to be 220-240 ℃, heating and reacting for 12-24 h, then carrying out suction filtration on the reaction solution to be neutral, and drying the obtained slurry to obtain the graphene-loaded cerium dioxide nano cubic composite with (200) exposed surfaces. However, the reaction conditions are strict, the reaction needs to be completed in a reaction kettle, the reaction temperature is high, repeated suction filtration is needed, and the operation is troublesome.
Chinese invention patent application (application publication No. CN105957732A, application publication date: 2016-09-21) discloses a preparation method of a large rod-group bundle-shaped nano cerium dioxide and activated carbon composite electrode material for a super capacitor; the preparation method comprises the steps of adding CeCl3 & 7H2O and urea into water, uniformly stirring, putting into a reaction kettle, heating, carrying out hydrothermal reaction, washing to obtain white precipitate, and calcining in a muffle furnace to obtain large rod-group beam-shaped nano cerium dioxide; preparing rod-group beam-shaped nano cerium dioxide/activated carbon composite from activated carbon and large rod-group beam-shaped nano cerium dioxide, and then preparing the large rod-group beam-shaped nano cerium dioxide/activated carbon composite electrode material with acetylene black serving as a conductive agent and a binder. The advantages are that: the preparation method is simple, has high specific capacitance and small charge transfer resistance, and is suitable for being used as a super capacitor electrode. Similarly, the reaction conditions are also relatively strict.
Disclosure of Invention
In order to solve the technical problems, the invention discloses a cerium dioxide graphene composite material for a supercapacitor and a preparation method thereof.
In order to achieve the purpose, the invention discloses a preparation method of a composite material for a cerium dioxide/graphene supercapacitor, which comprises the following steps of carrying out hydrothermal reaction on cerium nitrate hexahydrate and graphene oxide under the action of a silane coupling agent to prepare the composite material:
1) adding cerous nitrate hexahydrate into a silane coupling agent to obtain a solution A;
2) adding a silane coupling agent into cerous nitrate hexahydrate to obtain a suspension B;
3) mixing the solution A obtained in the step 1) and the suspension B obtained in the step 2) to obtain a mixed solution, pouring the mixed solution into graphene oxide, uniformly mixing, transferring the mixed solution into a hydrothermal reaction kettle, controlling the reaction temperature to be 120-180 ℃, reacting for 12-48 hours, cooling, post-treating and drying to obtain the composite material.
Further, the silane coupling agent comprises gamma-aminopropyltriethoxysilane, and after the gamma-aminopropyltriethoxysilane is subjected to functional modification, the lamellar spacing of the functionalized graphene is increased, the dispersion is uniform, and obvious lamellar wrinkles are formed. Further, the silane coupling agent includes gamma-aminopropyltriethoxysilane.
Further, in the step 1), the mass ratio of the silane coupling agent to the cerous nitrate hexahydrate is (1.5-2.2): 1, and the solvent in the solution A is water.
Preferably, in the step 1), the mass ratio of the silane coupling agent to the cerous nitrate hexahydrate is (1.8-2.0): 1,
further, in the step 2), the mass ratio of the silane coupling agent to the cerous nitrate hexahydrate is 1 (1.5-2.2), and the solvent in the suspension B is water.
Preferably, in the step 2), the mass ratio of the silane coupling agent to the cerous nitrate hexahydrate is 1 (1.8-2.0).
The two-time addition is different because the ratio of the silane coupling agent to the cerous nitrate hexahydrate is different in each addition, for example, the mass ratio of the silane coupling agent to the cerous nitrate hexahydrate (1.5-2.2): 1 is controlled for the first time, the cerous nitrate hexahydrate is selectively added into the silane coupling agent to obtain a yellow solution, the mass ratio of the silane coupling agent to the cerous nitrate hexahydrate is controlled for the second time to be 1- (1.5-2.2), and flocculent precipitates are generated by selectively adding the silane coupling agent into the cerous nitrate hexahydrate.
Further, in the step 3), the solution A obtained in the step 1) and the suspension B obtained in the step 2) are mixed to obtain a mixed solution, and the mixed solution is poured into graphene oxide and subjected to ultrasonic treatment for 1.5-3 hours.
Further, in the step 3), the addition amount of the graphene oxide is 1-3 mg/mL. Namely, in the step 3), 1-3 mg of graphene oxide is added to each mL of the mixed solution.
Further, in the step 3), the reaction temperature is 130-160 ℃.
Further, in the step 3), the post-treatment comprises washing with deionized water and absolute ethyl alcohol respectively for at least three times, and then drying in an oven.
Further, in the step 3), the temperature of the oven is controlled to be 50-80 ℃, and the drying time is 6-24 hours.
In order to better achieve the technical purpose of the invention, the invention also discloses a cerium dioxide/graphene composite material for the supercapacitor, which is prepared by the preparation method, wherein cerium dioxide in the composite material has a typical cubic structure, and the typical cubic structure is a regular polyhedral three-dimensional structure, such as a cube structure or a hexahedral structure. The cerium dioxide particle with the structure has a small structure and a large contact area, can increase the contact area with electrolyte, and has small volume change and higher stability in the charge and discharge process compared with the cerium dioxide with a porous structure.
The beneficial effects of the invention are mainly embodied in the following aspects:
1. the composite material prepared by the design method of the invention has the advantages of good cycle performance and large capacitance when being used for preparing the capacitor;
2. the design method of the invention has the advantages of simple operation, less energy consumption, less pollution and strong repeatability.
Drawings
FIG. 1 is an XRD spectrum of the composite material prepared by the present invention.
FIG. 2 is an SEM photograph of cerium oxide prepared by a two-step process in example 1.
FIG. 3 is a cyclic voltammogram of a composite prepared according to the present invention at scan rates of 5mV/s, 10mV/s, 20mV/s, 50mV/s, 100mV/s, and 200 mV/s.
Detailed Description
In order to better achieve the technical objects of the present invention, the following specific examples are disclosed in the present invention for detailed explanation.
Example 1
The embodiment discloses a preparation method of a cerium dioxide/graphene composite material for a supercapacitor, which comprises the following specific steps:
1) dissolving 1.0g of silane coupling agent KH550 in 20mL of deionized water, and adding 0.5g of cerous nitrate hexahydrate under stirring until the cerous nitrate is completely dissolved to obtain solution A;
2) dissolving 1.9g of cerous nitrate hexahydrate in 20mL of deionized water, and adding 1.0g of silane coupling agent KH550 to obtain a suspension B generating a precipitate;
3) mixing the solution A obtained in the step 1) and the suspension B obtained in the step 2) to obtain a mixed solution, and pouring the mixed solution into 40mg of graphene oxide to perform ultrasonic treatment for 1.5 h; and then transferring the mixture into a hydrothermal reaction kettle, controlling the reaction temperature to be 160 ℃, reacting for 24 hours, cooling, centrifuging, washing with water and alcohol for three times respectively, and drying in a drying oven at the temperature of 60 ℃ for 20 hours to obtain the composite material.
Example 2
The embodiment discloses a preparation method of a cerium dioxide/graphene composite material for a supercapacitor, which comprises the following specific steps:
1) dissolving 1.0g of silane coupling agent KH550 in 20mL of deionized water, and adding 0.5g of cerous nitrate hexahydrate under stirring until the cerous nitrate is completely dissolved to obtain solution A;
2) dissolving 1.9g of cerous nitrate hexahydrate in 20mL of deionized water, and adding 1.0g of silane coupling agent KH550 to obtain a suspension B generating a precipitate;
3) mixing the solution A obtained in the step 1) and the suspension B obtained in the step 2) to obtain a mixed solution, and pouring the mixed solution into 60mg of graphene oxide to perform ultrasonic treatment for 1.5 h; and then transferring the mixture into a hydrothermal reaction kettle, controlling the reaction temperature to be 120 ℃, reacting for 45 hours, cooling, centrifuging, washing with water and alcohol for three times respectively, and drying in a drying oven at 50 ℃ for 24 hours to obtain the composite material.
Example 3
The embodiment discloses a preparation method of a cerium dioxide/graphene composite material for a supercapacitor, which comprises the following specific steps:
1) dissolving 1.0g of silane coupling agent KH550 in 20mL of deionized water, and adding 0.5g of cerous nitrate hexahydrate under stirring until the cerous nitrate hexahydrate is completely dissolved to obtain solution A;
2) dissolving 1.9g of cerous nitrate hexahydrate in 20mL of deionized water, and adding 1.0g of silane coupling agent KH550 to obtain a suspension B generating a precipitate;
3) mixing the solution A obtained in the step 1) and the solution B obtained in the step 2) to obtain a mixed solution, and pouring the mixed solution into 80mg of graphene oxide to perform ultrasonic treatment for 1.5 h; and then transferring the mixture into a hydrothermal reaction kettle, controlling the reaction temperature to be 140 ℃, reacting for 30h, cooling, centrifuging, washing with water and alcohol for three times respectively, and drying in a drying oven at 70 ℃ for 12h to obtain the composite material.
Example 4
The embodiment discloses a preparation method of a cerium dioxide/graphene composite material for a supercapacitor, which comprises the following specific steps:
1) dissolving 1.0g of silane coupling agent KH550 in 20mL of deionized water, and adding 0.5g of cerous nitrate hexahydrate under stirring until the cerous nitrate is completely dissolved to obtain solution A;
2) dissolving 1.9g of cerous nitrate hexahydrate in 20mL of deionized water, and adding 1.0g of silane coupling agent KH550 to obtain a suspension B generating a precipitate;
3) mixing the solution A obtained in the step 1) and the suspension B obtained in the step 2) to obtain a mixed solution, and pouring the mixed solution into 100mg of graphene oxide to perform ultrasonic treatment for 2.5 hours; and then transferring the mixture into a hydrothermal reaction kettle, controlling the reaction temperature to be 160 ℃, reacting for 30 hours, cooling, centrifuging, washing with water and alcohol for three times respectively, and drying in a drying oven at the temperature of 60 ℃ for 20 hours to obtain the composite material.
Example 5
The embodiment discloses a preparation method of a cerium dioxide/graphene composite material for a supercapacitor, which comprises the following specific steps:
1) dissolving 1.0g of silane coupling agent KH550 in 20mL of deionized water, and adding 0.5g of cerous nitrate hexahydrate under stirring until the cerous nitrate is completely dissolved to obtain solution A;
2) dissolving 1.9g of cerous nitrate hexahydrate in 20mL of deionized water, and adding 1.0g of silane coupling agent KH550 to obtain a suspension B generating a precipitate;
3) mixing the solution A obtained in the step 1) and the suspension B obtained in the step 2) to obtain a mixed solution, and pouring the mixed solution into 120mg of graphene oxide to perform ultrasonic treatment for 1.5 h; and then transferring the mixture into a hydrothermal reaction kettle, controlling the reaction temperature to be 180 ℃, reacting for 20 hours, cooling, centrifuging, washing with water and alcohol for three times respectively, and drying in an oven at the temperature of 80 ℃ for 12 hours to obtain the composite material.
Example 6
The embodiment discloses a preparation method of a cerium dioxide/graphene composite material for a supercapacitor, which comprises the following specific steps:
1) dissolving 1.1g of silane coupling agent KH550 in 20mL of deionized water, and adding 0.5g of cerous nitrate hexahydrate under stirring until the cerous nitrate hexahydrate is completely dissolved to obtain solution A;
2) dissolving 2.2g of cerous nitrate hexahydrate in 20mL of deionized water, and adding 1.0g of silane coupling agent KH550 to obtain a suspension B generating a precipitate;
3) mixing the solution A obtained in the step 1) and the suspension B obtained in the step 2) to obtain a mixed solution, and pouring the mixed solution into 40mg of graphene oxide to perform ultrasonic treatment for 1.5 h; and then transferring the mixture into a hydrothermal reaction kettle, controlling the reaction temperature to be 160 ℃, reacting for 30 hours, cooling, centrifuging, washing with water and alcohol for three times respectively, and drying in an oven at the temperature of 80 ℃ for 6 hours to obtain the composite material.
Example 7
The embodiment discloses a preparation method of a cerium dioxide/graphene composite material for a supercapacitor, which comprises the following specific steps:
1) dissolving 1.1g of silane coupling agent KH550 in 20mL of deionized water, and adding 0.5g of cerous nitrate hexahydrate under stirring until the cerous nitrate hexahydrate is completely dissolved to obtain solution A;
2) dissolving 2.2g of cerous nitrate hexahydrate in 20mL of deionized water, and adding 1.0g of silane coupling agent KH550 to obtain a suspension B generating a precipitate;
3) mixing the solution A obtained in the step 1) and the suspension B obtained in the step 2) to obtain a mixed solution, and pouring the mixed solution into 60mg of graphene oxide to perform ultrasonic treatment for 2 hours; and then transferring the mixture into a hydrothermal reaction kettle, controlling the reaction temperature to be 130 ℃, reacting for 48 hours, cooling, centrifuging, washing with water and alcohol for three times respectively, and drying in a drying oven at 50 ℃ for 24 hours to obtain the composite material.
Example 8
The embodiment discloses a preparation method of a cerium dioxide/graphene composite material for a supercapacitor, which comprises the following specific steps:
1) dissolving 1.1g of silane coupling agent KH550 in 20mL of deionized water, and adding 0.5g of cerous nitrate hexahydrate under stirring until the cerous nitrate is completely dissolved to obtain solution A;
2) dissolving 2.2g of cerous nitrate hexahydrate in 20mL of deionized water, and adding 1.0g of silane coupling agent KH550 to obtain a suspension B generating a precipitate;
3) mixing the solution A obtained in the step 1) and the suspension B obtained in the step 2) to obtain a mixed solution, and pouring the mixed solution into 80mg of graphene oxide to perform ultrasonic treatment for 2 hours; and then transferring the mixture into a hydrothermal reaction kettle, controlling the reaction temperature to be 150 ℃, reacting for 30 hours, cooling, centrifuging, washing with water and alcohol for three times respectively, and drying in a drying oven at 70 ℃ for 10 hours to obtain the composite material.
Example 9
The embodiment discloses a preparation method of a cerium dioxide/graphene composite material for a supercapacitor, which comprises the following specific steps:
1) dissolving 1.1g of silane coupling agent KH550 in 20mL of deionized water, and adding 0.5g of cerous nitrate hexahydrate under stirring until the cerous nitrate is completely dissolved to obtain solution A;
2) dissolving 2.2g of cerous nitrate hexahydrate in 20mL of deionized water, and adding 1.0g of silane coupling agent KH550 to obtain a suspension B generating a precipitate;
3) mixing the solution A obtained in the step 1) and the suspension B obtained in the step 2) to obtain a mixed solution, and pouring the mixed solution into 100mg of graphene oxide to perform ultrasonic treatment for 2.5 hours; and then transferring the mixture into a hydrothermal reaction kettle, controlling the reaction temperature to be 170 ℃, reacting for 30h, cooling, centrifuging, washing with water and alcohol for three times respectively, and drying in a drying oven at the temperature of 60 ℃ for 12h to obtain the composite material.
Example 10
The embodiment discloses a preparation method of a cerium dioxide/graphene composite material for a supercapacitor, which comprises the following specific steps:
1) dissolving 1.1g of silane coupling agent KH550 in 20mL of deionized water, and adding 0.5g of cerous nitrate hexahydrate under stirring until the cerous nitrate is completely dissolved to obtain solution A;
2) dissolving 2.2g of cerous nitrate hexahydrate in 20mL of deionized water, and adding 1.0g of silane coupling agent KH550 to obtain a suspension B generating a precipitate;
3) mixing the solution A obtained in the step 1) and the suspension B obtained in the step 2) to obtain a mixed solution, and pouring the mixed solution into 120mg of graphene oxide to perform ultrasonic treatment for 1.5 h; and then transferring the mixture into a hydrothermal reaction kettle, controlling the reaction temperature to be 180 ℃, reacting for 24 hours, cooling, centrifuging, washing with water and alcohol for three times respectively, and drying in an oven at the temperature of 80 ℃ for 10 hours to obtain the composite material.
Example 11
The embodiment discloses a preparation method of a cerium dioxide/graphene composite material for a supercapacitor, which comprises the following specific steps:
1) dissolving 0.75g of silane coupling agent KH550 in 20mL of deionized water, and adding 0.5g of cerous nitrate hexahydrate under stirring until the cerous nitrate hexahydrate is completely dissolved to obtain solution A;
2) dissolving 1.9g of cerous nitrate hexahydrate in 20mL of deionized water, and adding 1.0g of silane coupling agent KH550 to obtain a suspension B generating a precipitate;
3) mixing the solution A obtained in the step 1) and the suspension B obtained in the step 2) to obtain a mixed solution, and pouring the mixed solution into 40mg of graphene oxide to perform ultrasonic treatment for 1.5 h; and then transferring the mixture into a hydrothermal reaction kettle, controlling the reaction temperature to be 180 ℃, reacting for 12 hours, cooling, centrifuging, washing with water and alcohol for three times respectively, and drying in a drying oven at the temperature of 60 ℃ for 15 hours to obtain the composite material.
Example 12
The embodiment discloses a preparation method of a cerium dioxide/graphene composite material for a supercapacitor, which comprises the following specific steps:
1) dissolving 0.75g of silane coupling agent KH550 in 20mL of deionized water, and adding 0.5g of cerous nitrate hexahydrate under stirring until the cerous nitrate is completely dissolved to obtain solution A;
2) dissolving 1.9g of cerous nitrate hexahydrate in 20mL of deionized water, and adding 1.0g of silane coupling agent KH550 to obtain a suspension B generating a precipitate;
3) mixing the solution A obtained in the step 1) and the suspension B obtained in the step 2) to obtain a mixed solution, and pouring the mixed solution into 60mg of graphene oxide to perform ultrasonic treatment for 1.5 h; and then transferring the mixture into a hydrothermal reaction kettle, controlling the reaction temperature to be 120 ℃, reacting for 40 hours, cooling, centrifuging, washing with water and alcohol for three times respectively, and drying in a drying oven at 50 ℃ for 20 hours to obtain the composite material.
Example 13
The embodiment discloses a preparation method of a cerium dioxide/graphene composite material for a supercapacitor, which comprises the following specific steps:
1) dissolving 0.75g of silane coupling agent KH550 in 20mL of deionized water, and adding 0.5g of cerous nitrate hexahydrate under stirring until the cerous nitrate is completely dissolved to obtain solution A;
2) dissolving 1.9g of cerous nitrate hexahydrate in 20mL of deionized water, and adding 1.0g of silane coupling agent KH550 to obtain a suspension B generating a precipitate;
3) mixing the solution A obtained in the step 1) and the suspension B obtained in the step 2) to obtain a mixed solution, and pouring the mixed solution into 80mg of graphene oxide to perform ultrasonic treatment for 1.5 h; and then transferring the mixture into a hydrothermal reaction kettle, controlling the reaction temperature to be 140 ℃, reacting for 30h, cooling, centrifuging, washing with water and alcohol for three times respectively, and drying in a drying oven at 70 ℃ for 12h to obtain the composite material.
Example 14
The embodiment discloses a preparation method of a cerium dioxide/graphene composite material for a supercapacitor, which comprises the following specific steps:
1) dissolving 0.75g of silane coupling agent KH550 in 20mL of deionized water, and adding 0.5g of cerous nitrate hexahydrate under stirring until the cerous nitrate is completely dissolved to obtain solution A;
2) dissolving 1.9g of cerous nitrate hexahydrate in 20mL of deionized water, and adding 1.0g of silane coupling agent KH550 to obtain a suspension B generating a precipitate;
3) mixing the solution A obtained in the step 1) and the suspension B obtained in the step 2) to obtain a mixed solution, and pouring the mixed solution into 100mg of graphene oxide to perform ultrasonic treatment for 2.5 hours; and then transferring the mixture into a hydrothermal reaction kettle, controlling the reaction temperature to be 160 ℃, reacting for 24 hours, cooling, centrifuging, washing with water and alcohol for three times respectively, and drying in a drying oven at the temperature of 60 ℃ for 24 hours to obtain the composite material.
Example 15
The embodiment discloses a preparation method of a cerium dioxide/graphene composite material for a supercapacitor, which comprises the following specific steps:
1) dissolving 0.75g of silane coupling agent KH550 in 20mL of deionized water, and adding 0.5g of cerous nitrate hexahydrate under stirring until the cerous nitrate is completely dissolved to obtain solution A;
2) dissolving 1.9g of cerous nitrate hexahydrate in 20mL of deionized water, and adding 1.0g of silane coupling agent KH550 to obtain a suspension B generating a precipitate;
3) mixing the solution A obtained in the step 1) and the suspension B obtained in the step 2) to obtain a mixed solution, and pouring the mixed solution into 120mg of graphene oxide for ultrasonic treatment for 1.5 hours; and then transferring the mixture into a hydrothermal reaction kettle, controlling the reaction temperature to be 180 ℃, reacting for 16h, cooling, centrifuging, washing with water and alcohol for three times respectively, and drying in an oven at the temperature of 80 ℃ for 15h to obtain the composite material.
Comparative example
The comparative example is that the silane coupling agent and cerous nitrate hexahydrate are mixed at one time and then react with graphene oxide; the properties of the obtained composite material are shown in the table 1;
fig. 1 is an XRD spectrum of the composite material prepared in example 1 of the present invention, and it can be known from fig. 1 that the graphene-supported cerium oxide has distinct absorption peaks near 28.5 °, 33.0 °, 47.2 °, 56.3 °, 69.3 °, and 77.0 °, the corresponding crystal planes are (111), (200), (220), (311), (400), and (331), and the peak positions and intensities are both equal to CeO2The diffraction data of the standard spectrum of the cubic system (JCPDS 34-0394) are matched, and the fact that the CeO loaded on the surface of the graphene is successfully prepared is proved2And (3) granules. CeO in the figure2the/rGO nano composite material does not have an absorption peak belonging to graphene oxide, which indicates that the graphene oxide is successfully reduced in the hydrothermal reduction process.
The composite materials prepared in the above examples 1 to 15 and comparative examples are made into electrodes of a supercapacitor, the specific capacitance under the condition that the current density is 0.5A/g is shown in Table 1 after a constant current charge-discharge test, and the capacity retention rate is tested after 1000 charge-discharge cycles, which is also shown in Table 1;
table 1 list of properties of the composite materials
As can be seen from table 1, the specific capacitance of the composite material obtained by the preparation method is relatively large, which is probably because compared with the method of preparing a large amount of agglomerated ceria by a one-step method, the ceria floc prepared by the step method can be better and uniformly compounded on the surface of the graphene oxide sheet layer after being uniformly dispersed by ultrasound, thereby being beneficial to improving the capacitance of the composite material. The change of the cyclic discharge performance is not large, which is presumably because the cerium dioxide is compounded between the graphene oxide layers of the sheets, so that the stacking of the graphene oxide sheets is effectively avoided, and the stability of the composite material is improved.
As can be seen from FIG. 2, CeO prepared by this two-step process2The particles are very dispersed and no agglomeration of the metal oxides occurs as is common.
FIG. 3 is a plot of cyclic voltammograms at scan rates of 5mV/s, 10mV/s, 20mV/s, 50mV/s, 100mV/s, and 200mV/s for the composite prepared in example 1 of the present invention. As can be seen from fig. 2, as the scanning rate increases, the oxidation peak moves toward the positive electrode, and the reduction peak moves toward the negative electrode, indicating that the electrode material has a certain internal resistance effect. After the scanning rate is changed, the cyclic voltammetry curve shape of the electrode does not change obviously, because the electrode material is a nano material, the fast mass transfer and charge transfer of the electrochemical reaction are facilitated, and the polarization phenomenon of the electrode reaction is reduced. CeO (CeO)2The cyclic voltammetry curve of the/rGO composite material has weak oxidation-reduction peaks and similar rectangular shapes, which shows that CeO2the/rGO composite material has both double electric layer behaviors and pseudo-capacitance behaviors in the electrochemical energy storage process.
The above examples are merely preferred examples and are not intended to limit the embodiments of the present invention. In addition to the above embodiments, the present invention has other embodiments. All technical solutions formed by adopting equivalent substitutions or equivalent transformations fall within the protection scope of the claims of the present invention.
Claims (6)
1. A preparation method of a composite material for a cerium dioxide/graphene supercapacitor comprises the following steps of taking cerous nitrate hexahydrate and graphene oxide to perform hydrothermal reaction under the action of a silane coupling agent to prepare the composite material:
1) adding cerous nitrate hexahydrate into a silane coupling agent to obtain a solution A;
2) adding a silane coupling agent into cerous nitrate hexahydrate to obtain a suspension B;
3) mixing the solution A obtained in the step 1) and the suspension B obtained in the step 2) to obtain a mixed solution, pouring the mixed solution into graphene oxide, carrying out ultrasonic treatment for 1.5-3 h, transferring the mixed solution into a hydrothermal reaction kettle, controlling the reaction temperature to be 120-180 ℃, reacting for 12-48 h, cooling, post-treating and drying to obtain a composite material;
the silane coupling agent is gamma-aminopropyltriethoxysilane.
2. The preparation method of the cerium dioxide/graphene composite material for the supercapacitor according to claim 1, wherein in the step 1), the mass ratio of the silane coupling agent to the cerous nitrate hexahydrate is (1.5-2.2): 1, and the solvent in the solution A is water.
3. The preparation method of the cerium dioxide/graphene composite material for the supercapacitor according to claim 1, wherein in the step 2), the mass ratio of the silane coupling agent to the cerous nitrate hexahydrate is 1 (1.5-2.2), and the solvent in the suspension B is water.
4. The method for preparing the ceria/graphene supercapacitor composite material according to claim 1, 2 or 3, wherein in the step 3), the addition amount of the graphene oxide is 1-3 mg/mL.
5. The method for preparing the ceria/graphene supercapacitor composite material according to claim 1, 2 or 3, wherein the reaction temperature in the step 3) is 130 to 160 ℃.
6. The cerium dioxide/graphene composite material for the supercapacitor, which is prepared by the preparation method of claim 1, wherein the cerium dioxide in the composite material has a typical cubic structure.
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