CN108597891B - Silica @ metal oxide/graphene aerogel dual-load dual-coating composite material and preparation method and application thereof - Google Patents
Silica @ metal oxide/graphene aerogel dual-load dual-coating composite material and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 88
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000002131 composite material Substances 0.000 title claims abstract description 72
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 63
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 47
- 239000004964 aerogel Substances 0.000 title claims abstract description 38
- 239000011248 coating agent Substances 0.000 title claims abstract description 23
- 238000000576 coating method Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003990 capacitor Substances 0.000 claims abstract description 9
- 239000007772 electrode material Substances 0.000 claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 32
- 150000004706 metal oxides Chemical class 0.000 claims description 28
- 229910002804 graphite Inorganic materials 0.000 claims description 25
- 239000010439 graphite Substances 0.000 claims description 25
- 239000002105 nanoparticle Substances 0.000 claims description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 11
- 238000004108 freeze drying Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910021382 natural graphite Inorganic materials 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims 5
- 238000011068 loading method Methods 0.000 abstract description 10
- 238000009776 industrial production Methods 0.000 abstract description 3
- 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 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 229910052681 coesite Inorganic materials 0.000 description 18
- 229910052906 cristobalite Inorganic materials 0.000 description 18
- 229910052682 stishovite Inorganic materials 0.000 description 18
- 229910052905 tridymite Inorganic materials 0.000 description 18
- 229910001868 water Inorganic materials 0.000 description 17
- 239000011259 mixed solution Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- -1 graphene compound Chemical class 0.000 description 10
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- 239000000203 mixture Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
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- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
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- 238000003756 stirring Methods 0.000 description 5
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
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- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
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- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 239000011229 interlayer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
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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
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/13—Energy storage using capacitors
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Abstract
The invention discloses a silicon dioxide @ metal oxide/graphene aerogel dual-loading dual-coating composite material and a preparation method and application thereof. The composite material is applied as a super capacitor electrode material, shows good electrochemical performance, has a simple preparation method, is low in cost and environment-friendly, and meets industrial production standards.
Description
Technical Field
The invention relates to a silicon dioxide @ metal oxide/graphene aerogel (SiO)2@ MOx/GA), in particular to a double-load double-coated composite material formed by dispersedly loading silicon dioxide coated metal oxide nanoparticles in a pore structure of graphene aerogel, a preparation method thereof and application of the composite material as a supercapacitor electrode material, and belongs to the technical field of preparation of energy storage devices.
Background
The rapid development of economy and science and technology improves the quality of life of people and causes energy consumption and environmental pollution. Nowadays, people are more and more aware of the energy crisis and the severity of environmental pollution, and therefore, efforts are being made to develop new energy sources that are efficient and pollution-free. In order to fully utilize the new energy, research and development of the energy storage device need to be carried out, and the super capacitor is widely regarded and researched as a green energy storage device. The electrode material of the super capacitor directly influences the development and application of the super capacitor.
Graphene has an important application as a carbon material in supercapacitor electrode materials due to its large specific surface area, high electrical conductivity and good cycling stability. But the application of graphene is limited due to the low specific capacitance and easy agglomeration. Therefore, solving the problem of graphene agglomeration and improving the specific capacitance are the keys for realizing the practicability of the graphene super capacitor. In order to solve the problems, the specific capacitance of graphene is improved by adopting graphene loaded metal oxide at present. However, many metal oxides such as cobaltosic oxide, tin oxide, nickel oxide and the like have the problem of volume expansion, so that the specific capacity of the composite material is seriously attenuated in the circulating process, and the performance of the composite material is not ideal. For example, the Zhangjuan is prepared into a cobaltosic oxide/graphene oxide composite material by taking cobalt chloride hexahydrate as a raw material through a hydrothermal method, and the specific capacitance can only reach 444F/g under the current density of 0.5A/g; the circulating sub-capacitance loss rate of the cobaltosic oxide/graphene compound prepared by a hydrothermal method under the current density of 2A/g reaches twenty percent. Therefore, the improvement of the specific capacitance and the stability of the material are very important for the electrode material of the supercapacitor.
Disclosure of Invention
Aiming at the defects that the metal oxide is easy to generate volume expansion loss specific capacitance and the like in the process of using the metal oxide/graphene composite material prepared in the prior art as an electrode material, the invention aims to provide SiO formed by loading silica-coated metal oxide particles in a graphene aerogel pore structure2@ MOx/GA combined material, this combined material have realized silica and graphite alkene aerogel to metal oxide's double-deck cladding, have improved the stability of material greatly, can effectively prevent metal oxide charge-discharge to cross as the condenser use in-processThe volume expansion occurs in the process, and the specific capacitance and the cycling stability of the capacitor are improved.
Another purpose of the invention is to provide a method for preparing SiO with simple operation, environmental protection and low cost2The method of the @ MOx/GA composite material is favorable for industrial production.
Another object of the present invention is to provide a SiO2The application of the @ MOx/GA double-load double-coating composite material as an electrode material of a supercapacitor enables an energy storage device prepared from the material to have good electrochemical performance.
In order to achieve the technical purpose, the invention provides a silica @ metal oxide/graphene aerogel dual-loading dual-coating composite material which is formed by dispersing silica-coated metal oxide nanoparticles in a pore structure of a loaded graphene aerogel.
The composite material disclosed by the invention coats a silicon dioxide layer on the surface of the metal oxide nano particle, and the silicon dioxide has excellent ionic conductivity, shaping property and high theoretical specific capacitance, is more favorable than other rigid coating materials, not only can effectively prevent the capacitance loss caused by the volume expansion of the metal oxide in the charging process, but also can effectively improve the specific capacitance of the composite material. The silicon dioxide coated metal oxide nanoparticles are dispersed and loaded in the graphene aerogel pore structure, the graphene aerogel has a large specific surface and a three-dimensional pore structure, the silicon dioxide coated metal oxide nanoparticles can be uniformly dispersed in the pore structure, so that secondary coating of the metal oxide particles is equivalently realized, the metal nanoparticles can be effectively prevented from agglomerating, and the stability of the composite material is further improved.
In a preferred embodiment, the metal oxide nanoparticles include at least one of cobalt oxide nanoparticles, nickel oxide nanoparticles, and manganese oxide nanoparticles. The cobalt oxide nanoparticles, nickel oxide nanoparticles, and manganese oxide nanoparticles are all metal oxides such as Co with relatively stable oxidation states3O4、NiO、Mn3O4And the like.
The invention also provides a preparation method of the silica @ metal oxide/graphene aerogel dual-load dual-coating composite material, which comprises the steps of dropwise adding a solution containing a metal source and a silicon source into a graphite oxide dispersion liquid, carrying out ultrasonic mixing, carrying out hydrothermal reaction, and carrying out freeze drying and calcination on a product obtained by the hydrothermal reaction to obtain the silica @ metal oxide/graphene aerogel dual-load dual-coating composite material.
According to the preparation method of the silica @ metal oxide/graphene aerogel dual-loading dual-coating composite material, the composite colloid is formed by hydrolysis of the silicon source and the metal source, the colloid can be well adsorbed on the surface and the interlayer of the graphene hydrogel, and the silica @ metal oxide is generated in situ in the pore structure of the graphene aerogel through drying and calcining, so that the stability of the composite material is greatly improved, and particularly, the silica @ metal oxide/graphene aerogel dual-loading dual-coating composite material has higher loading stability compared with the condition that the metal oxide particles and the graphene aerogel are directly compounded.
In a preferred embodiment, the metal source includes at least one of a cobalt salt, a manganese salt, and a nickel salt. The cobalt, manganese and nickel salts are all water soluble salts, e.g. CoCl2·6H2O，Ni(NO3)2·6H2O，MnSO4·H2O，Co(NO3)2·6H2O, and the like.
In a preferred scheme, the silicon source is tetraethoxysilane.
In a preferred scheme, the graphite oxide is prepared from natural graphite flakes by a modified Hummers method. The improved Hummers method adopted by the invention for preparing graphite oxide is a common method in the field, and the most classical improved Hummers method is exemplified as follows: adding 1g of natural graphite flakes and 6g of potassium permanganate into 90mL of concentrated sulfuric acid and 10mL of phosphoric acid mixed solution, magnetically stirring and heating at 50 ℃ for 12h, cooling to room temperature after reaction, slowly adding 200mL of ice water, stirring for several minutes, then adding a proper amount of 30% hydrogen peroxide to reduce the residual oxidant until the mixed solution is bright yellow and no bubbles are generated, sequentially carrying out centrifugal washing with 5% hydrochloric acid, ethanol and deionized water until the mixed solution is neutral, and drying the obtained solution in a vacuum drying oven at 60 ℃ for 12h to obtain graphite oxide.
In a preferred scheme, the mass ratio of the graphene oxide to the metal source is 1: 1-8: 1.
In the preferable scheme, the mass ratio of the graphene oxide to the silicon source is 1: 1-8: 1.
In a preferred scheme, the temperature of the hydrothermal reaction is 120-180 ℃, and the time is 10-18 h.
In a preferred scheme, the calcining temperature is 250-800 ℃, and the time is 2-4 h.
In the preferable scheme, the concentration of the graphene oxide in the aqueous solution in which the graphene oxide is dispersed is 1-5 mg/mL.
In a preferable scheme, the freeze drying time is 18-24 h.
The invention also provides an application of the silica @ metal oxide/graphene aerogel dual-load dual-coating composite material, and the application of the silica @ metal oxide/graphene aerogel dual-load dual-coating composite material as an electrode material of a super capacitor.
The invention provides a preparation method of a metal oxide @ silicon dioxide/graphene aerogel dual-load dual-coating composite material, which comprises the following steps of:
1) preparing graphite oxide by a modified Hummers method;
2) taking a certain amount of graphite oxide in the step 1) to be dissolved in water in a beaker A, and then carrying out ultrasonic dispersion to form a graphene oxide dispersion liquid; taking a certain amount of metal oxide from a beaker B, adding water for dissolving, then adding a certain amount of tetraethoxysilane, and carrying out ultrasonic treatment to uniformly mix the metal oxide and the tetraethoxysilane;
3) dropwise adding the mixed solution in the beaker B into the beaker A, uniformly mixing by ultrasonic waves, and then putting into a reaction kettle for hydrothermal reaction;
4) and washing, freeze-drying and calcining the hydrothermal reaction product to obtain the catalyst.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1) according to the technical scheme, the metal oxide nanoparticles are coated in situ by using silicon dioxide, and the silicon dioxide nanoparticles can be subjected to dispersed loading by using the graphene aerogel, so that secondary coating is performed, the stability of the composite material is greatly improved, the metal oxide can be effectively prevented from volume expansion in the chemical reaction process, and the specific capacitance of the composite material can be effectively improved;
2) the invention prepares SiO2The method of the @ MOx/GA composite material is simple to operate, low in energy consumption and cost, simple in process and environment-friendly, and is beneficial to industrial production.
3) According to the invention, metal oxidation is loaded on GA, so that Faraday capacitance can be brought to GA, and at the moment, the composite material not only generates electric double layer capacitance. The metal oxide has the defect of capacitance attenuation caused by volume expansion by introducing SiO2Coating layer of SiO2The coating layer has good coating and shaping characteristics, can inhibit the volume expansion of the metal oxide, and obviously improves the specific capacitance of the composite material. SiO prepared by the invention2Compared with the graphene aerogel alone, the @ MOx/GA double-loading double-coating composite material has better electrochemical performance, such as SiO2@Co3O4When the current density of the/GA composite material is 1A/g, the specific capacitance reaches 464F/g, which is improved by nearly 119% compared with that of pure graphene aerogel (200F/g); is relatively Co3O4The @ GA composite (360F/g) increased by nearly 29%. From this it can be seen that SiO2The electrochemical performance of the @ MOx/GA dual-load dual-coating composite material is more excellent than that of a pure graphene aerogel and a metal oxide/graphene aerogel composite material.
Drawings
FIG. 1 shows SiO prepared in example 12@Co3O4And (3) a/GA composite material cyclic voltammogram. The cyclic voltammetry is rectangular and stable in performance.
FIG. 2 is a charge/discharge diagram of each of the composite materials prepared in examples 1 to 5. As can be seen from the graph, SiO is present at a current density of 1A/g2@Co3O4The specific capacitance of the/GA composite material reaches 463F/g, Co3O4The specific capacitance of the/GA composite material reaches 360F/g, and the specific capacitance of the GA composite material reaches 200F/g.
FIG. 3 is a FT-IR chart of each material prepared in examples 1 to 3. It can also be seen from the figure that the carbon skeleton C ═ C still exists in the composite material after the oxide loading, and the C-OH/C-O stretching vibration peak is obviously weakened, indicating that the oxide is successfully loaded, the oxygen-containing functional group in the composite material is reduced, and the conductivity of the material is improved.
FIG. 4 is an SEM photograph of GA prepared in example 2.
FIG. 5 shows SiO prepared in example 12@Co3O4SEM image of/GA. It can be seen from the figure that SiO is successfully loaded on GA2@Co3O4Spherical particles and due to SiO2The graphene surface is coated with a film in the presence of a silicon film.
FIG. 6 is an XRD pattern of each material prepared in examples 1 to 3. It can be seen from the figure that the load Co3O4The width of the rear peak is obviously reduced, SiO2@Co3O4the/GA composite material is formed by amorphous SiO2Added with Co having a wider peak width3O4the/GA broadens.
Detailed Description
The present invention is described in further detail below with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Example 1
Preparing graphite oxide: adding 1g of natural graphite flakes and 6g of potassium permanganate into 90mL of concentrated sulfuric acid and 10mL of phosphoric acid mixed solution, magnetically stirring and heating at 50 ℃ for 12h, cooling to room temperature after reaction, slowly adding 200mL of ice water, stirring for several minutes, then adding a proper amount of 30% hydrogen peroxide to reduce the residual oxidant until the mixed solution is bright yellow and no bubbles are generated, sequentially carrying out centrifugal washing with 5% hydrochloric acid, ethanol and deionized water until the mixed solution is neutral, and drying the obtained solution in a vacuum drying oven at 60 ℃ for 12h to obtain graphite oxide.
And (3) putting 0.32g of graphite oxide in a beaker A, adding 130m of water for dissolving, and performing ultrasonic dispersion for 4 hours to form a graphene oxide aqueous solution. 0.08g of cobalt chloride hexahydrate is taken to be put in a beaker B, 30mL of water is added for dissolving, then 0.08g of tetraethoxysilane is added, and the two are mixed evenly by ultrasonic; and dropwise adding the mixed solution in the beaker B into the beaker A, uniformly mixing by ultrasonic waves, and then putting the mixture into a 200mL polytetrafluoroethylene reaction kettle for hydrothermal reaction at 120 ℃ for 12 hours.
Centrifugally washing the product with ethanol and deionized water, freeze-drying, and placing in a tubular furnace at 350 deg.CCalcining for 3 hours at a temperature to obtain SiO2@Co3O4a/GA composite material.
The SiO obtained2@Co3O4An SEM image of the/GA double-supported double-coated composite material is shown in figure 1, and it can be seen that cobaltosic oxide and silica are both supported on graphene aerogel, and the graphene aerogel and the silica are used for double-coating the cobaltosic oxide, so that the whole composite material has a good pore structure with rich three-dimensional structural domains.
The method for testing the electrochemical performance of the metal oxide/silicon dioxide/graphene aerogel dual-load dual-coating composite material comprises the following steps: mixing a composite material, acetylene black and polyvinylidene fluoride (PVDF) according to a mass ratio of 8: 1:1, adding a proper amount of N-methyl-2-pyrrolidone (NMP), ultrasonically dispersing for 30min, stirring into paste, and coating on a surface of 1cm2Round foam nickel matrix. And (3) drying the pole piece in vacuum at 110 ℃ for 12h, then pressurizing to 15MPa by using an oil press, and keeping for 1min to obtain the pole piece used for testing. A three-electrode system is adopted to perform cyclic voltammetry and constant-current charge-discharge electrochemical tests on a CHI660E electrochemical workstation. Wherein Hg/HgO is used as a reference electrode, foamed nickel is used as an auxiliary electrode, and 6mol/L KOH solution is used as electrolyte.
The cyclic voltammetry of the composite material is shown in FIG. 2, and it can be seen from the graph that the graph is rectangular-like at the scanning speeds of 1, 2, 5, 10, and 20mV/s, which shows that the composite material has good capacitance performance and is suitable for being used as a supercapacitor material.
The constant current charge and discharge results of the composite material are shown in FIG. 3, and SiO can be seen from FIG. 32@Co3O4The specific capacitance of the/GA composite material is the largest, the specific capacitance is obviously improved, and the double load and double coating both have the effect of improving the specific capacitance of the graphene, so that the composite material is suitable for cathode materials of super capacitors and lithium batteries, and has good cycle stability.
Example 2
The graphite oxide was prepared in the same manner as in example 1. And (3) putting 0.32g of graphite oxide in a beaker A, adding 160m of water for dissolving, and performing ultrasonic dispersion for 4 hours to form a graphene oxide aqueous solution. Then pouring the solution into a 200mL polytetrafluoroethylene reaction kettle for hydrothermal reaction at 120 ℃ for 12 h. And (4) centrifugally washing the product with ethanol and deionized water, and freeze-drying to obtain the graphene aerogel.
The prepared graphene aerogel is subjected to constant current charge and discharge test at a current density of 1A/g, and the result is shown in FIG. 3, wherein the specific capacitance of the graphene aerogel is about 200F/g.
Example 3
The graphite oxide was prepared in the same manner as in example 1. And (3) putting 0.32g of graphite oxide in a beaker A, adding 130m of water for dissolving, and performing ultrasonic dispersion for 4 hours to form a graphene oxide aqueous solution. 0.08g of cobalt chloride hexahydrate is taken into a beaker B and dissolved by adding 30mL of water; and dropwise adding the mixed solution in the beaker B into the beaker A, uniformly mixing by ultrasonic waves, and then putting the mixture into a 200mL polytetrafluoroethylene reaction kettle for hydrothermal reaction at 120 ℃ for 12 hours.
Centrifugally washing the product with ethanol and deionized water, freeze-drying, calcining in a tubular furnace at 350 ℃ for 3 hours to obtain Co3O4a/GA composite material.
Prepared Co3O4The result of the constant current charge and discharge test of the/GA composite material at a current density of 1A/g is shown in FIG. 3, and the specific capacitance is about 360F/g.
Example 4
The graphite oxide was prepared in the same manner as in example 1. And (3) putting 0.32g of graphite oxide in a beaker A, adding 130m of water for dissolving, and performing ultrasonic dispersion for 4 hours to form a graphene oxide aqueous solution. 0.08g of cobalt chloride hexahydrate is taken to be put in a beaker B, 30mL of water is added for dissolving, then 0.08g of tetraethoxysilane is added, and the two are mixed evenly by ultrasonic; and dropwise adding the mixed solution in the beaker B into the beaker A, uniformly mixing by ultrasonic waves, and then putting the mixture into a 200mL polytetrafluoroethylene reaction kettle for hydrothermal reaction at 180 ℃ for 12 hours.
Centrifugally washing the product with ethanol and deionized water, freeze-drying, calcining in a tubular furnace at 350 ℃ for 3 hours to obtain SiO2@Co3O4a/GA composite material.
Prepared SiO2@Co3O4The result of the constant current charge/discharge test of the/GA composite material at a current density of 1A/g is shown in FIG. 3, and the specific capacitance thereof is about 395F/g.
Example 5
The graphite oxide was prepared in the same manner as in example 1. And (3) putting 0.32g of graphite oxide in a beaker A, adding 130m of water for dissolving, and performing ultrasonic dispersion for 4 hours to form a graphene oxide aqueous solution. 0.08g of cobalt chloride hexahydrate is taken to be put in a beaker B, 30mL of water is added for dissolving, then 0.08g of tetraethoxysilane is added, and the two are mixed evenly by ultrasonic; and dropwise adding the mixed solution in the beaker B into the beaker A, uniformly mixing by ultrasonic waves, and then putting the mixture into a 200mL polytetrafluoroethylene reaction kettle for hydrothermal reaction at 120 ℃ for 12 hours.
Centrifugally washing the product with ethanol and deionized water, freeze-drying, calcining in a tubular furnace at 300 ℃ for 4 hours to obtain SiO2@Co3O4a/GA composite material.
Prepared SiO2@Co3O4The result of the constant current charge/discharge test of the/GA composite material at a current density of 1A/g is shown in FIG. 3, and the specific capacitance thereof is about 425F/g.
Example 6
The graphite oxide was prepared in the same manner as in example 1. And (3) putting 0.32g of graphite oxide in a beaker A, adding 130m of water for dissolving, and performing ultrasonic dispersion for 4 hours to form a graphene oxide aqueous solution. 0.08g of cobalt chloride hexahydrate is taken to be put in a beaker B, 30mL of water is added for dissolving, then 0.16g of tetraethoxysilane is added, and the two are mixed evenly by ultrasonic; and dropwise adding the mixed solution in the beaker B into the beaker A, uniformly mixing by ultrasonic waves, and then putting the mixture into a 200mL polytetrafluoroethylene reaction kettle for hydrothermal reaction at 120 ℃ for 12 hours.
Centrifugally washing the product with ethanol and deionized water, freeze-drying, calcining in a tubular furnace at 300 ℃ for 4 hours to obtain SiO2@Co3O4a/GA composite material.
Prepared SiO2@Co3O4the/GA composite material is subjected to constant current charge and discharge test at the current density of 1A/g, and the specific capacitance of the composite material is about 405F/g.
Example 7
The graphite oxide was prepared in the same manner as in example 1. And (3) putting 0.32g of graphite oxide in a beaker A, adding 130m of water for dissolving, and performing ultrasonic dispersion for 4 hours to form a graphene oxide aqueous solution. Adding 0.08g of cobalt chloride hexahydrate into a beaker B, adding 30mL of water for dissolving, then adding 0.04g of tetraethoxysilane, and carrying out ultrasonic treatment to uniformly mix the two; and dropwise adding the mixed solution in the beaker B into the beaker A, uniformly mixing by ultrasonic waves, and then putting the mixture into a 200mL polytetrafluoroethylene reaction kettle for hydrothermal reaction at 120 ℃ for 12 hours.
Centrifugally washing the product with ethanol and deionized water, freeze-drying, calcining in a tubular furnace at 300 ℃ for 4 hours to obtain SiO2@Co3O4a/GA composite material.
Prepared SiO2@Co3O4the/GA composite material is subjected to constant current charge and discharge test at the current density of 1A/g, and the specific capacitance of the composite material is about 370F/g.
The invention is only exemplified by SiO2@Co3O4The system of the/GA series, but different metal oxides can be selected for carrying. It should be understood that the above description is illustrative of the preferred embodiment of the present invention and is not to be construed as limiting the scope of the invention, which is defined by the appended claims.
Claims (6)
1. The silica @ metal oxide/graphene aerogel dual-load dual-coating composite material is characterized in that: the composite material is formed by dispersing silicon dioxide coated metal oxide nano particles in a pore structure of loaded graphene aerogel; the metal oxide nanoparticles include at least one of cobalt oxide nanoparticles, nickel oxide nanoparticles, and manganese oxide nanoparticles.
2. The preparation method of the silica @ metal oxide/graphene aerogel dual-supported dual-coated composite material as claimed in claim 1, is characterized in that: dropwise adding a solution containing a metal source and a silicon source into the graphite oxide dispersion liquid, carrying out ultrasonic mixing, carrying out hydrothermal reaction, and carrying out freeze drying and calcination on a product obtained by the hydrothermal reaction to obtain the graphite oxide dispersion liquid; the mass ratio of the graphene oxide to the metal source is 1: 1-8: 1; the mass ratio of the graphene oxide to the silicon source is 1: 1-8: 1.
3. The preparation method of the silica @ metal oxide/graphene aerogel dual-supported dual-coated composite material as claimed in claim 2, wherein the preparation method comprises the following steps: the metal source comprises at least one of a cobalt salt, a manganese salt and a nickel salt; the silicon source is tetraethoxysilane; the graphite oxide is prepared from natural graphite flakes by a modified Hummers method.
4. The preparation method of the silica @ metal oxide/graphene aerogel dual-supported dual-coated composite material as claimed in claim 2 or 3, wherein the preparation method comprises the following steps: the temperature of the hydrothermal reaction is 120-180 ℃, and the time is 10-18 h.
5. The preparation method of the silica @ metal oxide/graphene aerogel dual-supported dual-coated composite material as claimed in claim 2 or 3, wherein the preparation method comprises the following steps: the calcining temperature is 250-800 ℃, and the time is 2-4 h.
6. The application of the silica @ metal oxide/graphene aerogel dual-supported dual-coated composite material as claimed in claim 1, is characterized in that: the material is applied as an electrode material of a super capacitor.
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