CN108597891A - Composite material and preparation method and application are covered in a kind of double load double-contractings of silica@metal oxides/graphene aerogel - Google Patents
Composite material and preparation method and application are covered in a kind of double load double-contractings of silica@metal oxides/graphene aerogel Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a kind of double load double-contractings of silica@metal oxides/graphene aerogel to cover composite material and preparation method and application, composite material in the pore structure of coated with silica metal oxide nanoparticles dispersion load graphene aerogel by constituting, its preparation process is that the solution for containing source metal and silicon source is added dropwise in graphite oxide dispersion, after ultrasonic mixing, carry out hydro-thermal reaction, hydro-thermal reaction products therefrom by freeze-drying and calcine to get.The composite material shows good chemical property as electrode material for super capacitor application, and preparation method is simple, inexpensive, environmental-friendly, meets industrial production standard.
Description
Technical field
The present invention relates to a kind of silica@metal oxides/graphene aerogel (SiO2@MOx/GA) tri compound material
Material, and in particular to structure in the pore structure of graphene aerogel is supported on by the dispersion of coated with silica metal oxide nanoparticles
At the double clad composite materials of double loads, and preparation method thereof and as electrode material for super capacitor application, belong to energy storage
Device preparing technical field.
Background technology
The economic fast development with science and technology also results in energy consumption while improving our qualities of the life and environment is dirty
Dye.Nowadays, people are increasingly able to recognize energy crisis and the seriousness of environmental pollution, therefore are dedicated to developing efficient and nothing
The new energy of pollution.In order to make full use of these new energy, the research and development of energy storage device should just be needed and be given birth to, super
Capacitor has obtained extensive attention and research as a kind of green energy storage device.And electrode material for super capacitor directly affects
To the development and application of ultracapacitor.
Graphene is because having becomes with big specific surface area, high electric conductivity and good cyclical stability super
There is the carbon material of important application in grade capacitor electrode material.But graphene specific capacitance it is relatively low and it is easy reunion limit it
Using.Therefore it solves the agglomeration traits of graphene and improves specific capacitance to be the key that graphene ultracapacitor realizes practical.
In order to solve problem above, graphene-supported metal oxide is mostly used at present to improve the specific capacitance of graphene.But it is very much
There is volume expansion in metal oxide such as cobaltosic oxide, tin oxide, nickel oxide etc., which results in cyclic process
In its special capacity fade it is serious, composite property is not ideal enough.Such as Zhang Yujuan is with cobalt chloride hexahydrate by hydro-thermal method
Raw material is prepared for cobaltosic oxide/graphene oxide composite material, and specific capacitance can be only capable of reaching under the current density of 0.5A/g
444F/g；He Guangyu is prepared for recycling time electricity under the current density of cobalt oxide/graphene compound 2A/g using hydro-thermal method
Capacitance loss rate has reached 20 percent.It can be seen that the stability for improving specific capacitance and material carrys out electrode material for super capacitor
It says most important.
Invention content
It is golden as existing during electrode material for the metal oxide/graphene composite material prepared in the prior art
Belong to the defects of volume expansion-loss specific capacitance easily occurs for oxide, the purpose of the invention is to provide one kind by silica packet
It covers metal oxide particle and is supported on the SiO constituted in graphene aerogel pore structure2@MOx/GA composite materials, the composite wood
Material realizes silica with graphene aerogel to the double-coating of metal oxide, substantially increases the stability of material,
It can effectively prevent that volume expansion occurs in metal oxide charge and discharge process during using as capacitor, improve capacitance
Device specific capacitance and cyclical stability.
Another object of the present invention is to be to provide one kind easy to operate, preparation SiO environmentally friendly, at low cost2@ MOx/GA
The method of composite material, this method are conducive to industrialized production.
Another object of the present invention is to be to provide a kind of SiO2The double clad composite materials of the bis- loads of@MOx/GA are as super
The application of grade capacitor electrode material shows good chemical property with the energy storage device of its preparation.
In order to achieve the above technical purposes, the present invention provides a kind of silica@metal oxides/graphene aerogels
Double double clad composite materials of load, disperse load graphene aerogel by coated with silica metal oxide nanoparticles
It is constituted in pore structure.
The composite material of the present invention coats layer of silicon dioxide layer, silica tool on metal oxide nanoparticles surface
There are excellent ionic conductivity, moulding characteristic and high theoretical specific capacitance, it is more advantageous than other rigid coating materials, can not only have
It imitates the volume expansion for preventing metal oxide in charging process and causes capacitance loss, and can effectively improve composite material
Specific capacitance.The dispersion of coated with silica metal oxide nanoparticles is supported in graphene aerogel pore structure, graphene
Aeroge specific surface is big, has three-D pore structure, can be dispersed in coated with silica metal oxide nanoparticles
In its pore structure, it is equivalent to the secondary cladding realized to metal oxide particle, metal nanoparticle group can be effectively prevent
It is poly-, further improve the stability of composite material.
Preferred scheme, metal oxide nanoparticles be include cobalt/cobalt oxide nano particle, nickel oxide nano particle,
At least one of manganese oxide nanoparticles.Cobalt/cobalt oxide nano particle, nickel oxide nano particle and Mn oxide nanometer
Grain is the metastable metal oxide of oxidation state such as Co3O4、NiO、Mn3O4Deng.
The present invention also provides a kind of double load double-contractings of silica@metal oxides/graphene aerogel to cover composite wood
The preparation method of material, this method is that the solution for containing source metal and silicon source is added dropwise in graphite oxide dispersion, after ultrasonic mixing,
Carry out hydro-thermal reaction, hydro-thermal reaction products therefrom by freeze-drying and calcine to get.
The preparation side of the double clad composite materials of the double loads of silica metal oxide/graphene aerogel of the present invention
Using the composite colloid that hydrolyzes to form of silicon source and source metal in method, colloid can be particularly well adsorbed in graphene hydrogel surface and
Interlayer, by drying and calcination, in-situ preparation silica metal oxide, carries significantly in graphene aerogel pore structure
The high stability of composite material, is combined especially by the metal oxide particle of coated with silica with graphene aerogel
Well, opposing metallic oxide particle has higher load stability with graphene aerogel direct combination.
Preferred scheme, the source metal include at least one of cobalt salt, manganese salt and nickel salt.Cobalt salt, manganese salt and nickel salt are equal
For water soluble salt, such as CoCl2·6H2O, Ni (NO3)2·6H2O, MnSO4·H2O, Co (NO3)2·6H2O etc..
Preferred scheme, the silicon source ethyl orthosilicate.
Preferred scheme, the graphite oxide are made by natural graphite scale by improved Hummers methods.The present invention adopts
It is the common method in this field that improved Hummers methods, which prepare graphite oxide method, and exemplified below a kind of most classical changes
Into Hummers methods：1g natural graphite scales, 6g potassium permanganate are added in 90mL concentrated sulfuric acid 10mL phosphoric acid mixed liquors, 50 DEG C
Lower magnetic agitation heats 12h, waits for that reaction is cooled to room temperature, and is slowly added to 200mL ice water and stirs several minutes, is then added appropriate
The remaining oxidant of 30% hydrogen-peroxide reduction is generated to mixed liquor in glassy yellow and bubble-free, successively with 5% hydrochloric acid, second
Alcohol, deionized water centrifuge washing to neutrality, acquired solution dry 12h in 60 DEG C of vacuum drying chambers, obtain graphite oxide.
The mass ratio of preferred scheme, graphene oxide and source metal is 1:1~8:1.
The mass ratio 1 of preferred scheme, graphene oxide and silicon source:1~8:1.
The temperature of preferred scheme, the hydro-thermal reaction is 120 DEG C~180 DEG C, and the time is 10~18h.
The temperature of preferred scheme, the calcining is 250 DEG C~800 DEG C, and the time is 2~4h.
Preferred scheme is dispersed with a concentration of 1~5mg/mL of graphene oxide in the aqueous solution of graphene oxide.
Preferred scheme, time of freeze-drying is 18~for 24 hours.
The present invention also provides a kind of double load double-contractings of silica@metal oxides/graphene aerogel to cover composite wood
The application of material, as the application of electrode material for super capacitor.
The present invention provides a kind of double clad composite materials of the double loads of metal oxide silica/graphene aerogel
Preparation method comprising following steps：
1) graphite oxide is prepared by improved Hummers methods；
2) take it is a certain amount of 1) in graphite oxide in A beakers, be dissolved in water, then ultrasonic disperse formed graphene oxide
Dispersion liquid；It takes a certain amount of metal oxide in B beakers, is dissolved in water, then adds a certain amount of ethyl orthosilicate, surpass
Sound makes the two be uniformly mixed；
3) mixed solution in B beakers is added dropwise in A beakers, is put into reaction kettle and carries out after ultrasonic mixing is uniform
Hydro-thermal reaction；
4) hydro-thermal reaction product after freeze-drying, is calcined by washing to obtain the final product.
Compared with prior art, the advantageous effect that technical scheme of the present invention is brought：
1) technical scheme of the present invention carries out in-stiu coating using silica to metal oxide nanoparticles, recycles
Graphene aerogel can carry out dispersion load to silica nanometer, be equivalent to and carry out secondary cladding, substantially increase compound
The stability of material, it is improper that metal oxide can be effectively prevent to occur volume expansion in chemical reaction process, and can be with
Effectively improve the specific capacitance of composite material；
2) present invention prepares SiO2The method of@MOx/GA composite materials is easy to operate, energy consumption with it is at low cost, simple for process,
It is environmental-friendly, be conducive to industrialized production.
3) present invention is aoxidized by metal on load GA, can be that GA bring faraday's capacitance, composite material is not only at this time
Only generate electric double layer capacitance.And metal oxide the shortcomings that leading to capacitance fade there are volume expansion, pass through and introduces SiO2Cladding
Layer, SiO2Clad has good cladding and moulding characteristic, metal oxide volume can be inhibited to expand, the ratio of composite material
Capacitance is obviously improved.SiO prepared by the present invention2The double clad composite materials of the bis- loads of@MOx/GA and individual graphene aerogel
It compares, shows better chemical property, such as SiO2@Co3O4/ GA composite materials are when current density is 1A/g, specific capacitance
Reach 464F/g, purer graphene aerogel (200F/g) improves nearly 119%；Compared with Co3O4@GA composite materials (360F/g) improve
Nearly 29%.It can be seen that SiO2The double clad composite materials of the bis- loads of@MOx/GA are aoxidized than pure graphene aerogel and metal
Object/graphene aerogel composite material chemical property is more excellent.
Description of the drawings
【Fig. 1】The SiO prepared for embodiment 12@Co3O4/ GA composite material cyclic voltammograms.As can be seen from the figure it recycles
Rectangle is presented in volt-ampere, and performance is stablized.
【Fig. 2】Electrograph is compared for each composite material charge and discharge prepared by Examples 1 to 5.It can be seen from the figure that close in electric current
When degree is 1A/g, SiO2@Co3O4/ GA composite material specific capacitances reach 463F/g, Co3O4/ GA composite material specific capacitances reach
360F/g, GA specific capacitance reach 200F/g.
【Fig. 3】Each material FT-IR curve graphs prepared for Examples 1 to 3.It is from figure it can also be seen that negative carrying out oxide
Carbon skeleton C=C still has in composite material after load, and C-OH/C-O stretching vibration peaks obviously weaken, and shows oxide success
It loads, oxygen-containing functional group has been reduced in composite material, and material conductivity improves.
【Fig. 4】The SEM figures of GA are prepared for embodiment 2.
【Fig. 5】The SiO prepared for embodiment 12@Co3O4The SEM of/GA schemes.As can be seen from the figure it is successfully loaded on GA
SiO2@Co3O4Spherical particle, and due to SiO2Silicon fiml there are graphene surface films.
【Fig. 6】For the XRD diagram of each material prepared by Examples 1 to 3.As can be seen from the figure load C o3O4Peak width is apparent afterwards
Reduce, SiO2@Co3O4/ GA composite materials are due to unformed SiO2Addition peak width compared with Co3O4/ GA broadens.
Specific implementation mode
The present invention is described in further detail with reference to example and attached drawing, but embodiments of the present invention are not limited to
This.
Embodiment 1
The preparation of graphite oxide：1g natural graphite scales, 6g potassium permanganate are added 90mL concentrated sulfuric acid 10mL phosphoric acid and mixed
In liquid, at 50 DEG C magnetic agitation heat 12h, wait for reaction being cooled to room temperature, be slowly added to 200mL ice water and stir several minutes, so
After the appropriate remaining oxidant of 30% hydrogen-peroxide reduction be added generated to mixed liquor in glassy yellow and bubble-free, successively with 5%
Hydrochloric acid, ethyl alcohol, deionized water centrifuge washing to neutrality, acquired solution dries 12h in 60 DEG C of vacuum drying chambers, obtains oxidation stone
Ink.
It takes 0.32g graphite oxides in A beakers, 130m water dissolutions, ultrasonic 4h is added to disperse to form graphene oxide water solution.It takes
0.08g cobalt chloride hexahydrates add 30mL water dissolutions in B beakers, then add 0.08g ethyl orthosilicates, and ultrasound makes the two
It is uniformly mixed；Mixed solution in B beakers is added dropwise in A beakers, 200mL polytetrafluoroethyl-nes are put into after ultrasonic mixing is uniform
120 DEG C of hydro-thermal reaction 12h in alkene reaction kettle.
By product ethyl alcohol and deionized water centrifuge washing, it is small that 350 DEG C of calcining at constant temperature 3 in tube furnace are put into after freeze-drying
When calcine up to SiO2@Co3O4/ GA composite materials.
SiO obtained2@Co3O4The SEM of the double clad composite materials of the bis- loads of/GA schemes as shown in Figure 1, it can be seen that four
Co 3 O and silica have all been supported on graphene aerogel, and graphene aerogel is with silica to cobaltosic oxide
Double-coating, entire composite material has the abundant pore structure in good three-dimensional structure domain.
The test of the double clad composite material chemical properties of the double loads of metal oxide/silica/graphene aerogel
Method：By composite material, acetylene black, Kynoar (PVDF) in mass ratio 8：1：1 ratio is uniformly mixed, and appropriate N- is added
N-methyl-2-2-pyrrolidone N (NMP), ultrasonic disperse 30min are applied to area as 1cm after stirring into paste2Circular shaped foam Ni substrate
On.It is dried in vacuo pole piece 12h at 110 DEG C, is then forced into 15MPa with hydraulic press, keeps 1min to get pole used in test
Piece.Cyclic voltammetric, constant current charge-discharge electro-chemical test are carried out on CHI660E electrochemical workstations using three-electrode system.Its
In, using Hg/HgO as reference electrode, nickel foam is auxiliary electrode, using 6mol/L KOH solutions as electrolyte.
The cyclic voltammetric of composite material as shown in Fig. 2, as seen from the figure sweep speed be 1,2,5,10, under 20mV/s, figure
Shape is in similar rectangular-shaped, illustrates capacitive property well suitable for as super capacitor material.
The results are shown in Figure 3 for the constant current charge-discharge of composite material, by can be seen that SiO in Fig. 32@Co3O4/ GA composite woods
The specific capacitance of material is maximum, and specific capacitance is obviously improved, it is seen that and double loads cover the specific capacitance to graphene with double-contracting and are improved effect,
Suitable for ultracapacitor and lithium cell cathode material, cyclical stability is preferable.
Embodiment 2
The preparation method is the same as that of Example 1 for graphite oxide.It takes 0.32g graphite oxides in A beakers, adds 160m water dissolutions, ultrasound
4h disperses to form graphene oxide water solution.Then solution is poured into 120 DEG C of hydro-thermal reactions in 200mL ptfe autoclaves
12h.By product ethyl alcohol and deionized water centrifuge washing, up to graphene aerogel after freeze-drying.
The graphene aerogel of preparation carries out constant current charge-discharge test, result such as Fig. 3 in the case where current density is 1A/g
Shown, specific capacitance is about 200F/g.
Embodiment 3
The preparation method is the same as that of Example 1 for graphite oxide.It takes 0.32g graphite oxides in A beakers, adds 130m water dissolutions, ultrasound
4h disperses to form graphene oxide water solution.It takes 0.08g cobalt chloride hexahydrates in B beakers, adds 30mL water dissolutions；By B beakers
In mixed solution be added dropwise in A beakers, 120 DEG C are put into 200mL ptfe autoclaves after ultrasonic mixing is uniform
Hydro-thermal reaction 12h.
By product ethyl alcohol and deionized water centrifuge washing, it is small that 350 DEG C of calcining at constant temperature 3 in tube furnace are put into after freeze-drying
When calcine up to Co3O4/ GA composite materials.
The Co of preparation3O4/ GA composite materials carry out constant current charge-discharge test in the case where current density is 1A/g, and result is such as
Shown in Fig. 3, specific capacitance is about 360F/g.
Embodiment 4
The preparation method is the same as that of Example 1 for graphite oxide.It takes 0.32g graphite oxides in A beakers, adds 130m water dissolutions, ultrasound
4h disperses to form graphene oxide water solution.It takes 0.08g cobalt chloride hexahydrates in B beakers, adds 30mL water dissolutions, then add again
Enter 0.08g ethyl orthosilicates, ultrasound makes the two be uniformly mixed；Mixed solution in B beakers is added dropwise in A beakers, is surpassed
Sound is put into 180 DEG C of hydro-thermal reaction 12h in 200mL ptfe autoclaves after mixing.
By product ethyl alcohol and deionized water centrifuge washing, it is small that 350 DEG C of calcining at constant temperature 3 in tube furnace are put into after freeze-drying
When calcine up to SiO2@Co3O4/ GA composite materials.
The SiO of preparation2@Co3O4/ GA composite materials carry out constant current charge-discharge test, knot in the case where current density is 1A/g
Fruit is as shown in figure 3, its specific capacitance is about 395F/g.
Embodiment 5
The preparation method is the same as that of Example 1 for graphite oxide.It takes 0.32g graphite oxides in A beakers, adds 130m water dissolutions, ultrasound
4h disperses to form graphene oxide water solution.It takes 0.08g cobalt chloride hexahydrates in B beakers, adds 30mL water dissolutions, then add again
Enter 0.08g ethyl orthosilicates, ultrasound makes the two be uniformly mixed；Mixed solution in B beakers is added dropwise in A beakers, is surpassed
Sound is put into 120 DEG C of hydro-thermal reaction 12h in 200mL ptfe autoclaves after mixing.
By product ethyl alcohol and deionized water centrifuge washing, it is small that 300 DEG C of calcining at constant temperature 4 in tube furnace are put into after freeze-drying
When calcine up to SiO2@Co3O4/ GA composite materials.
The SiO of preparation2@Co3O4/ GA composite materials carry out constant current charge-discharge test, knot in the case where current density is 1A/g
Fruit is as shown in figure 3, its specific capacitance is about 425F/g.
Embodiment 6
The preparation method is the same as that of Example 1 for graphite oxide.It takes 0.32g graphite oxides in A beakers, adds 130m water dissolutions, ultrasound
4h disperses to form graphene oxide water solution.It takes 0.08g cobalt chloride hexahydrates in B beakers, adds 30mL water dissolutions, then add again
Enter 0.16g ethyl orthosilicates, ultrasound makes the two be uniformly mixed；Mixed solution in B beakers is added dropwise in A beakers, is surpassed
Sound is put into 120 DEG C of hydro-thermal reaction 12h in 200mL ptfe autoclaves after mixing.
By product ethyl alcohol and deionized water centrifuge washing, it is small that 300 DEG C of calcining at constant temperature 4 in tube furnace are put into after freeze-drying
When calcine up to SiO2@Co3O4/ GA composite materials.
The SiO of preparation2@Co3O4/ GA composite materials carry out constant current charge-discharge test in the case where current density is 1A/g, ratio
Capacitance is about 405F/g.
Embodiment 7
The preparation method is the same as that of Example 1 for graphite oxide.It takes 0.32g graphite oxides in A beakers, adds 130m water dissolutions, ultrasound
4h disperses to form graphene oxide water solution.It takes 0.08g cobalt chloride hexahydrates in B beakers, adds 30mL water dissolutions, then add again
Enter 0.04g ethyl orthosilicates, ultrasound makes the two be uniformly mixed；Mixed solution in B beakers is added dropwise in A beakers, is surpassed
Sound is put into 120 DEG C of hydro-thermal reaction 12h in 200mL ptfe autoclaves after mixing.
By product ethyl alcohol and deionized water centrifuge washing, it is small that 300 DEG C of calcining at constant temperature 4 in tube furnace are put into after freeze-drying
When calcine up to SiO2@Co3O4/ GA composite materials.
The SiO of preparation2@Co3O4/ GA composite materials carry out constant current charge-discharge test in the case where current density is 1A/g, ratio
Capacitance is about 370F/g.
The present invention only enumerates SiO2@Co3O4/ GA series systems, but different metal oxides can also be chosen and born
It carries.It should be understood that the above-mentioned statement for present pre-ferred embodiments is more detailed, can not therefore be considered to this
The limitation of invention patent protection range, scope of patent protection of the invention should be determined by the appended claims.
Claims (8)
1. a kind of double clad composite materials of the double loads of silica metal oxide/graphene aerogel, it is characterised in that：By
It is constituted in the pore structure of coated with silica metal oxide nanoparticles dispersion load graphene aerogel.
2. a kind of double covered composite yarns of the double loads of silica metal oxide/graphene aerogel according to claim 1
Material, it is characterised in that：Metal oxide nanoparticles include cobalt/cobalt oxide nano particle, nickel oxide nano particle, manganese oxygen
At least one of compound nano particle.
3. a kind of double covered composite yarns of the double loads of silica metal oxide/graphene aerogel as claimed in claim 1 or 2
The preparation method of material, it is characterised in that：Solution containing source metal and silicon source is added dropwise in graphite oxide dispersion, ultrasound is mixed
After conjunction, carry out hydro-thermal reaction, hydro-thermal reaction products therefrom by freeze-drying and calcine to get.
4. a kind of double covered composite yarns of the double loads of silica metal oxide/graphene aerogel according to claim 3
The preparation method of material, it is characterised in that：The source metal includes at least one of cobalt salt, manganese salt and nickel salt；The silicon source is
Ethyl orthosilicate；The graphite oxide is made by natural graphite scale by improved Hummers methods.
5. a kind of double covered composite yarns of the double loads of silica metal oxide/graphene aerogel according to claim 4
The preparation method of material, it is characterised in that：Graphene oxide and the mass ratio of source metal are 1:1~8:1；Graphene oxide and silicon
The mass ratio in source be 1:1~8:1.
6. according to a kind of double loads of silica@metal oxides/graphene aerogel of claim 3~5 any one of them
The preparation method of double clad composite materials, it is characterised in that：The temperature of the hydro-thermal reaction is 120 DEG C~180 DEG C, the time 10
~18h.
7. according to a kind of double loads of silica@metal oxides/graphene aerogel of claim 3~5 any one of them
The preparation method of double clad composite materials, it is characterised in that：The temperature of the calcining is 250 DEG C~800 DEG C, and the time is 2~4h.
8. a kind of double covered composite yarns of the double loads of silica metal oxide/graphene aerogel as claimed in claim 1 or 2
The application of material, it is characterised in that：Application as electrode material for super capacitor.
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| CN109560269A (en) * | 2018-11-15 | 2019-04-02 | 齐鲁工业大学 | A kind of hollow tin dioxide titanium dioxide/graphene aerogel composite and preparation method thereof |
| CN109817929A (en) * | 2019-01-25 | 2019-05-28 | 安徽师范大学 | A kind of helical form silica/cobaltosic oxide composite nano materials and preparation method thereof and the application in lithium ion battery |
| CN109817928A (en) * | 2019-01-25 | 2019-05-28 | 安徽师范大学 | A kind of helical form silica/iron oxide composite nano materials and preparation method thereof and the application in lithium ion battery |
| CN112794705A (en) * | 2021-01-13 | 2021-05-14 | 兰州大学 | Method for preparing hyperelastic silicon oxide nano ceramic aerogel based on graphene serving as template |
| CN115041230A (en) * | 2022-07-13 | 2022-09-13 | 苏州大学 | Metal-loaded nickel-manganese spinel nanosphere aerogel and preparation method and application thereof |
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| CN109560269A (en) * | 2018-11-15 | 2019-04-02 | 齐鲁工业大学 | A kind of hollow tin dioxide titanium dioxide/graphene aerogel composite and preparation method thereof |
| CN109560269B (en) * | 2018-11-15 | 2023-09-12 | 齐鲁工业大学 | Hollow tin dioxide@titanium dioxide/graphene aerogel composite material and preparation method thereof |
| CN109817929A (en) * | 2019-01-25 | 2019-05-28 | 安徽师范大学 | A kind of helical form silica/cobaltosic oxide composite nano materials and preparation method thereof and the application in lithium ion battery |
| CN109817928A (en) * | 2019-01-25 | 2019-05-28 | 安徽师范大学 | A kind of helical form silica/iron oxide composite nano materials and preparation method thereof and the application in lithium ion battery |
| CN109817929B (en) * | 2019-01-25 | 2020-11-03 | 安徽师范大学 | Spiral silicon dioxide/cobaltosic oxide composite nano material, preparation method thereof and application thereof in lithium ion battery |
| CN109817928B (en) * | 2019-01-25 | 2020-11-03 | 安徽师范大学 | Spiral silicon dioxide/iron oxide composite nano material, preparation method thereof and application thereof in lithium ion battery |
| CN112794705A (en) * | 2021-01-13 | 2021-05-14 | 兰州大学 | Method for preparing hyperelastic silicon oxide nano ceramic aerogel based on graphene serving as template |
| CN115041230A (en) * | 2022-07-13 | 2022-09-13 | 苏州大学 | Metal-loaded nickel-manganese spinel nanosphere aerogel and preparation method and application thereof |
| CN115041230B (en) * | 2022-07-13 | 2024-02-06 | 苏州大学 | Metal-supported nickel-manganese spinel nanosphere aerogel and preparation method and application thereof |
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