CN108428562A - A kind of composite material and its two-step synthesis method of ternary cobalt nickel molybdenum oxide growth in situ on graphene - Google Patents
A kind of composite material and its two-step synthesis method of ternary cobalt nickel molybdenum oxide growth in situ on graphene Download PDFInfo
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- CN108428562A CN108428562A CN201810343599.7A CN201810343599A CN108428562A CN 108428562 A CN108428562 A CN 108428562A CN 201810343599 A CN201810343599 A CN 201810343599A CN 108428562 A CN108428562 A CN 108428562A
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- molybdenum oxide
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 27
- WBSVIJYYSBSHSI-UHFFFAOYSA-N cobalt nickel oxomolybdenum Chemical compound [Mo]=O.[Ni].[Co] WBSVIJYYSBSHSI-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000001308 synthesis method Methods 0.000 title claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 50
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 20
- 239000010941 cobalt Substances 0.000 claims abstract description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002073 nanorod Substances 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- NLPVCCRZRNXTLT-UHFFFAOYSA-N dioxido(dioxo)molybdenum;nickel(2+) Chemical compound [Ni+2].[O-][Mo]([O-])(=O)=O NLPVCCRZRNXTLT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 235000019441 ethanol Nutrition 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 14
- 238000002604 ultrasonography Methods 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- 239000013049 sediment Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229910004619 Na2MoO4 Inorganic materials 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- 239000011684 sodium molybdate Substances 0.000 claims description 4
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000002023 wood Substances 0.000 claims 1
- 229910000428 cobalt oxide Inorganic materials 0.000 abstract description 13
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 abstract description 13
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 4
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 3
- 150000004706 metal oxides Chemical class 0.000 abstract description 3
- 239000011149 active material Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 11
- 238000005303 weighing Methods 0.000 description 10
- 229910015667 MoO4 Inorganic materials 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- CIHYROJTBKFOPR-UHFFFAOYSA-N nickel;oxomolybdenum Chemical class [Ni].[Mo]=O CIHYROJTBKFOPR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 206010040007 Sense of oppression Diseases 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention provides a kind of composite materials and its two-step synthesis method of ternary cobalt nickel molybdenum oxide growth in situ on graphene, it is related to graphene and metal oxide composite field, the composite material is using graphene as substrate, and growth in situ is combined with the oxidation cobalt nanorod of club shaped structure on the graphene-based bottom；Growth in situ is combined with the nickel molybdenum oxide nanometer rods of club shaped structure on the oxidation cobalt nanorod.Composite material provided by the invention, very thin graphene increase the specific surface area of material, increase the utilization rate of active material；Graphene links together cobalt oxide material so that material is integrally connected, and avoids the material failure situation caused by conductive capability is weak；Well-bedded structure avoids the agglomeration of material, forms three-dimensional loose porous pattern, further increases the specific surface area of material so that material capacitance is improved.
Description
Technical field
The present invention relates to graphenes and metal oxide composite field, and in particular to a kind of ternary cobalt nickel molybdenum oxide
The composite material and its two-step synthesis method of growth in situ on graphene.
Background technology
With the fast development of global economy, the continuous consumption of fossil energy and the worsening of environment, people are urgent
It needs to find the effective ways for coping with energy and environment double oppression problem, the green regenerating of the energy how is carried out, at scientific research
The matter of utmost importance of worker's research.The reserves critical shortage of various fossil energies on earth, it was predicted that oil is on the year two thousand fifty left side
The right side will be depleted, and coal is still used 100 years again, and natural gas will not exist after 30 years yet, likewise,
The problem of environmental pollution brought using fossil energy also forces people actively to find new fungible energy source, excites people couple
In the research of efficient, clean energy conversion and memory device.
Ultracapacitor is as the novel energy storage system to grow up the seventies and eighties in last century, by decades
It continues to develop, nowadays suffers from excellent application in the every field such as military, civilian.Compared with lithium battery, power density height,
Charging time is short, service life is long, good temp characteristic, and green pollution-free.With the rapid development of nowadays nanotechnology,
The good characteristic of the nano materials such as ultracapacitor combination graphene, also in continuous perfect the properties of itself.It is super
Capacitor is divided into double electric layers supercapacitor and fake capacitance ultracapacitor, and double electric layers supercapacitor mainly utilizes carbon material
The specific surface area of superelevation, in charge and discharge process, for the ion in electrolyte provide can attachment site, to form conductive return
Road, specific surface area is bigger, and ion adheres to more, and the charge of storage is more, and capacity is bigger, and classical electric double layer is super
Capacitor is with activated carbon as positive and negative pole material, and cycle life is up to million ranks.Fake capacitance ultracapacitor is main
The storage of charge is carried out using the redox reaction of transition metal oxide, it is common to have the metals such as Fe, Co, Ni, Zn, Mn first
The ultracapacitor theoretical capacity of element, this type is higher than double electric layers supercapacitor, but cycle life need scientific research personnel
Continue study.Above description is it is found that double electric layers supercapacitor service life is long, but its capacity depends on specific surface area；It is counterfeit
Capacitance capacity of super capacitor is big, but a big difficulty that its service life is still studied, and hinders ultracapacitor to meet the longevity simultaneously at present
One key factor of life and capacity requirement is exactly that electrode material performance does not reach requirement also.
Nowadays, ternary material just plays increasingly important role in ultracapacitor, such as Chinese patent (CN
Nickel-cobalt electrode material for super capacitor 102656650A) has directly been mixed with the oxide of nickel and cobalt, this patent describes
A kind of improved capacitor is prepared using the mixed-metal oxides of transition metal nickel and cobalt in conjunction with binder and carbon nanotube
A kind of excellent ultracapacitor, specific surface area is high, and still possesses under higher voltage scan rate higher than electricity
Capacitance.But still remain problems with：
1, between cobalt oxide and cobalt oxide have reuniting effect, be unfavorable in electrochemical reaction process in electrolyte from
Son enters material internal, and then is unfavorable for carrying out charge-exchange, reduces the specific surface area of material so that material capacitance is difficult to
It improves；
2, some materials are isolated because of conductivity problems, cause some materials not to be utilized and the nothing that generates
Imitate quality；
3, the mutual doping between cobalt and nickel molybdenum so that amorphous state ratio increases in the material morphology of preparation, influences
The sizing of material, and with the progress of the electrochemical reaction of material, inevitably make material volume expansion or dusting, from
And it is serious that the performance using the ultracapacitor later stage of the material preparation can be caused to decline, and influences ultracapacitor service life.
Invention content
The present invention provides a kind of ternary cobalt nickel the molybdenum oxide composite material of growth in situ and its conjunction of two steps on graphene
Cheng Fa, to solve the technical issues of existing electrode material performance is also not achieved while meeting service life and capacity requirement.
The purpose of the present invention can be realized by technical solution below：
A kind of composite material of ternary cobalt nickel molybdenum oxide growth in situ on graphene, the composite material is with graphene
For substrate, growth in situ is combined with the oxidation cobalt nanorod of club shaped structure on the graphene-based bottom；The oxidation cobalt nanorod
Upper growth in situ is combined with the nickel molybdenum oxide nanometer rods of club shaped structure.
Preferably, the thickness at the graphene-based bottom is 0.1-5nm.
Preferably, the length of the oxidation cobalt nanorod is 0.1-5 μm.
Preferably, the length of the nickel molybdenum oxide nanometer rods is 10-500nm.
A kind of two-step synthesis method of ternary cobalt nickel molybdenum oxide composite material of growth in situ on graphene, including it is as follows
Step：
1) weigh graphene, add water be sufficiently stirred with ultrasound, obtain graphene solution；
2) Co (NO are weighed3)2, urea and NH4F powder is added in the good graphene solution of ultrasound, stirs 5 minutes；
3) it weighs polyvinylpyrrolidonepowder powder to be added in the mixed liquor obtained in step 2), stir 5 minutes；
4) mixed liquor that step 3) obtains is placed at 100-200 DEG C and is reacted, the time is 6-24 hours；
5) reaction solution that after reaction, step 4) is obtained filters, and taking precipitate carries out sediment with water and ethyl alcohol
Centrifuge washing；
6) deionized water is added to be stirred the sediment washed；
7) Ni (NO are weighed3)2, Na2MoO4Solid is added in the solution that step 6) obtains, stirring；
8) ethyl alcohol is measured, is added drop-wise in the mixed liquor that step 7) obtains, is stirred；
9) mixed solution that step 8) obtains is transferred in ptfe autoclave and is reacted at 100-200 DEG C, when
Between 1-10 hours；
10) reaction solution that after reaction, step 9) is obtained filters, taking precipitate, with water and ethyl alcohol to sediment into
Row centrifuge washing；
11) the clean sediment for obtaining step 10) is 12 hours dry in the baking oven that temperature is 30-100 DEG C, and gained is
For final product.
Preferably, in step 1) graphene a concentration of 0.5-2g/L.
Preferably, in step 3) polyvinylpyrrolidone a concentration of 0.1-5g/L.
Preferably, the Ni (NO in step 7)3)2With Na2MoO4Molar ratio be 1：1.
Preferably, the volume of the mixed liquor described in step 8) is 1-5 times of ethyl alcohol, and the two total volume is not more than
The maximum capacity of reaction kettle.
In conclusion by adopting the above-described technical solution, the beneficial effects of the invention are as follows：
1, composite material provided by the invention, very thin graphene increase the specific surface area of material, increase active material
The utilization rate of material；Graphene links together cobalt oxide material so that material is integrally connected, and avoids and draws because conductive capability is weak
The material failure situation risen；Growth in situ of the rodlike cobalt oxide on graphene platelet, growth in situ again on rodlike cobalt oxide
Go out rodlike nickel molybdenum oxide, well-bedded structure avoids the agglomeration of material, forms three-dimensional loose porous shape
Looks are conducive to the ion in electrolyte and enter material internal in electrochemical reaction process, carry out charge-exchange, further increase
The big specific surface area of material so that material capacitance is improved.
2, the growth in situ using rodlike cobalt oxide on graphene platelet is to being closely combined together, and
It uniformly lines up on graphene platelet, has not only separated the reuniting effect between cobalt oxide and cobalt oxide, but also electric conductivity
Almost all of cobalt material is also connected in parallel by the good graphene of energy, forms a perfect conductive network, reduces portion
Point material is isolated because of conductivity problems, so avoid some materials is caused not to be utilized and the invalid matter that generates
Amount；
3, the present invention is with hydro-thermal method growth in situ cobalt oxide on the surface of graphene, and under high temperature, cobalt precursor is cracked into cobalt
Ion, a large amount of and uniform nucleation on the surface of graphene are grown, and this growth in situ is more conducive to uniform point of cobalt material
Cloth, it is therefore prevented that the reunion growth between material and material increases the effective ratio area of cobalt material, and reacted for second step
Provide numerous growth sites；Two-step method is different from the direct synthesis of metal oxide material of one-step method, although without one-step method
It is simple, conveniently, but two-step method provides guarantee for the clearly demarcated level of material, and two-step method prevents between cobalt and nickel molybdenum
Mutual doping, avoid the generation of material morphology amorphous state, improve the stability of material, also improve making for material
Use the service life；
4, in first step reaction, the unique structure of polyvinylpyrrolidone firmly combines graphene and cobalt oxide one
It rises；In second step reaction, oxidation cobalt nanorod also links together three kinds of nickel molybdenum oxides with graphene, increases whole material
The conductive capability of material, and in second step reaction, form mixed solvent with traditional deionized water by adding ethyl alcohol, change anti-
It answers the pressure and atmosphere in kettle, the two to complement each other, promotes the formation of the with different levels stereochemical structure of the three-dimensional；Two-step method
Implementation, avoid the unfavorable situation that traditional one-step method is substituted for each other various metallic elements, made a kind of level point
Bright superior structural；
5, for angle is implemented in experiment, the scheme that this patent uses is simple to operation, and can carry out factory on a large scale
Production.
Description of the drawings
Fig. 1 is the electron scanning micrograph of 1 gained final product of embodiment；
Fig. 2 is the cycle performance curve graph of 1 gained composite material of embodiment；
Fig. 3 is the electron scanning micrograph of 2 gained final product of embodiment；
Fig. 4 is the cycle performance curve graph of 2 gained composite material of embodiment；
Fig. 5 is the cyclic curve figure of 3 resulting materials of embodiment；
Fig. 6 is the cycle performance curve graph of 3 gained composite material of embodiment；
Fig. 7 is the cyclic curve figure of 4 resulting materials of embodiment；
Fig. 8 is the cycle performance curve graph of 4 gained composite material of embodiment；
Fig. 9 is the cyclic curve figure of 5 resulting materials of embodiment；
Figure 10 is the cycle performance curve graph of 5 gained composite material of embodiment；
Figure 11 is the structural schematic diagram of the composite material.
Specific implementation mode
The present invention is further illustrated in the following with reference to the drawings and specific embodiments.
Embodiment 1
1) graphene for weighing 10mg is sufficiently stirred and ultrasound；
2) Co (NO of 1g are weighed3)2, the urea of 50mg and the NH of 50mg4F powder is added to the good graphene solution of ultrasound
In, it stirs 5 minutes；
3) polyvinylpyrrolidone (PVP) powder for weighing 20mg is added in above-mentioned mixed liquor, is stirred 5 minutes；
4) it is reacted at 100 DEG C, the time is 6 hours；
5) after reaction, taking precipitate water and ethyl alcohol carry out centrifuge washing；
6) deionized water is added to be stirred the sediment washed；
7) Ni (NO of 200mg are weighed3)2, the Na of 200mg2MoO4Solid is added in above-mentioned solution, stirring；
8) 5mL ethyl alcohol is measured, is added drop-wise in mixed liquor, is stirred；
9) it is transferred in ptfe autoclave and is reacted at 100 DEG C, 5 hours time；
10) after reaction, taking precipitate water and ethyl alcohol carry out centrifuge washing；
11) structural representation to get composite material as shown in Figure 1 in dry 12 hours in the baking oven that temperature is 60 DEG C
Figure, Fig. 2 are the cycle performance curve graph of the composite material.
The composite material of the pattern is loose porous, and cobalt oxide nanorod growth is on the surface of graphene, the oxidation of nickel molybdenum
Object regrowth oxidation cobalt nanorod on so that composite material level is clearly demarcated, be conducive to electrolyte intermediate ion conveying with exchange.
After 1000 wheels, the energy density of the composite material has decayed 4.1%, and cyclicity is fine.
Embodiment 2
1) graphene for weighing 100mg is sufficiently stirred and ultrasound；
2) Co (NO of 1g are weighed3)2, the urea of 200mg and the NH of 200mg4It is molten to be added to the good graphene of ultrasound for F powder
In liquid, stir 5 minutes；
3) polyvinylpyrrolidone (PVP) powder for weighing 100mg is added in above-mentioned mixed liquor, is stirred 5 minutes；
4) it is reacted at 200 DEG C, the time is 12 hours；
5) after reaction, taking precipitate water and ethyl alcohol carry out centrifuge washing；
6) deionized water is added to be stirred the sediment washed；
7) Ni (NO of 500mg are weighed3)2, the Na of 500mg2MoO4Solid is added in above-mentioned solution, stirring；
8) 15mL ethyl alcohol is measured, is added drop-wise in mixed liquor, is stirred；
9) it is transferred in ptfe autoclave and is reacted at 200 DEG C, 10 hours time；
10) after reaction, taking precipitate water and ethyl alcohol carry out centrifuge washing；
11) structural representation to get composite material as shown in Figure 3 in dry 12 hours in the baking oven that temperature is 60 DEG C
Figure, Fig. 4 are the cycle performance curve graph of the composite material.
The composite material is grown in graphene platelet surface, and club shaped structure is apparent, whole not have agglomeration, is conducive to multiple
Condensation material gives full play to its chemical property.After 1000 wheels, the energy density of the composite material has decayed 6.2%, cycle
Property is fine.
Embodiment 3
1) graphene for weighing 50mg is sufficiently stirred and ultrasound；
2) Co (NO of 1g are weighed3)2, the urea of 150mg and the NH of 150mg4It is molten to be added to the good graphene of ultrasound for F powder
In liquid, stir 5 minutes；
3) polyvinylpyrrolidone (PVP) powder for weighing 50mg is added in above-mentioned mixed liquor, is stirred 5 minutes；
4) it is reacted at 150 DEG C, the time is 24 hours；
5) after reaction, taking precipitate water and ethyl alcohol carry out centrifuge washing；
6) deionized water is added to be stirred the sediment washed；
7) Ni (NO of 300mg are weighed3)2, the Na of 300mg2MoO4Solid is added in above-mentioned solution, stirring；
8) 10mL ethyl alcohol is measured, is added drop-wise in mixed liquor, is stirred；
9) it is transferred in ptfe autoclave and is reacted at 150 DEG C, 6 hours time；
10) after reaction, taking precipitate water and ethyl alcohol carry out centrifuge washing；
11) structural representation to get composite material as shown in Figure 5 in dry 12 hours in the baking oven that temperature is 60 DEG C
Figure, Fig. 6 are the cycle performance curve graph of the composite material.
The rodlike structure of the composite material is still apparent, thereon the also more intensive shorter nano bar-shape of length that grows
Nickel molybdenum oxide grown the smaller chondritic material of scale, on the whole, composite material is loose porous, receives in remaining place
Rice club shaped structure has been connected to entire composite material so that composite material integrally connects together, there is not the part isolated and
As inactive material.After 1000 wheels, the energy density of the composite material has decayed 7.1%, and cyclicity is fine.
Embodiment 4
1) graphene for weighing 50mg is sufficiently stirred and ultrasound；
2) Co (NO of 1g are weighed3)2, the urea of 150mg and the NH of 100mg4It is molten to be added to the good graphene of ultrasound for F powder
In liquid, stir 5 minutes；
3) polyvinylpyrrolidone (PVP) powder for weighing 80mg is added in above-mentioned mixed liquor, is stirred 5 minutes；
4) it is reacted at 120 DEG C, the time is 24 hours；
5) after reaction, taking precipitate water and ethyl alcohol carry out centrifuge washing；
6) deionized water is added to be stirred the sediment washed；
7) Ni (NO of 300mg are weighed3)2, the Na of 200mg2MoO4Solid is added in above-mentioned solution, stirring；
8) 10mL ethyl alcohol is measured, is added drop-wise in mixed liquor, is stirred；
9) it is transferred in ptfe autoclave and is reacted at 180 DEG C, 4 hours time；
10) after reaction, taking precipitate water and ethyl alcohol carry out centrifuge washing；
11) structural representation to get composite material as shown in Figure 7 in dry 12 hours in the baking oven that temperature is 60 DEG C
Figure, Fig. 8 are the cycle performance curve graph of the composite material.
The cobalt oxide of the composite material nanometer nano bar-shape structure is grown on the surface of graphene, the nickel molybdenum oxygen of near-spherical structure
Compound is evenly distributed in oxidation cobalt nanorod and graphene surface, and smaller composite material granular is Nano grade, and is distributed
Uniformly, the conducting being conducive between composite material entirety.After 1000 wheels, the energy density of the composite material decays
10.9%, cyclicity is fine.
Embodiment 5
1) graphene for weighing 20mg is sufficiently stirred and ultrasound；
2) Co (NO of 1g are weighed3)2, the urea of 150mg and the NH of 90mg4It is molten to be added to the good graphene of ultrasound for F powder
In liquid, stir 5 minutes；
3) polyvinylpyrrolidone (PVP) powder for weighing 20mg is added in above-mentioned mixed liquor, is stirred 5 minutes；
4) it is reacted at 150 DEG C, the time is 12 hours；
5) after reaction, taking precipitate water and ethyl alcohol carry out centrifuge washing；
6) deionized water is added to be stirred the sediment washed；
7) Ni (NO of 250mg are weighed3)2, the Na of 200mg2MoO4Solid is added in above-mentioned solution, stirring；
8) 8mL ethyl alcohol is measured, is added drop-wise in mixed liquor, is stirred；
9) it is transferred in ptfe autoclave and is reacted at 140 DEG C, 4 hours time；
10) after reaction, taking precipitate water and ethyl alcohol carry out centrifuge washing；
11) structural representation to get composite material as shown in Figure 9 in dry 12 hours in the baking oven that temperature is 60 DEG C
Figure, Figure 10 are the cycle performance curve graph of the composite material.
Composite material oxidation cobalt nanorod is longer, grown more rodlike nickel molybdenum oxides thereon, and material is whole
Upper loose porous, distribution is uniform, apparent agglomeration does not occur, the ion exchange being conducive in Electrochemical Test Procedure.
After 1000 wheels, the energy density of the composite material has decayed 13%, and cyclicity is fine.
The above, only presently preferred embodiments of the present invention, are not intended to limit the invention, patent protection model of the invention
It encloses and is subject to claims, equivalent structure variation made by every specification and accompanying drawing content with the present invention, similarly
It should be included within the scope of the present invention.
Claims (9)
1. a kind of composite material of ternary cobalt nickel molybdenum oxide growth in situ on graphene, it is characterised in that：The composite wood
Material is using graphene as substrate, and growth in situ is combined with the oxidation cobalt nanorod of club shaped structure on the graphene-based bottom；The oxygen
Change the nickel molybdenum oxide nanometer rods that growth in situ on cobalt nanorod is combined with club shaped structure.
2. a kind of composite material of ternary cobalt nickel molybdenum oxide growth in situ on graphene as described in claim 1, special
Sign is：The thickness at the graphene-based bottom is 0.1-5nm.
3. a kind of composite material of ternary cobalt nickel molybdenum oxide growth in situ on graphene as described in claim 1, special
Sign is：The length of the oxidation cobalt nanorod is 0.1-5 μm.
4. a kind of composite material of ternary cobalt nickel molybdenum oxide growth in situ on graphene as described in claim 1, special
Sign is：The length of the nickel molybdenum oxide nanometer rods is 10-500nm.
5. a kind of two-step synthesis method of ternary cobalt nickel molybdenum oxide composite material of growth in situ on graphene, feature exist
In including the following steps：
1) weigh graphene, add water be sufficiently stirred with ultrasound, obtain graphene solution；
2) Co (NO are weighed3)2, urea and NH4F powder is added in the good graphene solution of ultrasound, stirs 5 minutes；
3) it weighs polyvinylpyrrolidonepowder powder to be added in the mixed liquor obtained in step 2), stir 5 minutes；
4) mixed liquor that step 3) obtains is placed at 100-200 DEG C and is reacted, the time is 6-24 hours；
5) reaction solution that after reaction, step 4) is obtained filters, and taking precipitate centrifuges sediment with water and ethyl alcohol
Washing；
6) deionized water is added to be stirred the sediment washed；
7) Ni (NO are weighed3)2, Na2MoO4Solid is added in the solution that step 6) obtains, stirring；
8) ethyl alcohol is measured, is added drop-wise in the mixed liquor that step 7) obtains, is stirred；
9) mixed solution that step 8) obtains is transferred in ptfe autoclave and is reacted at 100-200 DEG C, time 1-
10 hours；
10) reaction solution that after reaction, step 9) is obtained filters, taking precipitate, with water and ethyl alcohol to sediment carry out from
The heart washs；
11) the clean sediment for obtaining step 10) is 12 hours dry in the baking oven that temperature is 30-100 DEG C, and gained is most
Final product.
6. a kind of two steps of ternary cobalt nickel molybdenum oxide composite material of growth in situ on graphene as claimed in claim 5
Synthetic method, it is characterised in that：A concentration of 0.5-2g/L of graphene in step 1).
7. a kind of two steps of ternary cobalt nickel molybdenum oxide composite material of growth in situ on graphene as claimed in claim 5
Synthetic method, it is characterised in that：A concentration of 0.1-5g/L of polyvinylpyrrolidone in step 3).
8. a kind of two steps of ternary cobalt nickel molybdenum oxide composite material of growth in situ on graphene as claimed in claim 5
Synthetic method, it is characterised in that：N i (NO in step 7)3)2With Na2MoO4Molar ratio be 1：1.
9. a kind of two steps of ternary cobalt nickel molybdenum oxide composite material of growth in situ on graphene as claimed in claim 5
Synthetic method, it is characterised in that：The volume of mixed liquor described in step 8) is 1-5 times of ethyl alcohol, and the two total volume is not more than
The maximum capacity of reaction kettle.
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| CN111564319A (en) * | 2020-05-06 | 2020-08-21 | 电子科技大学 | Preparation method of three-dimensional nanostructure material with porous core-shell heterostructure |
| CN111584245A (en) * | 2020-05-06 | 2020-08-25 | 电子科技大学 | Three-dimensional network structure composite material and preparation method and application thereof |
| CN114582638A (en) * | 2022-03-01 | 2022-06-03 | 福建工程学院 | Method for preparing flexible porous nickel-cobalt-molybdenum-based supercapacitor electrode by electrochemically assisting etching template |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109786136A (en) * | 2019-02-25 | 2019-05-21 | 天津艾克凯胜石墨烯科技有限公司 | The method of Ni-Co-Mn nanoneedle is grown on a kind of 3D graphene |
| CN109786136B (en) * | 2019-02-25 | 2021-10-08 | 天津艾克凯胜石墨烯科技有限公司 | Method for growing Ni-Co-Mn nanoneedle on 3D graphene |
| CN111564319A (en) * | 2020-05-06 | 2020-08-21 | 电子科技大学 | Preparation method of three-dimensional nanostructure material with porous core-shell heterostructure |
| CN111584245A (en) * | 2020-05-06 | 2020-08-25 | 电子科技大学 | Three-dimensional network structure composite material and preparation method and application thereof |
| CN111564319B (en) * | 2020-05-06 | 2021-07-06 | 电子科技大学 | Preparation method of three-dimensional nanostructure material with porous core-shell heterostructure |
| CN114582638A (en) * | 2022-03-01 | 2022-06-03 | 福建工程学院 | Method for preparing flexible porous nickel-cobalt-molybdenum-based supercapacitor electrode by electrochemically assisting etching template |
| CN114582638B (en) * | 2022-03-01 | 2023-04-11 | 福建工程学院 | Method for preparing flexible porous nickel-cobalt-molybdenum-based supercapacitor electrode by electrochemically assisting etching template |
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