CN108428562B - Composite material for in-situ growth of ternary cobalt-nickel-molybdenum oxide on graphene and two-step synthesis method thereof - Google Patents
Composite material for in-situ growth of ternary cobalt-nickel-molybdenum oxide on graphene and two-step synthesis method thereof Download PDFInfo
- Publication number
- CN108428562B CN108428562B CN201810343599.7A CN201810343599A CN108428562B CN 108428562 B CN108428562 B CN 108428562B CN 201810343599 A CN201810343599 A CN 201810343599A CN 108428562 B CN108428562 B CN 108428562B
- Authority
- CN
- China
- Prior art keywords
- graphene
- composite material
- molybdenum oxide
- situ
- precipitate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 25
- 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 abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 45
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 26
- 239000002073 nanorod Substances 0.000 claims abstract description 19
- 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 9
- 239000000758 substrate Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 62
- 238000003756 stirring Methods 0.000 claims description 41
- 239000002244 precipitate Substances 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 238000005303 weighing Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 17
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 17
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 229910004619 Na2MoO4 Inorganic materials 0.000 claims description 9
- 239000011684 sodium molybdate Substances 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 1
- 238000005054 agglomeration Methods 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 5
- 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
- 239000003990 capacitor Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 12
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 2
- CIHYROJTBKFOPR-UHFFFAOYSA-N nickel;oxomolybdenum Chemical class [Ni].[Mo]=O CIHYROJTBKFOPR-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 230000006866 deterioration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- 238000009827 uniform distribution Methods 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 invention provides a composite material of ternary cobalt-nickel-molybdenum oxide in-situ growth on graphene and a two-step synthesis method thereof, and relates to the field of graphene and metal oxide composite materials, wherein the composite material takes graphene as a substrate, and a cobalt oxide nanorod with a rod-shaped structure is combined on the substrate of the graphene in-situ growth; and a nickel-molybdenum oxide nanorod with a rod-shaped structure grows and is combined on the cobalt oxide nanorod in situ. According to the composite material provided by the invention, the extremely thin graphene increases the specific surface area of the material, and the utilization rate of an active material is increased; the graphene connects the cobalt oxide materials together, so that the materials are integrally conducted, and the material failure condition caused by weak conductivity is avoided; the well-arranged structure avoids the agglomeration phenomenon of the material, forms a three-dimensional loose porous shape, further increases the specific surface area of the material and improves the capacitance of the material.
Description
Technical Field
the invention relates to the field of graphene and metal oxide composite materials, in particular to a composite material with ternary cobalt-nickel-molybdenum oxide growing in situ on graphene and a two-step synthesis method thereof.
background
with the rapid development of global economy, the continuous consumption of fossil energy and the gradual deterioration of the environment, people urgently need to find an effective method for dealing with the problem of double stress of energy and environment, and how to carry out green regeneration of the energy becomes the first problem of research of scientific researchers. The reserves of various fossil energy sources on the earth are seriously short, according to prediction, petroleum is exhausted in 2050 years, coal can be reused for one hundred years, and natural gas does not exist after thirty years.
the super capacitor is used as a novel energy storage system developed in seventy-eight years of the last century, and has excellent application in various fields such as military, civil use and the like through continuous development for decades. Compared with a lithium battery, the lithium battery has the advantages of high power density, short charging time, long service life, good temperature characteristic, environmental protection and no pollution. With the rapid development of the current nanotechnology, the supercapacitor combines the excellent characteristics of the graphene and other nanomaterials, and various performances of the supercapacitor are continuously improved. The super capacitor is divided into a double-electric-layer super capacitor and a pseudo-capacitor super capacitor, the double-electric-layer super capacitor mainly utilizes the ultrahigh specific surface area of a carbon material to provide attachable sites for ions in an electrolyte in the charging and discharging process so as to form a conductive loop, the larger the specific surface area is, the more ions are attached, the more charges are stored, the larger the capacity is, and the classical double-electric-layer super capacitor adopts activated carbon as a positive electrode material and a negative electrode material, and the cycle life of the classical double-electric-layer super capacitor can reach the million-order level. The pseudocapacitance super capacitor mainly utilizes the redox reaction of transition metal oxides to store charges, metal elements such as Fe, Co, Ni, Zn, Mn and the like are commonly used, the theoretical capacity of the pseudocapacitance super capacitor is higher than that of a double electric layer super capacitor, but the cycle life of the pseudocapacitance super capacitor is still subject to continuous research by scientific researchers. As can be seen from the above description, the electric double layer supercapacitor has a long service life, but its capacity depends on the specific surface area; the pseudocapacitance super capacitor has large capacity, but the service life of the pseudocapacitance super capacitor is a big difficulty for research, and an important factor which prevents the super capacitor from meeting the requirements of service life and capacity at the same time is that the performance of an electrode material cannot meet the requirements.
Nowadays, ternary materials are playing an increasingly important role in supercapacitors, such as the chinese patent (CN 102656650a) that prepares nickel-cobalt supercapacitor electrode materials by direct mixing of nickel and cobalt oxides, which describes an improved capacitor that utilizes mixed metal oxides of transition metals nickel and cobalt in combination with a binder and carbon nanotubes to prepare a superior supercapacitor that has a high specific surface area and still possesses a high specific capacitance at higher voltage scan rates. However, the following problems still remain:
1. The cobalt oxide and the cobalt oxide have an agglomeration effect, so that ions in electrolyte can not enter the material in the electrochemical reaction process, charge exchange is not facilitated, the specific surface area of the material is reduced, and the capacitance of the material is difficult to improve;
2. Some of the material is isolated due to conductivity problems, resulting in an inefficient quality of some of the material not being utilized;
3. The cobalt and the nickel-molybdenum are doped with each other, so that the amorphous state proportion in the prepared material is increased, the shaping of the material is influenced, and the volume expansion or pulverization of the material is inevitably caused along with the proceeding of the electrochemical reaction of the material, so that the later performance of the super capacitor prepared by the material is seriously reduced, and the service life of the super capacitor is influenced.
Disclosure of Invention
The invention provides a composite material of ternary cobalt-nickel-molybdenum oxide grown in situ on graphene and a two-step synthesis method thereof, which are used for solving the technical problem that the performance of the existing electrode material cannot meet the requirements of service life and capacity at the same time.
The purpose of the invention can be realized by the following technical scheme:
a composite material of ternary cobalt nickel molybdenum oxide in-situ growth on graphene takes graphene as a substrate, and cobalt oxide nanorods of a rod-like structure are combined on the substrate in-situ growth; and a nickel-molybdenum oxide nanorod with a rod-shaped structure grows and is combined on the cobalt oxide nanorod in situ.
preferably, the thickness of the graphene substrate is 0.1-5 nm.
Preferably, the length of the cobalt oxide nanorod is 0.1-5 μm.
Preferably, the length of the nickel molybdenum oxide nanorod is 10-500 nm.
a two-step synthesis method of a composite material with ternary cobalt-nickel-molybdenum oxide in-situ growth on graphene comprises the following steps:
1) weighing graphene, adding water, fully stirring and performing ultrasonic treatment to obtain a graphene solution;
2) weighing Co (NO)3)2Urea and NH4adding the powder F into the graphene solution subjected to ultrasonic treatment, and stirring for 5 minutes;
3) weighing polyvinylpyrrolidone powder, adding the polyvinylpyrrolidone powder into the mixed solution obtained in the step 2), and stirring for 5 minutes;
4) Placing the mixed solution obtained in the step 3) at 100-200 ℃ for reaction for 6-24 hours;
5) after the reaction is finished, filtering the reaction solution obtained in the step 4), taking a precipitate, and centrifugally washing the precipitate by using water and ethanol;
6) adding deionized water into the washed precipitate and stirring;
7) Weighing Ni (NO)3)2，Na2MoO4adding the solid into the solution obtained in the step 6), and stirring;
8) measuring ethanol, dropwise adding the ethanol into the mixed solution obtained in the step 7), and stirring;
9) transferring the mixed solution obtained in the step 8) into a polytetrafluoroethylene reaction kettle to react at 100-200 ℃ for 1-10 hours;
10) after the reaction is finished, filtering the reaction solution obtained in the step 9), taking a precipitate, and centrifugally washing the precipitate by using water and ethanol;
11) drying the clean precipitate obtained in the step 10) in an oven at the temperature of 30-100 ℃ for 12 hours to obtain the final product.
preferably, the concentration of the graphene in the step 1) is 0.5-2 g/L.
Preferably, the concentration of polyvinylpyrrolidone in step 3) is 0.1-5 g/L.
preferably, Ni (NO) in step 7)3)2with Na2MoO4in a molar ratio of 1: 1.
Preferably, the volume of the mixed solution in the step 8) is 1-5 times of that of the ethanol, and the total volume of the two is not more than the maximum capacity of the reaction kettle.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. according to the composite material provided by the invention, the extremely thin graphene increases the specific surface area of the material, and the utilization rate of an active material is increased; the graphene connects the cobalt oxide materials together, so that the materials are integrally conducted, and the material failure condition caused by weak conductivity is avoided; the rodlike cobalt oxide grows in situ on the graphene sheet, and the rodlike nickel-molybdenum oxide grows in situ on the rodlike cobalt oxide, so that the material is prevented from agglomerating due to a well-layered structure, a three-dimensional loose porous shape is formed, ions in the electrolyte can enter the material to exchange charges in the electrochemical reaction process, the specific surface area of the material is further increased, and the capacitance of the material is improved.
2. The rodlike cobalt oxide is tightly combined together by in-situ growth on the graphene sheet and is uniformly arranged on the graphene sheet, so that the agglomeration effect between the cobalt oxide and the cobalt oxide is cut off, almost all cobalt materials are connected in parallel by the graphene with good conductivity to form a perfect conductive network, part of the materials are isolated due to the conductivity problem, and the invalid quality caused by that part of the materials are not utilized is avoided;
3. According to the method, cobalt oxide is grown on the surface of graphene in situ by a hydrothermal method, a cobalt precursor is cracked into cobalt ions at high temperature, and a large amount of cobalt ions are uniformly nucleated and grown on the surface of the graphene, so that the in-situ growth is more favorable for uniform distribution of cobalt materials, the agglomeration growth between the materials is prevented, the effective specific surface area of the cobalt materials is increased, and a plurality of growth sites are provided for the second-step reaction; the two-step method is different from the one-step method for directly synthesizing the metal oxide material, although the one-step method is not simple and convenient, the two-step method provides guarantee for clear layers of the material, prevents mutual doping between cobalt and nickel molybdenum, avoids the generation of amorphous state of the material appearance, improves the stability of the material and also prolongs the service life of the material;
4. In the first step of reaction, the unique structure of polyvinylpyrrolidone firmly combines graphene and cobalt oxide together; in the second step of reaction, the cobalt oxide nanorod connects the three nickel-molybdenum oxides with the graphene, so that the conductivity of the whole material is improved, and in the second step of reaction, the mixed solvent is formed by adding ethanol and the traditional deionized water, so that the pressure and the gas atmosphere in the reaction kettle are changed, and the two supplement each other, so that the formation of the three-dimensional layered three-dimensional structure is promoted; the implementation of the two-step method avoids the unfavorable situation that various metal elements are mutually replaced by the traditional one-step method, and a good structure with clear levels is created;
5. From the experimental implementation perspective, the scheme that this patent used is simple easy to operate, and can carry out the factory production on a large scale.
Drawings
FIG. 1 is a scanning electron micrograph of a final product obtained in example 1;
FIG. 2 is a graph of cycle performance of the composite obtained in example 1;
FIG. 3 is a scanning electron micrograph of a final product obtained in example 2;
FIG. 4 is a graph of cycle performance of the composite material obtained in example 2;
FIG. 5 is a graph showing the cycle profile of the material obtained in example 3;
FIG. 6 is a graph of cycle performance of the composite obtained in example 3;
FIG. 7 is a graph showing the cycle profile of the material obtained in example 4;
FIG. 8 is a graph of cycle performance of the composite obtained in example 4;
FIG. 9 is a graph showing the cycle profile of the material obtained in example 5;
FIG. 10 is a graph of cycle performance of the composite obtained in example 5;
fig. 11 is a schematic structural view of the composite material.
Detailed Description
The invention is further described with reference to the following figures and specific embodiments.
Example 1
1) weighing 10mg of graphene, and fully stirring and ultrasonically treating;
2) Weighing 1g of Co (NO)3)250mg of urea and 50mg of NH4adding the powder F into the graphene solution subjected to ultrasonic treatment, and stirring for 5 minutes;
3) Weighing 20mg of polyvinylpyrrolidone (PVP) powder, adding into the mixed solution, and stirring for 5 minutes;
4) Reacting at 100 ℃ for 6 hours;
5) After the reaction is finished, taking the precipitate, and centrifugally washing the precipitate by using water and ethanol;
6) Adding deionized water into the washed precipitate and stirring;
7) 200mg of Ni (NO) are weighed out3)2200mg of Na2MoO4Adding the solid into the solution, and stirring;
8) measuring 5mL of ethanol, dropwise adding the ethanol into the mixed solution, and stirring;
9) Transferring the mixture into a polytetrafluoroethylene reaction kettle to react at 100 ℃ for 5 hours;
10) After the reaction is finished, taking the precipitate, and centrifugally washing the precipitate by using water and ethanol;
11) drying in an oven at 60 deg.C for 12 hr to obtain the composite material shown in FIG. 1, and FIG. 2 is a graph of cycle performance of the composite material.
The composite material with the appearance is loose and porous, the cobalt oxide nanorod grows on the surface of the graphene, and the nickel-molybdenum oxide grows on the cobalt oxide nanorod again, so that the composite material is well-arranged, and is beneficial to the transportation and exchange of ions in electrolyte. After 1000 cycles, the energy density of the composite decayed by 4.1%, with good cyclicity.
example 2
1) weighing 100mg of graphene, and fully stirring and ultrasonically treating;
2) Weighing 1g of Co (NO)3)2200mg of urea and 200mg of NH4adding the powder F into the graphene solution subjected to ultrasonic treatment, and stirring for 5 minutes;
3) weighing 100mg of polyvinylpyrrolidone (PVP) powder, adding into the mixed solution, and stirring for 5 minutes;
4) reacting at 200 ℃ for 12 hours;
5) After the reaction is finished, taking the precipitate, and centrifugally washing the precipitate by using water and ethanol;
6) Adding deionized water into the washed precipitate and stirring;
7) 500mg of Ni (NO) are weighed out3)2500mg of Na2MoO4adding the solid into the solution, and stirring;
8) Measuring 15mL of ethanol, dropwise adding the ethanol into the mixed solution, and stirring;
9) Transferring the mixture into a polytetrafluoroethylene reaction kettle to react at the temperature of 200 ℃ for 10 hours;
10) After the reaction is finished, taking the precipitate, and centrifugally washing the precipitate by using water and ethanol;
11) Drying in an oven at 60 deg.C for 12 hr to obtain the composite material shown in FIG. 3, and FIG. 4 is a graph of cycle performance of the composite material.
The composite material grows on the surface of a graphene sheet, has an obvious rod-shaped structure, does not agglomerate integrally, and is beneficial to the composite material to give full play to the electrochemical performance. After 1000 cycles, the energy density of the composite decayed by 6.2%, with good cyclicity.
Example 3
1) weighing 50mg of graphene, and fully stirring and ultrasonically treating;
2) Weighing 1g of Co (NO)3)2150mg of urea and 150mg of NH4adding the powder F into the graphene solution subjected to ultrasonic treatment, and stirring for 5 minutes;
3) Weighing 50mg of polyvinylpyrrolidone (PVP) powder, adding into the mixed solution, and stirring for 5 minutes;
4) reacting at 150 ℃ for 24 hours;
5) After the reaction is finished, taking the precipitate, and centrifugally washing the precipitate by using water and ethanol;
6) adding deionized water into the washed precipitate and stirring;
7) Weighing 300mg of Ni (NO)3)2300mg of Na2MoO4Adding the solid into the solution, and stirring;
8) Measuring 10mL of ethanol, dropwise adding the ethanol into the mixed solution, and stirring;
9) transferring the mixture into a polytetrafluoroethylene reaction kettle to react at 150 ℃ for 6 hours;
10) after the reaction is finished, taking the precipitate, and centrifugally washing the precipitate by using water and ethanol;
11) Drying in an oven at 60 deg.C for 12 hr to obtain the composite material shown in FIG. 5, and FIG. 6 is a graph of cycle performance of the composite material.
the rod-shaped structure of the composite material is still obvious, the nano rod-shaped nickel-molybdenum oxide with short length is densely grown on the composite material, the spherical structural material with small size is grown on the rest places, the composite material is loose and porous as a whole, and the nano rod-shaped structure is communicated with the whole composite material, so that the composite material is integrally connected, and an isolated part does not appear, so that the composite material becomes an invalid material. After 1000 cycles, the energy density of the composite decayed by 7.1%, with good cyclicity.
Example 4
1) Weighing 50mg of graphene, and fully stirring and ultrasonically treating;
2) weighing 1g of Co (NO)3)2150mg of urea and 100mg of NH4Adding the powder F into the graphene solution subjected to ultrasonic treatment, and stirring for 5 minutes;
3) Weighing 80mg of polyvinylpyrrolidone (PVP) powder, adding into the mixed solution, and stirring for 5 minutes;
4) reacting at 120 ℃ for 24 hours;
5) After the reaction is finished, taking the precipitate, and centrifugally washing the precipitate by using water and ethanol;
6) adding deionized water into the washed precipitate and stirring;
7) weighing 300mg of Ni (NO)3)2200mg of Na2MoO4adding the solid into the solution, and stirring;
8) Measuring 10mL of ethanol, dropwise adding the ethanol into the mixed solution, and stirring;
9) Transferring the mixture into a polytetrafluoroethylene reaction kettle to react at 180 ℃ for 4 hours;
10) After the reaction is finished, taking the precipitate, and centrifugally washing the precipitate by using water and ethanol;
11) Drying in an oven at 60 deg.C for 12 hr to obtain the composite material shown in FIG. 7, and FIG. 8 is the cycle performance curve chart of the composite material.
The cobalt oxide of the nano-rod-shaped structure of the composite material grows on the surface of the graphene, the nickel-molybdenum oxide of the spheroidal structure is uniformly distributed on the surfaces of the cobalt oxide nano-rods and the graphene, the particles of the composite material are small and in nano level, and the particles are uniformly distributed, so that the whole composite material is favorably conducted. After 1000 cycles, the energy density of the composite decayed by 10.9%, with good cyclicity.
Example 5
1) weighing 20mg of graphene, and fully stirring and ultrasonically treating;
2) weighing 1g of Co (NO)3)2150mg of urea and 90mg of NH4adding the powder F into the graphene solution subjected to ultrasonic treatment, and stirring for 5 minutes;
3) weighing 20mg of polyvinylpyrrolidone (PVP) powder, adding into the mixed solution, and stirring for 5 minutes;
4) reacting at 150 ℃ for 12 hours;
5) after the reaction is finished, taking the precipitate, and centrifugally washing the precipitate by using water and ethanol;
6) adding deionized water into the washed precipitate and stirring;
7) 250mg of Ni (NO) are weighed out3)2200mg of Na2MoO4adding the solid into the solution, and stirring;
8) Measuring 8mL of ethanol, dropwise adding the ethanol into the mixed solution, and stirring;
9) Transferring the mixture into a polytetrafluoroethylene reaction kettle to react at 140 ℃ for 4 hours;
10) After the reaction is finished, taking the precipitate, and centrifugally washing the precipitate by using water and ethanol;
11) drying in an oven at 60 deg.C for 12 hr to obtain the composite material shown in FIG. 9, and FIG. 10 is a graph of cycle performance of the composite material.
the cobalt oxide nanorod of the composite material is longer, more rod-shaped nickel molybdenum oxides grow on the cobalt oxide nanorod, the material is loose and porous on the whole, is uniformly distributed, does not have an obvious agglomeration phenomenon, and is beneficial to ion exchange in an electrochemical test process. After 1000 cycles, the energy density of the composite decayed by 13% with good cyclicity.
The above description is only a preferred embodiment of the present invention, and not intended to limit the present invention, the scope of the present invention is defined by the appended claims, and all structural changes that can be made by using the contents of the description and the drawings of the present invention are intended to be embraced therein.
Claims (8)
1. a composite material of ternary cobalt nickel molybdenum oxide in-situ growth on graphene is characterized in that: the composite material takes graphene as a substrate, and a cobalt oxide nanorod with a rod-shaped structure is grown and combined on the graphene substrate in situ; a nickel-molybdenum oxide nanorod with a rod-shaped structure grows and is combined with the cobalt oxide nanorod in situ;
The preparation method comprises the following steps:
1) Weighing graphene, adding water, fully stirring and performing ultrasonic treatment to obtain a graphene solution;
2) Weighing Co (NO)3)2Urea and NH4adding the powder F into the graphene solution subjected to ultrasonic treatment, and stirring for 5 minutes;
3) Weighing polyvinylpyrrolidone powder, adding the polyvinylpyrrolidone powder into the mixed solution obtained in the step 2), and stirring for 5 minutes;
4) Putting the mixed solution obtained in the step 3) into a hydrothermal reaction at 100-200 ℃ for 6-24 hours;
5) after the reaction is finished, filtering the reaction solution obtained in the step 4), taking a precipitate, and centrifugally washing the precipitate by using water and ethanol;
6) adding deionized water into the washed precipitate and stirring;
7) weighing Ni (NO)3)2，Na2MoO4solid additionstirring the solution obtained in the step 6);
8) measuring ethanol, dropwise adding the ethanol into the mixed solution obtained in the step 7), and stirring;
9) transferring the mixed solution obtained in the step 8) into a polytetrafluoroethylene reaction kettle to react at 100-200 ℃ for 1-10 hours;
10) After the reaction is finished, filtering the reaction solution obtained in the step 9), taking a precipitate, and centrifugally washing the precipitate by using water and ethanol;
11) drying the clean precipitate obtained in the step 10) in an oven at the temperature of 30-100 ℃ for 12 hours to obtain the final product.
2. The composite material of claim 1, wherein the ternary cobalt nickel molybdenum oxide is grown in situ on graphene, and wherein: the thickness of the graphene substrate is 0.1-5 nm.
3. the composite material of claim 1, wherein the ternary cobalt nickel molybdenum oxide is grown in situ on graphene, and wherein: the length of the cobalt oxide nano rod is 0.1-5 μm.
4. the composite material of claim 1, wherein the ternary cobalt nickel molybdenum oxide is grown in situ on graphene, and wherein: the length of the nickel molybdenum oxide nano rod is 10-500 nm.
5. the composite material of claim 1, wherein the ternary cobalt nickel molybdenum oxide is grown in situ on graphene, and wherein: the concentration of the graphene in the step 1) is 0.5-2 g/L.
6. the composite material of claim 1, wherein the ternary cobalt nickel molybdenum oxide is grown in situ on graphene, and wherein: the concentration of the polyvinylpyrrolidone in the step 3) is 0.1-5 g/L.
7. The composite material of claim 1, wherein the ternary cobalt nickel molybdenum oxide grows on graphene in situThe material is characterized in that: ni (NO) in step 7)3)2With Na2MoO4In a molar ratio of 1: 1.
8. the composite material of claim 1, wherein the ternary cobalt nickel molybdenum oxide is grown in situ on graphene, and wherein: the volume of the mixed solution in the step 8) is 1-5 times of that of the ethanol, and the total volume of the two is not more than the maximum capacity of the reaction kettle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810343599.7A CN108428562B (en) | 2018-04-17 | 2018-04-17 | Composite material for in-situ growth of ternary cobalt-nickel-molybdenum oxide on graphene and two-step synthesis method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810343599.7A CN108428562B (en) | 2018-04-17 | 2018-04-17 | Composite material for in-situ growth of ternary cobalt-nickel-molybdenum oxide on graphene and two-step synthesis method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108428562A CN108428562A (en) | 2018-08-21 |
| CN108428562B true CN108428562B (en) | 2019-12-13 |
Family
ID=63161327
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810343599.7A Active CN108428562B (en) | 2018-04-17 | 2018-04-17 | Composite material for in-situ growth of ternary cobalt-nickel-molybdenum oxide on graphene and two-step synthesis method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108428562B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN111584245B (en) * | 2020-05-06 | 2021-06-01 | 电子科技大学 | Three-dimensional network structure composite material and preparation method and application thereof |
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105470000A (en) * | 2016-01-08 | 2016-04-06 | 广东工业大学 | Integrated composite electrode for supercapacitor and preparation method of integrated composite electrode |
| CN107464937A (en) * | 2017-07-17 | 2017-12-12 | 北京师范大学 | Cobaltosic oxide graphene nanocomposite material, preparation method and the usage |
-
2018
- 2018-04-17 CN CN201810343599.7A patent/CN108428562B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108428562A (en) | 2018-08-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Hierarchical nickel cobalt sulfide nanosheet on MOF-derived carbon nanowall arrays with remarkable supercapacitive performance | |
| Luo et al. | Hollow Co3S4/C anchored on nitrogen-doped carbon nanofibers as a free-standing anode for high-performance Li-ion batteries | |
| Zhang et al. | Constructing ultra-thin Ni-MOF@ NiS2 nanosheets arrays derived from metal organic frameworks for advanced all-solid-state asymmetric supercapacitor | |
| Zhou et al. | Applications of M x Se y (M= Fe, Co, Ni) and their composites in electrochemical energy storage and conversion | |
| CN108428562B (en) | Composite material for in-situ growth of ternary cobalt-nickel-molybdenum oxide on graphene and two-step synthesis method thereof | |
| Su et al. | Construction of CoP@ C embedded into N/S-co-doped porous carbon sheets for superior lithium and sodium storage | |
| Pore et al. | Review on recent progress in hydrothermally synthesized MCo2O4/rGO composite for energy storage devices | |
| CN111540610B (en) | Electrode material for super capacitor and preparation method and application thereof | |
| Wei et al. | Self-assembled ZnO-carbon dots anode materials for high performance nickel-zinc alkaline batteries | |
| Zhang et al. | 3D carbon coated NiCo2S4 nanowires doped with nitrogen for electrochemical energy storage and conversion | |
| Huo et al. | Facile synthesis of manganese cobalt oxide/nickel cobalt oxide composites for high-performance supercapacitors | |
| Guo et al. | Facile fabrication of CoNi-Layered Double Hydroxide/NiCo2S4/Reduced Graphene Oxide composites by in situ hydrothermal growth strategy for supercapacitor performance | |
| Liu et al. | Porous CuCo2O4/CuO microspheres and nanosheets as cathode materials for advanced hybrid supercapacitors | |
| Chen et al. | Wood-derived scaffolds decorating with nickel cobalt phosphate nanosheets and carbon nanotubes used as monolithic electrodes for assembling high-performance asymmetric supercapacitor | |
| Huang et al. | Fe-based metal-organic frameworks and their derivatives for electrochemical energy conversion and storage | |
| Qin et al. | Nitrogen-doped Ni2P/Ni12P5/Ni3S2 three-phase heterostructure arrays with ultrahigh areal capacitance for high-performance asymmetric supercapacitor | |
| Zhang et al. | 3D heterostructured cobalt oxide@ layered double hydroxide core–shell networks on nickel foam for high-performance hybrid supercapacitor | |
| Li et al. | Engineering novel Ni2-XCoxP structures for high performance lithium-ion storage | |
| Zhang et al. | Rational design of NiMn-based electrode materials for high-performance supercapacitors | |
| Zhang et al. | Three-dimensional core-branch α-Fe2O3@ NiO/carbon cloth heterostructured electrodes for flexible supercapacitors | |
| Lin et al. | Prospect of Ni-related metal oxides for high-performance supercapacitor electrodes | |
| Shi et al. | Ultrathin NiO confined within hollow carbon sphere for efficient electrochemical energy storage | |
| Moghimian et al. | One-step hydrothermal synthesis of GQDs-MoS2 nanocomposite with enhanced supercapacitive performance | |
| Singhal et al. | Recent developments in transition metal-based nanomaterials for supercapacitor applications | |
| Xuan et al. | Synthesis of hierarchical porous Co (OH) 2/Ni2Mn1Ox composites on Ni foam for high performance battery-supercapacitor hybrid devices |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |