CN111009423A - Carbon nanotube/basic nickel cobalt carbonate composite electrode material, preparation method and prepared super capacitor - Google Patents
Carbon nanotube/basic nickel cobalt carbonate composite electrode material, preparation method and prepared super capacitor Download PDFInfo
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- CN111009423A CN111009423A CN202010025493.XA CN202010025493A CN111009423A CN 111009423 A CN111009423 A CN 111009423A CN 202010025493 A CN202010025493 A CN 202010025493A CN 111009423 A CN111009423 A CN 111009423A
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- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 73
- IEWUUVGDINEFTP-UHFFFAOYSA-J cobalt(2+) nickel(2+) dicarbonate Chemical compound [Co++].[Ni++].[O-]C([O-])=O.[O-]C([O-])=O IEWUUVGDINEFTP-UHFFFAOYSA-J 0.000 title claims abstract description 49
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- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims abstract description 9
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims abstract description 9
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- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 14
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
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- 238000001816 cooling Methods 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 6
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- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
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- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
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- DZJUVKRYUDHJEY-UHFFFAOYSA-K cobalt(2+);nickel(2+);carbonate;hydroxide Chemical compound [OH-].[Co+2].[Ni+2].[O-]C([O-])=O DZJUVKRYUDHJEY-UHFFFAOYSA-K 0.000 abstract 1
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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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
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Abstract
The invention provides a carbon nano tube/nickel cobalt carbonate hydroxide composite electrode material, a preparation method and a prepared super capacitor, wherein the composite electrode material is a composite material formed by uniformly coating the nickel cobalt carbonate hydroxide on the surface of a carbon nano tube, the thickness of the composite electrode material is 10-50 nm, and the molecular formula of the composite electrode material is CNTs @ NixCo1‑x(CO3)1/2(OH) 0.11H2O, wherein x is more than or equal to 0.3 and less than or equal to 0.5. The carbon nano tube/basic nickel cobalt carbonate composite electrode material provided by the invention is prepared by taking urea, deionized water, absolute ethyl alcohol, a carbon nano tube, nickel nitrate hexahydrate and cobalt nitrate hexahydrate as raw materials through a one-step hydrothermal method, and the preparation method is simple, low in cost, free of pollution, high in efficiency and wide in application prospect.
Description
Technical Field
The invention relates to the field of electrode materials of supercapacitors, in particular to a carbon nano tube/basic nickel cobalt carbonate composite electrode material, a preparation method and a prepared supercapacitor.
Background
At present, the low utilization rate of electrode materials is one of the urgent problems for further development of supercapacitors. The traditional solution is to increase the contact area between the electrode material and the collector by a micro-nano method, so as to obtain more active sites and further improve the utilization rate of the material. However, the conventional nano material can only react on a limited contact surface, and the measured capacitance is far lower than the theoretical capacitance. Breaking through the dilemma, realizing the perfect combination of the high theoretical capacitance electrode material and the high conductivity nano carbon material, especially constructing the nano active material on the nano carbon material in situ, is a currently recognized research direction with great potential and is also an attractive challenge.
Disclosure of Invention
The invention provides a carbon nano tube/basic nickel cobalt carbonate composite electrode material, a preparation method and a prepared super capacitor. The composite material has the characteristics of short synthesis period, high electrochemical activity, good stability and the like.
The technical scheme for realizing the invention is as follows:
a composite electrode material of carbon nano tube/nickel cobalt basic carbonate is a composite material of the surface of the carbon nano tube uniformly coated with the nickel basic carbonate, the thickness is 10-50 nm, and the molecular formula is CNTs @ NixCo1-x(CO3)1/2(OH)0.11H2O, wherein x is more than or equal to 0.3 and less than or equal to 0.5.
The carbon nano tube/basic nickel cobalt carbonate composite electrode material is a tubular electrode material formed by compounding basic nickel cobalt carbonate with the thickness of 25 nm on a carbon nano tube, and the molecular formula is CNTs @ Ni1/3Co2/3(CO3)1/2(OH)0.11H2O。
The preparation method of the carbon nano tube/basic nickel cobalt carbonate composite electrode material comprises the following steps:
(1) adding urea, deionized water, nickel nitrate hexahydrate, cobalt nitrate hexahydrate, carbon nano tubes and absolute ethyl alcohol into a closed reaction kettle, and then uniformly stirring for reaction at constant temperature to obtain a turbid liquid of the composite electrode material;
(2) and (3) cooling the turbid liquid of the composite electrode material obtained in the step (1) to room temperature, and then separating, cleaning and drying to obtain the carbon nano tube/basic nickel cobalt carbonate composite electrode material.
The mass parts of the substances in the step (1) are as follows: 0.1-2 parts of urea, 1-10 parts of deionized water, 0.05-0.4 part of nickel nitrate hexahydrate, 0.05-1 part of cobalt nitrate hexahydrate, 1-50 parts of carbon nano tubes and 3-8 parts of absolute ethyl alcohol.
And (2) reacting at the constant temperature of 70-120 ℃ for 6-30 h in the step (1).
Cooling the turbid liquid of the composite electrode material in the step (2) to room temperature, then separating the turbid liquid into two layers of supernatant and lower-layer precipitate, pouring out the supernatant, cleaning the lower-layer precipitate with deionized water, performing suction filtration separation treatment, and performing centrifugal washing with the deionized water and absolute ethyl alcohol for 3-5 times respectively to obtain the carbon nano tube/basic nickel cobalt carbonate composite wet electrode material; and (3) drying the carbon nano tube/basic nickel cobalt carbonate composite wet electrode material in a vacuum drying oven at the temperature of 60 ℃ for 6-20 h to obtain the carbon nano tube/basic nickel cobalt carbonate composite electrode material.
A solid-state supercapacitor comprises electrolyte, a positive electrode, a negative electrode and a non-woven fabric diaphragm positioned between the positive electrode and the negative electrode, wherein the electrolyte is PVA/KOH gel electrolyte; the positive electrode comprises the carbon nano tube/basic nickel cobalt carbonate composite electrode material prepared according to any one of claims 2 to 5, a conductive agent, a positive electrode binder and a positive electrode current collector, wherein the mass ratio of the carbon nano tube/basic nickel cobalt carbonate composite electrode material to the conductive agent to the positive electrode binder is (80-A-B): (30+ A): (20+ B), wherein A is more than or equal to 0 and less than or equal to 20, B is more than or equal to 0 and less than or equal to 10, and the loading capacity of the carbon nano tube/basic nickel cobalt carbonate composite electrode material is 3-8 mg/cm2(ii) a The negative electrode comprises activated carbon, a negative electrode binder and a negative electrode current collector, wherein the mass ratio of the activated carbon to the negative electrode binder is (6-10): 1, activated carbon loadingThe amount is 10-30 mg/cm2。
The conductive agent is one or more of acetylene black and conductive graphite; the positive adhesive and the negative adhesive are one or more of polytetrafluoroethylene and polyvinylidene fluoride; the positive current collector and the negative current collector are foamed nickel.
The super capacitor further comprises a shell, the shell is made of organic plastics, stainless steel or composite materials of the organic plastics and the stainless steel, and the shell is in a button type, a column type or a square shape.
The preparation method of the solid-state supercapacitor comprises the following steps:
(1) preparation of the positive electrode: the preparation method comprises the following steps of (1) dispersing and mixing a carbon nano tube/basic nickel cobalt carbonate composite electrode material, a conductive agent and a positive electrode adhesive to prepare positive electrode slurry, coating the positive electrode slurry on a positive electrode current collector, and then drying and tabletting to prepare a positive electrode;
(2) preparation of a negative electrode: dispersing and mixing the activated carbon and the negative adhesive to prepare negative slurry, coating the negative slurry on a negative current collector, and then drying and tabletting to prepare a negative electrode;
(3) assembling the solid-state supercapacitor: the method comprises the following steps of taking PVA/KOH gel electrolyte as solid electrolyte, using a piece of non-woven fabric as a separator, completely immersing a working electrode and a counter electrode into the PVA/KOH gel electrolyte for 30 min, assembling a non-woven fabric diaphragm between the working electrode and the counter electrode, solidifying electrolyte for 1 hour, wrapping the whole device by a preservative film, arranging a small part of nickel strap outside the device, and filling the device into a shell to obtain the super capacitor.
The invention has the beneficial effects that: the carbon nano tube/basic nickel cobalt carbonate composite electrode material provided by the invention is prepared by taking urea, deionized water, absolute ethyl alcohol, a carbon nano tube, nickel nitrate hexahydrate and cobalt nitrate hexahydrate as raw materials through a one-step hydrothermal method, and the preparation method is simple, low in cost, free of pollution, high in efficiency and wide in application prospect. During the reaction, the metal ion M in the solution2+(M = Ni or Co) and NH3Coordination synthesis of [ M (NH)3)4]2+，NH3Adsorbed on the surface of the carbon nano tube. Then, metal ion (M)2+) AndCO2OH on carbon nanotubes-And (4) polymerizing. And continuously adding metal ions substituted by strong metal bonds in the reaction until the surface of the carbon nano tube is covered by the nano thin layer. The residual metal ions are polymerized to form the rod-shaped basic nickel carbonate cobalt until the reaction is finished. The nickel cobalt hydroxycarbonate and the nickel cobalt hydroxycarbonate-coated carbon nanotubes form a two-dimensional network.
In addition, the basic nickel cobalt carbonate was successfully built in situ on the carbon nanotubes by simple hydrothermal treatment. The high contact between the electrode material and the liquid collector improves the utilization rate of the material and achieves the aim of optimizing the electrochemical performance. In a device assembled by taking the carbon nano tube/basic nickel cobalt carbonate composite electrode material as a positive electrode, in a 2M KOH electrolyte, when the current density is 0.5A g-1When the specific capacitance reaches 102.9F g-1. In the PVA/KOH gel electrolyte, the carbon nano tube/basic nickel carbonate cobalt still shows good cycling stability. This result provides a new direction for the development of supercapacitor electrode materials.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a scanning electron micrograph of the carbon nanotube/nickel cobalt hydroxycarbonate composite electrode material prepared in example 1, wherein: and a is a scanning electron microscope picture enlarged to 200 nm.
Fig. 2 is an X-ray diffraction spectrum of the carbon nanotube/nickel cobalt hydroxycarbonate composite electrode material prepared in example 1.
Fig. 3 is a spectrum diagram of the carbon nanotube/nickel cobalt hydroxycarbonate composite electrode material prepared in example 1.
FIG. 4 is a graph of the discharge curves of the supercapacitor made in example 2 at different current densities in a PVA/KOH gel electrolyte.
FIG. 5 is a graph of the discharge of the supercapacitor made in example 3 at different current densities in 2M KOH electrolyte.
FIG. 6 is a plot of the specific capacity of the supercapacitor made in example 3 at different current densities in 2M KOH electrolyte.
FIG. 7 shows 10A g in 2M KOH electrolyte for the supercapacitor made in example 3-1Stability and coulombic efficiency curves.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The embodiment provides a preparation method of a carbon nanotube/basic nickel cobalt carbonate composite electrode material, which comprises the following steps:
0.4 part of urea, 0.05 part of nickel nitrate hexahydrate and 0.1 part of cobalt nitrate hexahydrate are sequentially added into a 30 mL polytetrafluoroethylene reaction kettle inner container, 5 parts of absolute ethyl alcohol, 3 parts of deionized water and 8 parts of carbon nano tubes are added, and magnetic stirring is carried out for 30 min, so that all raw materials are uniformly dispersed in the solution.
And (3) placing the polytetrafluoroethylene inner container filled with the reaction raw materials into an outer container of a stainless steel reaction kettle, and reacting for 12 hours in a constant-temperature air-blast drying oven at the temperature of 100 ℃.
And after the reaction is finished, cooling to room temperature, pouring out the supernatant, respectively washing the lower layer precipitate in a filter flask with deionized water and alcohol for three times, and drying the obtained wet electrode material in a vacuum drying oven at 60 ℃ for 12 hours to obtain the carbon nano tube/basic nickel cobalt carbonate composite electrode material shown in figure 1.
Fig. 1 is a scanning electron microscope of the carbon nanotube/nickel cobalt hydroxycarbonate composite electrode material obtained in the present example, which shows that the carbon nanotube/nickel cobalt hydroxycarbonate composite electrode material has a thickness of about 25 nmThe basic nickel cobalt carbonate is coated on the tubular active material of the carbon nano tube; FIG. 2 is an XRD pattern of the carbon nanotube/nickel cobalt hydroxycarbonate composite electrode material obtained in the example, the pattern being related to Co (CO)3)1/2(OH) 0.11H2O spectra are similar, all diffraction peaks in XRD are shifted due to the addition of nickel ions, and the electrode material is proved to be CNTs @ NixCo1-x(CO3)1/2(OH) 0.11H2O; fig. 3 is an energy spectrum of the carbon nanotube/nickel cobalt hydroxycarbonate composite electrode material obtained in the present example, and according to the energy spectrum data, the atomic ratio of Ni and Co in the material is 1: 2, the molecular formula of the electrode material is CNTs @ Ni1/3Co2/3(CO3)1/2(OH) 0.11H2O。
Example 2
Preparation of the positive electrode: the carbon nanotube/basic nickel cobalt carbonate composite electrode material prepared in example 1, acetylene black, and polyvinylidene fluoride in a mass ratio of 8: 1: 1, weighing, placing the weighed materials into a 10 mL beaker, pulping by dispersion and mixing, coating the pulp on foamed nickel, drying, tabletting and the like to obtain the anode, wherein the loading capacity of the carbon nano tube/basic nickel cobalt carbonate composite electrode material of the anode is 5 mg/cm2；
Preparation of a negative electrode: the composite material is prepared from commercial activated carbon and polyvinylidene fluoride according to a mass ratio of 8: 2 weighing the materials, putting the materials into a 10 mL beaker, preparing pulp by dispersion and mixing, coating the pulp on foamed nickel, drying, tabletting and the like to obtain the cathode, wherein the loading capacity of the active carbon of the cathode is 30 mg/cm2；
Assembling the solid-state supercapacitor: PVA/KOH gel electrolyte is used as solid electrolyte, and a piece of non-woven fabric is used as a separator. The working electrode and the counter electrode were completely immersed in the PVA/KOH gel electrolyte for 30 min, and then a nonwoven fabric separator was fitted between them to allow the electrolyte to solidify for 1 hour. The whole device is wrapped by a preservative film, and a small part of nickel strap is arranged outside the device. And preparing the solid-state supercapacitor.
The discharge current density of the super capacitor in PVA/KOH gel electrolyte is from 0.5A g-1Increased to 20 Ag-1See fig. 4 for the discharge curve of (a).
Example 3
The embodiment provides a super capacitor, which is prepared by the following steps:
preparation of the positive electrode: the carbon nanotube/basic nickel cobalt carbonate composite electrode material prepared in example 1, acetylene black, and polyvinylidene fluoride in a mass ratio of 8: 1: 1, weighing, placing the weighed materials into a 10 mL beaker, pulping by dispersion and mixing, coating the pulp on foamed nickel, drying, tabletting and the like to obtain the anode, wherein the loading capacity of the carbon nano tube/basic nickel cobalt carbonate composite electrode material of the anode is 5 mg/cm2；
Preparation of a negative electrode: the composite material is prepared from commercial activated carbon and polyvinylidene fluoride according to a mass ratio of 8: 2 weighing the materials, putting the materials into a 10 mL beaker, preparing pulp by dispersion and mixing, coating the pulp on foamed nickel, drying, tabletting and the like to obtain the cathode, wherein the loading capacity of the active carbon of the cathode is 30 mg/cm2；
Assembling the super capacitor: compounding the prepared positive electrode, negative electrode and non-woven fabric diaphragm together in a lamination mode, putting the combined positive electrode, negative electrode and non-woven fabric diaphragm into a container, and injecting a proper amount of 2 mol L-1And sealing the KOH aqueous solution by paraffin, and then filling the KOH aqueous solution into a square stainless steel shell to obtain the super capacitor.
The discharge current density of the super capacitor is controlled to be 0.5A g-1Increased to 20A g-1See fig. 5 for the discharge curve of (a).
Referring to fig. 6, the specific capacity curve of the supercapacitor at different discharge rates is from 0.5A g with the discharge current density-1Increased to 20A g-1And the specific capacity performance of the super capacitor is good. Referring to fig. 7, the supercapacitor is at 10A g-1Stability and coulombic efficiency curves for the supercapacitor at 5A g -110000 cycles are circulated under the current density of (a), and the coulomb efficiency of the super capacitor is close to 100% all the time in the circulation process.
Example 4
The preparation method of the carbon nano tube/basic nickel cobalt carbonate composite electrode material comprises the following steps:
(1) adding 0.1 part of urea, 1 part of deionized water, 0.1 part of nickel nitrate hexahydrate, 0.2 part of cobalt nitrate hexahydrate, 1 part of carbon nano tube and 3 parts of absolute ethyl alcohol into a closed reaction kettle, uniformly stirring, and reacting at a constant temperature of 70 ℃ for 30 hours to obtain a turbid liquid of the carbon nano tube/basic nickel cobalt carbonate composite electrode material;
(2) cooling the turbid liquid of the composite electrode material in the step (1) to room temperature, then dividing the turbid liquid into two layers of supernatant and lower-layer precipitate, pouring out the supernatant, cleaning the lower-layer precipitate with deionized water, performing suction filtration separation treatment, and performing centrifugal washing with the deionized water and absolute ethyl alcohol for 3 times respectively to obtain the carbon nano tube/basic nickel cobalt carbonate composite wet electrode material; and (3) drying the carbon nano tube/basic nickel cobalt carbonate composite wet electrode material in a vacuum drying oven at the temperature of 60 ℃ for 6 hours to obtain the carbon nano tube/basic nickel cobalt carbonate composite electrode material.
Example 5
The preparation method of the carbon nano tube/basic nickel cobalt carbonate composite electrode material comprises the following steps:
(1) adding 2 parts by mass of urea, 10 parts by mass of deionized water, 0.4 part by mass of nickel nitrate hexahydrate, 1 part by mass of cobalt nitrate hexahydrate, 50 parts by mass of carbon nanotubes and 8 parts by mass of absolute ethyl alcohol into a closed reaction kettle, uniformly stirring, and reacting at a constant temperature of 120 ℃ for 6 hours to obtain a turbid liquid of the carbon nanotube/basic nickel cobalt carbonate composite electrode material;
(2) cooling the turbid liquid of the composite electrode material in the step (1) to room temperature, then dividing the turbid liquid into two layers of supernatant and lower-layer precipitate, pouring out the supernatant, cleaning the lower-layer precipitate with deionized water, performing suction filtration separation treatment, and performing centrifugal washing with the deionized water and absolute ethyl alcohol for 5 times respectively to obtain the carbon nano tube/basic nickel cobalt carbonate composite wet electrode material; and (3) drying the carbon nano tube/basic nickel cobalt carbonate composite wet electrode material in a vacuum drying oven at the temperature of 60 ℃ for 20 hours to obtain the carbon nano tube/basic nickel cobalt carbonate composite electrode material.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. A carbon nano tube/nickel cobalt carbonate hydroxide composite electrode material is characterized in that: the composite electrode material is a composite material formed by uniformly coating basic nickel cobalt carbonate on the surface of a carbon nano tube, the thickness of the composite electrode material is 10-50 nm, and the molecular formula of the composite electrode material is CNTs @ NixCo1-x(CO3)1/2(OH) 0.11H2O, wherein x is more than or equal to 0.3 and less than or equal to 0.5.
2. The method for preparing the carbon nanotube/nickel cobalt hydroxycarbonate composite electrode material of claim 1, characterized by the steps of:
(1) adding urea, deionized water, nickel nitrate hexahydrate, cobalt nitrate hexahydrate, carbon nano tubes and absolute ethyl alcohol into a closed reaction kettle, and then uniformly stirring for reaction at constant temperature to obtain a turbid liquid of the composite electrode material;
(2) and (3) cooling the turbid liquid of the composite electrode material obtained in the step (1) to room temperature, and then separating, cleaning and drying to obtain the carbon nano tube/basic nickel cobalt carbonate composite electrode material.
3. The method for preparing a carbon nanotube/nickel cobalt hydroxycarbonate composite electrode material according to claim 2, wherein: the mass parts of the substances in the step (1) are as follows: 0.1-2 parts of urea, 1-10 parts of deionized water, 0.05-0.4 part of nickel nitrate hexahydrate, 0.05-1 part of cobalt nitrate hexahydrate, 1-50 parts of carbon nano tubes and 3-8 parts of absolute ethyl alcohol.
4. The method for preparing a carbon nanotube/nickel cobalt hydroxycarbonate composite electrode material according to claim 2, wherein: and (2) reacting at the constant temperature of 70-120 ℃ for 6-30 h in the step (1).
5. The method for preparing a carbon nanotube/nickel cobalt hydroxycarbonate composite electrode material according to claim 2, wherein: cooling the turbid liquid of the composite electrode material in the step (2) to room temperature, then separating the turbid liquid into two layers of supernatant and lower-layer precipitate, pouring out the supernatant, cleaning the lower-layer precipitate with deionized water, performing suction filtration separation treatment, and performing centrifugal washing with the deionized water and absolute ethyl alcohol for 3-5 times respectively to obtain the carbon nano tube/basic nickel cobalt carbonate composite wet electrode material; and (3) drying the carbon nano tube/basic nickel cobalt carbonate composite wet electrode material in a vacuum drying oven at the temperature of 60 ℃ for 6-20 h to obtain the carbon nano tube/basic nickel cobalt carbonate composite electrode material.
6. The utility model provides a solid-state ultracapacitor system, includes electrolyte, anodal, negative pole and is located the non-woven fabrics diaphragm between anodal and the negative pole, its characterized in that: the electrolyte is PVA/KOH gel electrolyte; the positive electrode comprises the carbon nano tube/basic nickel cobalt carbonate composite electrode material prepared according to any one of claims 2 to 5, a conductive agent, a positive electrode binder and a positive electrode current collector, wherein the mass ratio of the carbon nano tube/basic nickel cobalt carbonate composite electrode material to the conductive agent to the positive electrode binder is (80-A-B): (30+ A): (20+ B), wherein A is more than or equal to 0 and less than or equal to 20, B is more than or equal to 0 and less than or equal to 10, and the loading capacity of the carbon nano tube/basic nickel cobalt carbonate composite electrode material is 3-8 mg/cm2(ii) a The negative electrode comprises activated carbon, a negative electrode binder and a negative electrode current collector, wherein the mass ratio of the activated carbon to the negative electrode binder is (6-10): 1, the loading capacity of the active carbon is 10-30 mg/cm2。
7. The solid-state supercapacitor according to claim 6, wherein: the conductive agent is one or more of acetylene black and conductive graphite; the positive adhesive and the negative adhesive are one or more of polytetrafluoroethylene and polyvinylidene fluoride; the positive current collector and the negative current collector are foamed nickel.
8. The method for preparing a solid-state supercapacitor according to claim 6 or 7, characterized by the steps of:
(1) preparation of the positive electrode: the preparation method comprises the following steps of (1) dispersing and mixing a carbon nano tube/basic nickel cobalt carbonate composite electrode material, a conductive agent and a positive electrode adhesive to prepare positive electrode slurry, coating the positive electrode slurry on a positive electrode current collector, and then drying and tabletting to prepare a positive electrode;
(2) preparation of a negative electrode: dispersing and mixing the activated carbon and the negative adhesive to prepare negative slurry, coating the negative slurry on a negative current collector, and then drying and tabletting to prepare a negative electrode;
(3) assembling the solid-state supercapacitor: and (2) taking a PVA/KOH gel electrolyte as a solid electrolyte, completely immersing the working electrode and the counter electrode into the PVA/KOH gel electrolyte for 30 min, assembling a non-woven fabric diaphragm between the working electrode and the counter electrode, solidifying the electrolyte for 1 hour, and wrapping the whole device by a preservative film to obtain the super capacitor.
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