CN112992552B - Nickel cobaltate-titanium nitride array electrode material, preparation method and energy storage application thereof - Google Patents
Nickel cobaltate-titanium nitride array electrode material, preparation method and energy storage application thereof Download PDFInfo
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- CN112992552B CN112992552B CN202011617146.2A CN202011617146A CN112992552B CN 112992552 B CN112992552 B CN 112992552B CN 202011617146 A CN202011617146 A CN 202011617146A CN 112992552 B CN112992552 B CN 112992552B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 239000007772 electrode material Substances 0.000 title claims abstract description 78
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000004146 energy storage Methods 0.000 title abstract description 20
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000011148 porous material Substances 0.000 claims abstract description 47
- 239000003792 electrolyte Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 48
- 239000004793 Polystyrene Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 229920002223 polystyrene Polymers 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 25
- 239000004005 microsphere Substances 0.000 claims description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 16
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- 238000004070 electrodeposition Methods 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 150000001868 cobalt Chemical class 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- 239000002149 hierarchical pore Substances 0.000 claims description 12
- 150000002815 nickel Chemical class 0.000 claims description 12
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 11
- 238000007598 dipping method Methods 0.000 claims description 11
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 11
- 229910001868 water Inorganic materials 0.000 claims description 11
- 239000012452 mother liquor Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
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- 239000010413 mother solution Substances 0.000 claims description 9
- 238000004729 solvothermal method Methods 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
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- 238000000967 suction filtration Methods 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
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- 239000004094 surface-active agent Substances 0.000 claims description 4
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- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 241000257465 Echinoidea Species 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 3
- 238000004945 emulsification Methods 0.000 claims description 3
- 238000010556 emulsion polymerization method Methods 0.000 claims description 3
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- 238000004321 preservation Methods 0.000 claims description 2
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- 239000000463 material Substances 0.000 abstract description 18
- 150000002500 ions Chemical class 0.000 abstract description 15
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- 238000003411 electrode reaction Methods 0.000 abstract description 3
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
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- 229910016287 MxOy Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
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- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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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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- Engineering & Computer Science (AREA)
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- Chemical & Material Sciences (AREA)
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a nickel cobaltate/titanium nitride array electrode material which has a three-dimensional ordered multi-stage pore channel structure, wherein open macropores provide more active sites and transmission spaces for adsorption and transportation of electrode reaction electrolyte ions, and high-conductivity titanium nitride provides a rapid electron transmission channel for nickel cobaltate, so that the defects of poor multiplying power performance and low energy storage efficiency caused by difficulty in rapid transmission of the electrolyte ions and electrons of the electrode material are effectively overcome. The mesoporous structure of the pore wall effectively increases the specific surface area of the material, provides more active sites for reaction, and thus improves the electrochemical energy storage performance. The material can be directly used as a new energy storage electrode material, and has higher practical value and industrial production potential; the preparation process of the electrode material is reliable and easy to implement, and has good industrial production prospect.
Description
Technical Field
The invention relates to the technical field of energy materials, in particular to a nickel cobaltate-titanium nitride array electrode material, a preparation method and an energy storage application thereof.
Background
The electrode material is a core element influencing the performance of energy storage elements such as a super capacitor and a battery. At present, the requirement of human life on high-energy storage devices is more and more urgent, more and more mechanical equipment, automobiles and the like begin to gradually use energy storage devices such as super capacitors and the like as power sources, and correspondingly, the improvement of the performance of electrode materials is very necessary. The permeation of electrolyte ions, the transport of reactant products, and the transport efficiency of electrons are important factors that affect the energy storage properties of the electrode material; by regulating the appearance of the electrode material, a rapid electron and ion transmission channel can be obtained, so that the energy storage performance of the electrode material is enhanced. However, the electrode material is designed into a nanowire or nanotube structure, so that the electrolyte ion transport space is increased, and meanwhile, compared with a powder sample, the specific surface area of the electrode material is remarkably reduced, so that the reaction active sites are reduced, and the performance of the energy storage property is not facilitated.
The three-dimensional ordered macroporous material has the advantages of strong pore channel arrangement periodicity, uniform distribution, low material diffusion resistance, large pore volume, good compatibility of pore wall components, large adjustable denaturation of chemical environment in pores and the like, and the dielectric constant of the material is also in periodic distribution, so that functional groups such as an embedded type or a copolymerization type and the like are easily introduced through molecular design and assembly, and therefore, the material has very important functions in catalyst carriers, filtering and separating materials, electrode materials, photonic crystal materials, thermal resistance materials and the like. In addition, the three-dimensional ordered macroporous structure has highly ordered nanometer-scale interpenetrated pore channels, greatly shortens the diffusion distance of electrolyte ions, and is more beneficial to charge transfer between an active material and an electrolyte interface. The three-dimensional ordered macroporous structure is optimized into a three-dimensional ordered multi-level pore channel material with mesoporous pore walls, so that the high specific surface area provided by the mesoporous structure of the pore walls is increased, the contact area of the electrode and the electrolyte is increased, and the reactive sites are increased; the macroporous structure can improve the mass transfer performance of the material, so that the electrolyte can well permeate into the electrode, and the advantages of the structures can improve the energy storage performance of the electrode material. Titanium nitride is widely applied to the fields of hard alloy, high-temperature ceramic conductive materials, heat-resistant and wear-resistant materials and the like due to the advantages of high hardness, good chemical stability, low friction coefficient and the like. In recent years, the conductive material has been found to have extremely strong conductivity, and the generated capacitor can be widely applied to new energy storage electrode materials.
Therefore, it is necessary to invent a nickel cobaltate-titanium nitride array electrode material with excellent energy storage performance, a preparation method thereof and energy storage application thereof.
Disclosure of Invention
The purpose of the invention is as follows: in order to overcome the defects in the prior art, the invention provides a nickel cobaltate-titanium nitride array electrode material with excellent energy storage performance, a preparation method and energy storage application thereof.
The technical scheme is as follows: in order to achieve the purpose, the nickel cobaltate/titanium nitride array electrode material comprises a flexible substrate, a titanium nitride nanowire array inner core and a nickel cobaltate shell layer; the nickel cobaltate shell layer is completely wrapped on the surface of the titanium nitride nanowire array core; the titanium nitride nanowire array kernel is internally provided with macroporous channels which are communicated with each other; the pore wall of the macroporous channel is composed of titanium nitride nano particles with mesoporous or microporous structures.
Further, the flexible substrate includes any one of carbon fiber, flexible carbon cloth, flexible carbon paper, and flexible carbon foam.
Further, the thickness of the nickel cobaltate shell layer is 10-40 nm; the nickel cobaltate shell layer is in any one shape structure of a nanowire, a nanosheet, a nanoflower and a sea urchin.
Further, the pore diameter of the macroporous channel is 150-400 nm; 3-6 small holes which are communicated with each other are arranged in each large hole channel; the aperture of the small hole is 40-120 nm; the wall thickness of the macroporous channel is 20-80 nm.
Further, the preparation method of the nickel cobaltate/titanium nitride array electrode material comprises the following steps: comprises the following steps of (a) carrying out,
step (A), preparing monodisperse polystyrene microspheres;
step (B), adopting a centrifugal self-assembly combined heating sedimentation method to obtain a hexagonal tightly-stacked colloidal template which is formed by assembling monodisperse colloidal microspheres on a flexible substrate and is arranged in order;
step (C), preparing an integrated three-dimensional ordered titanium nitride inner core with a hierarchical porous structure growing on a flexible substrate by adopting a vacuum impregnation combined calcination post-treatment method;
and (D) growing a nickel cobaltate shell layer on the surface of the titanium nitride with the three-dimensional ordered hierarchical pore structure by adopting a solvothermal method or an electrochemical deposition method, and finally preparing the nickel cobaltate/titanium nitride array electrode material.
Further, in the step (A), an emulsion polymerization method without an emulsifier is adopted, potassium persulfate is adopted as an initiator in the reaction process, and purified styrene and secondary distilled water are adopted as raw materials; wherein, the mol ratio of the styrene to the potassium persulfate to the secondary distilled water is as follows: 1: (1.0-1.7): (45-60); the reaction temperature is strictly controlled at 70 +/-0.5 ℃; the stirring speed is 400-1000 r/min; the reaction time is 7-24 hours; the whole reaction process is protected by nitrogen, the nitrogen flow rate initiation stage is controlled to be 40-60L/min, and the emulsification stage is controlled to be 20-40L/min;
before the styrene raw material is used, a polymerization inhibitor in the styrene is removed through alkali washing, water washing and reduced pressure distillation, and the method comprises the following specific operations: the alkaline washing adopts any one of sodium hydroxide and potassium hydroxide, the concentration is controlled to be 0.5-2M, and the volume ratio of styrene to sodium hydroxide solution is 1: (1.5-3); the number of alkali washing times is 3-5; then washing with secondary distilled water for 4-6 times until the solution is neutral; finally, carrying out reduced pressure distillation treatment to obtain purified styrene;
in the preparation process, after the secondary distilled water is heated to 70 plus or minus 0.5 ℃, nitrogen is introduced for deoxidation for 20 to 40 minutes, the nitrogen flow rate is controlled to be 40 to 60L/min, then purified styrene and potassium persulfate are sequentially added, the purified styrene and the potassium persulfate are heated to 70 plus or minus 0.5 ℃ before the addition, the nitrogen is introduced for 20 to 40 minutes after the addition, and the nitrogen flow rate is controlled to be 40 to 60L/min.
Further, in the step (B), the centrifugal rotating speed of the centrifugal self-assembly method is controlled to be 8000-; after removing supernatant liquid, uniformly coating the polystyrene microsphere suspension on the surface of the flexible substrate (1), and then heating and settling for 12-36 hours at the heating temperature of 50-100 ℃ by a heating and settling method; finally obtaining the hexagonal close packed polystyrene microsphere (PS) template growing on the flexible carbon substrate.
Further, in the step (C), any one of polystyrene microspheres (PS) and polymethyl methacrylate (PMMA) is used as a macroporous template; the surfactant adopts P123 or F127 nonionic surfactant as a mesoporous template; adopting isopropanol solution of tetrabutyl titanate and isopropyl titanate as mother solution;
n-butyl alcohol is used as a solvent to infiltrate the macroporous template, and the surface contact angle of the macroporous template is improved by the surface tension of the n-butyl alcohol, so that the surface infiltration is improved, and the isopropanol mother liquor of tetrabutyl titanate or isopropyl titanate can be more fully filled into the gaps of the macroporous template; the dipping time is 0.2 to 0.5 hour; carrying out suction filtration after dipping; repeating the steps for 2-5 times to finally obtain the surface modified PS template;
when an isopropanol solution of tetrabutyl titanate is used as a mother solution, the volume ratio of tetrabutyl titanate to isopropanol is 1 (4-8), and the addition amount of P123 or F127 is 3-8 mmol;
dipping the mother solution and the suspension of the PS template in a vacuum drying oven, and fully soaking the mother solution into the PS template by utilizing a vacuum environment so as to synthesize a three-dimensional ordered multi-stage pore canal structure with regular appearance and complete pore wall connection; wherein, the vacuum pressure is controlled to be 0.04-0.08MPa, the dipping time is controlled to be 6-12 hours, and then the suction filtration is carried out to remove the redundant residual mother liquor; repeating the above process for 2-4 times;
the calcination treatment is divided into two steps; the first step, calcining to obtain titanium dioxide with a three-dimensional ordered multilevel pore channel structure, wherein the process adopts inert gas protection, and the heating rate is as follows: the room temperature is 5 ℃/min at-200 ℃, the temperature is 3 ℃/min at 200-350 ℃, the temperature is 2 ℃/min at 350-550 ℃, and the temperature is kept for 1.5-3 hours at 550 ℃; secondly, obtaining the titanium nitride with the three-dimensional ordered hierarchical pore structure through high-temperature nitridation treatment, wherein the reaction conditions are as follows: the ammonia concentration is more than 99.7 percent, and the ammonia flow is 40-70 mL/min; the heating rate is as follows: 5 ℃/min from room temperature to 300 ℃, 2 ℃/min from 300 ℃ to 700 ℃, 1 ℃/min from 700 ℃ to 900 ℃, heat preservation for 1 hour at 900 ℃, and then naturally cooling to room temperature.
Further, the specific operation steps of the solvothermal method in the step (D) are as follows: the mother liquor adopts 0.4-0.7mmol of nickel salt, 0.8-1.5mmol of cobalt salt and 1.8-2.8mmol of urea in ethanol water solution, wherein the molar ratio of the nickel salt to the cobalt salt is 1: 2; the volume ratio of the ethanol to the water is 1: (3-7); the solvothermal reaction temperature is as follows: at the temperature of 100 ℃ and 160 ℃, the reaction time is 4-10 hours; then washing the electrode material by deionized water and ethanol for a plurality of times, calcining the electrode material under the protection of inert gas at the calcining temperature of 300-500 ℃ for 2-4 hours, and finally preparing the integrated flexible three-dimensional ordered hierarchical porous nickel cobaltate/titanium nitride array electrode material;
the specific operation steps of the electrochemical deposition method in the step (D) are as follows: in a standard three-electrode system, titanium nitride of an integrated three-dimensional ordered multi-level pore channel structure growing on a flexible substrate is used as a working electrode, a platinum sheet electrode is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode; the electrolyte adopts 0.02-0.06mmol of nickel salt and 0.08-0.15mmol of cobalt salt in ethanol water solution, wherein the molar ratio of the nickel salt to the cobalt salt is 1: 2; the volume ratio of the ethanol to the water is 1: (3-7); the electrochemical deposition adopts a constant potential method, the set potential is-0.07-1.0V (vs SCE), the deposition time is set to be 30-100 seconds, the prepared sample is carefully washed by absolute ethyl alcohol and deionized water for a plurality of times after the electrodeposition is finished, then the sample is dried in a vacuum oven at 60 ℃, and is calcined under the protection of inert gas, the calcination temperature is 300-.
Further, an ultracapacitor: the electrode material is nickel cobaltate/titanium nitride array electrode material.
Has the advantages that: the nickel cobaltate/titanium nitride array electrode material has a three-dimensional ordered multi-stage pore channel structure, the open macropores provide more active sites and transmission spaces for adsorption and transportation of electrode reaction electrolyte ions, and the high-conductivity titanium nitride provides a rapid electron transmission channel for the nickel cobaltate, so that the defects of poor multiplying power performance and low energy storage efficiency caused by difficulty in rapid transmission of the electrolyte ions and electrons of the electrode material are effectively overcome. The mesoporous structure of the pore wall effectively increases the specific surface area of the material, provides more active sites for reaction, and thus improves the electrochemical energy storage performance. The material can be directly used as a new energy storage electrode material, and has higher practical value and industrial production potential; the preparation process of the electrode material is reliable and easy to implement, and has good industrial production prospect.
Drawings
FIG. 1 is a schematic structural diagram of a nickel cobaltate/titanium nitride array electrode material;
FIG. 2 is a flow chart of a process for preparing a nickel cobaltate/titanium nitride array electrode material;
FIG. 3 is a mass transfer mechanism diagram of the electrode material with the three-dimensional ordered multilevel pore channel structure;
FIG. 4 is an X-ray diffraction spectrum of an integrated flexible three-dimensional ordered hierarchical porous nickel cobaltate/titanium nitride array electrode material, three-dimensional ordered hierarchical porous titanium nitride and nickel cobaltate;
FIG. 5 is a cyclic voltammogram of a nickel cobaltate/titanium nitride array electrode material at different scanning rates;
FIG. 6 is a scanning electron micrograph of the polystyrene template, the titanium nitride array electrode material and the nickel cobaltate/titanium nitride array electrode material;
FIG. 7 is a constant current charging and discharging curve diagram of the nickel cobaltate/titanium nitride array electrode material under different scanning rates.
FIG. 8 is a schematic diagram of the construction of an asymmetric supercapacitor;
fig. 9 is a constant current charge and discharge test curve of an asymmetric supercapacitor.
Wherein, curves a, b and c in fig. 4 represent the X-ray diffraction spectra of the three-dimensional ordered hierarchical porous titanium nitride, nickel cobaltate and integrated flexible three-dimensional ordered hierarchical porous nickel cobaltate/titanium nitride array electrode material respectively; a, b, c, d, e, f and g in FIG. 5 represent cyclic voltammetry curves at different scan rates of 5, 10, 20, 30, 40, 50 and 80mV/s, respectively; in FIG. 6, A, B is a scanning electron microscope image of a polystyrene template, and C-F is a scanning electron microscope image of a three-dimensional ordered hierarchical pore structure titanium nitride array electrode material with different magnifications; in FIG. 7, a, B, c, d, e, f and g in section A represent charge and discharge test curves at different current densities of 1, 2, 3, 4, 5, 6 and 8A/g, respectively, and a, B, c, d and e in section B represent charge and discharge test curves at different current densities of 10, 20, 30, 40 and 50A/g, respectively; the asymmetric supercapacitor in fig. 8 adopts an integrated flexible three-dimensional ordered hierarchical porous nickel cobaltate/titanium nitride array electrode material as a positive electrode, an integrated flexible three-dimensional ordered hierarchical porous titanium nitride array as a negative electrode, and potassium hydroxide-polyvinyl alcohol as a gel electrolyte; the output voltage range of FIG. 9 is 0-1.2V, and the current density is 1-5A/g.
Detailed Description
The present invention will be further described with reference to the accompanying drawings.
Example 1
The structural schematic diagram of the integrated flexible three-dimensional ordered hierarchical porous nickel cobaltate/titanium nitride array electrode material disclosed by the invention is shown in detail in figure 1, and the integrated flexible three-dimensional ordered hierarchical porous nickel cobaltate/titanium nitride array electrode material comprises a flexible substrate (1), a titanium nitride nanowire array core (2) with three-dimensional ordered hierarchical porous pores and a nickel cobaltate shell layer (3); the nickel cobaltate shell layer (3) is completely wrapped on the surface of the titanium nitride nanowire array core (2); the titanium nitride nanowire array has a macroporous channel with a regular height, openness, mutual through connection and an array structure, and the pore wall of the titanium nitride nanowire array is composed of titanium nitride nanoparticles with a mesoporous or microporous structure.
The flexible substrate (1) comprises carbon fiber, flexible carbon cloth, flexible carbon paper, flexible foam carbon and other flexible substrate materials.
The three-dimensional ordered multilevel pore channel titanium nitride nanowire array has a macroporous channel with a highly regular and open structure which is communicated with each other and has an array structure, and the pore wall of the array is composed of titanium nitride nanoparticles with a mesoporous or microporous structure.
The size of the macropores is adjustable, and the adjustable range of the pore size is 150-400 nm; 3-6 small holes can be seen in each big hole, the aperture of each small hole is about 40-120nm, and the holes are open, permeable and completely connected. The thickness of the large pore wall is basically consistent, the thickness of the pore wall is adjustable, and the adjustable range of the thickness is as follows: 20-80nm, and the titanium nitride composing the wall of the macropore is a nano particle with a mesoporous structure.
The thickness of the nickel cobaltate shell layer (3) is about 10-40nm, and the nickel cobaltate shell layer is in the shape of a nano wire, a nano sheet, a nano flower or sea urchin.
Example 2
The invention relates to a process flow chart of the preparation of an integrated flexible three-dimensional ordered hierarchical porous nickel cobaltate/titanium nitride array electrode material, which is detailed in figure 2 and mainly comprises the following steps: (A) preparing monodisperse polystyrene microspheres; (B) assembling monodisperse colloidal microspheres into a regularly arranged hexagonal close-packed colloidal template on a flexible substrate by adopting a centrifugal self-assembly combined heating sedimentation method; (C) preparing an integrated three-dimensional ordered titanium nitride inner core with a hierarchical pore structure, which grows on a flexible substrate, by adopting a vacuum impregnation combined with a calcination post-treatment method; (D) growing a nickel cobaltate shell layer on the surface of the titanium nitride with the integrated three-dimensional ordered hierarchical pore structure by a solvothermal method or an electrochemical deposition method:
(A) preparing monodisperse polystyrene microspheres: the polystyrene microsphere is prepared by an emulsifier-free emulsion polymerization method by using potassium persulfate as an initiator and styrene and secondary distilled water as raw materials.
The styrene can be used after removing a polymerization inhibitor in the styrene by alkali washing, water washing and reduced pressure distillation, wherein the alkali washing adopts alkali solution such as sodium hydroxide, potassium hydroxide and the like, preferably sodium hydroxide, the concentration is controlled to be 0.5-2M, and the volume ratio of the styrene to the sodium hydroxide solution is 1: (1.5-3); the number of alkali washing times is 3-5; then washing with secondary distilled water for 4-6 times until the solution is neutral; finally, the purified styrene is obtained by reduced pressure distillation treatment.
The mol ratio of the styrene to the potassium persulfate to the secondary distilled water is as follows: 1: (1.0-1.7): (45-60); the reaction temperature is strictly controlled at 70 +/-0.5 ℃; the stirring speed is controlled at 400-1000 r/min; the reaction time is 7-24 hours; the whole reaction process is protected by nitrogen, the nitrogen flow rate initiation stage is controlled to be 40-60L/min, and the emulsification stage is controlled to be 20-40L/min.
The synthesis uses a four-neck bottle, and nitrogen gas introduction, temperature measurement, mechanical stirring and feeding are respectively carried out at four openings. When the reaction starts, firstly adding secondary distilled water into a four-necked bottle, heating to 70 +/-0.5 ℃, introducing nitrogen for deoxidation (the flow rate is controlled to be 40-60L/min) for 20-40 minutes, then heating the purified styrene to 70 +/-0.5 ℃, adding the styrene into the four-necked bottle, introducing nitrogen for deoxidation for 20-40 minutes, finally adding potassium persulfate into a small amount of water for dissolution, heating to 70 +/-0.5 ℃, adding the mixture into the four-necked bottle, and mechanically stirring for reaction for 7-24 hours; finally obtaining the polystyrene microsphere.
(B) The method comprises the following steps of (1) assembling monodisperse colloidal microspheres on a flexible substrate to form a regularly arranged hexagonal close-packed colloidal template by adopting a centrifugal self-assembly combined heating sedimentation method: centrifuging the polystyrene microspheres prepared in the step (A) at a high speed for 24-48 hours, controlling the centrifugal rotating speed at 8000-; finally, the hexagonal close-packed PS template growing on the flexible carbon substrate is obtained.
(C) Preparing an integrated three-dimensional ordered titanium nitride inner core with a hierarchical porous structure growing on a flexible substrate by combining vacuum impregnation with a post-calcination treatment method: first of all with methanol (CH)3OH), n-butanol (C)4H9OH) and other solvents are used for infiltrating the hexagonal close packed PS template growing on the flexible carbon substrate, and methanol (CH) is used3OH), n-butanol (C)4H9OH) and the like to improve the surface contact angle of the macroporous templates such as polystyrene microspheres (PS), polymethyl methacrylate (PMMA) and the like, thereby improving the surface wettability, enabling isopropanol mother liquor of organic titanium such as tetrabutyl titanate, isopropyl titanate and the like to be fully filled in the gaps of the macroporous templates, the dipping time is 0.2-0.5 h, carrying out suction filtration and drying after dipping, and repeating the steps for 2-5 times to finally obtain the surface modified PS template. Isopropanol is used as a solvent of organic titanium such as tetrabutyl titanate, isopropyl titanate and the like, and nonionic surface active agents such as P123 or F127 and the like are added, wherein the volume ratio of tetrabutyl titanate to isopropanol is 1 (4-8), and the addition amount of the nonionic surface active agents such as P123 or F127 and the like is 3-8 mmol. And then, a vacuum impregnation method is used, and a vacuum environment is utilized to promote the organic titanium mother solution to be fully soaked into the polystyrene template so as to synthesize a three-dimensional ordered multi-stage pore channel structure with regular and perfect appearance and complete pore wall connection. Wherein, the vacuum pressure is controlled to be 0.04-0.08MPa, the dipping time is controlled to be 6-12 hours, and then the suction filtration is carried out to remove the redundant residual mother liquor; repeating the process for 2-4 times, calcining the product at high temperature under the protection of inert gases such as nitrogen, argon and the like, wherein the heating rate is as follows: the room temperature is 5 ℃/min at-200 ℃, the temperature is 3 ℃/min at 200-350 ℃, the temperature is 2 ℃/min at 350-550 ℃, and the temperature is kept for 1.5-3 hours at 550 ℃; then, performing high-temperature nitridation treatment to obtain the titanium nitride with the three-dimensional ordered hierarchical pore structure, wherein the reaction conditions are as follows: the ammonia concentration is more than 99.7 percent, and the ammonia flow is 40-70 mL/min; the heating rate is as follows: keeping the temperature of the mixture at the room temperature to 300 ℃ for 5 ℃/min, 300 to 700 ℃ for 2 ℃/min and 700 to 900 ℃ for 1 ℃/min, keeping the temperature of the mixture at 900 ℃ for 1 hour, and then naturally cooling the mixture to the room temperature; and preparing the titanium nitride inner core with the integrated three-dimensional ordered hierarchical pore canal structure growing on the flexible substrate.
(D) Growing a nickel cobaltate shell layer on the surface of the titanium nitride with the integrated three-dimensional ordered hierarchical pore structure by a solvothermal method or an electrochemical deposition method:
a solvothermal method: the mother liquor adopts 0.4-0.7mmol of nickel salt, 0.8-1.5mmol of cobalt salt and 1.8-2.8mmol of urea in ethanol water solution, wherein the molar ratio of the nickel salt to the cobalt salt is 1: 2; the volume ratio of the ethanol to the water is 1: (3-7). The solvothermal reaction temperature is as follows: 100 ℃ and 160 ℃, and the reaction time is 4-10 hours. And then, washing the precursor with deionized water and ethanol for several times, calcining under the protection of inert gas at the temperature of 300-500 ℃ for 2-4 hours, and finally obtaining the integrated flexible three-dimensional ordered hierarchical porous nickel cobaltate/titanium nitride array electrode material.
Electrochemical deposition method: the electrochemical deposition adopts an integrated three-dimensional ordered multilevel pore channel structure titanium nitride growing on a flexible substrate in a standard three-electrode system as a working electrode, a platinum sheet electrode as a counter electrode and a saturated calomel electrode as a reference electrode. The electrolyte adopts 0.02-0.06mmol of nickel salt and 0.08-0.15mmol of cobalt salt in ethanol water solution, wherein the molar ratio of the nickel salt to the cobalt salt is 1: 2; the volume ratio of the ethanol to the water is 1: (3-7). The electrochemical deposition adopts a constant potential method, the set potential is-0.07-1.0V (vs SCE), the deposition time is set to be 30-100 seconds, the prepared sample is carefully washed by absolute ethyl alcohol and deionized water for a plurality of times after the electrodeposition is finished, then the sample is dried in a vacuum oven at 60 ℃, and is calcined under the protection of inert gas at the calcination temperature of 300-500 ℃ for 2-4 hours, and finally the integrated flexible three-dimensional ordered hierarchical porous nickel cobaltate/titanium nitride array electrode material is prepared.
Example 3
The mass transfer mechanism diagram of the integrated flexible three-dimensional ordered hierarchical porous nickel cobaltate/titanium nitride array electrode material is shown in figure 3 in detail. The electrode material provided by the invention has ordered nanoscale interconnected pore channels, so that the diffusion distance of electrolyte ions is greatly shortened, and charge transfer between an active material and an electrolyte interface is facilitated. The open macroporous channel is more favorable to the transportation of electrolyte ion, greatly reduced mass transfer distance, the high specific surface area that the mesostructure of pore wall provided increases the area of contact of electrode and electrolyte, increases the reactive site. The advantages of the structures can effectively improve the energy storage performance of the electrode material.
Example 4
The integrated flexible three-dimensional ordered hierarchical porous nickel cobaltate/titanium nitride array electrode material and the X-ray diffraction spectrogram of the three-dimensional ordered hierarchical porous titanium nitride and the nickel cobaltate are shown in figure 4 in detail. As can be seen from the X-ray diffraction spectrum of the three-dimensionally ordered multi-level channel titanium nitride of FIG. 4a, the characteristic diffraction peaks at 36.9, 43.1 and 62.8 correspond to the (111), (200) and (220) crystal planes of titanium nitride, respectively. In addition, in the XRD spectrum of the titanium nitride, the characteristic peaks of the titanium dioxide at 25.4 degrees and 41.4 degrees disappear, and the characteristic diffraction peak of the titanium nitride with the diffraction angle 2 theta of 54.5 degrees appears, so that the titanium dioxide is converted into the titanium nitride with the cubic phase with high conductivity after the high-temperature nitridation treatment. From the X-ray diffraction spectra of the nickel cobaltate of FIG. 4b and the integrated flexible three-dimensional ordered multi-graded-channel nickel cobaltate/titanium nitride array of FIG. 4c, it can be seen that the characteristic diffraction peaks at 31.14 °, 36.69 °, 44.62 °, 59.09 ° and 64.98 ° correspond to the (220), (311), (400), (511) and (440) crystal planes of the spinel-structured nickel cobaltate. However, in fig. 4c, no distinct characteristic peak of titanium nitride is observed, but the diffraction peaks corresponding to the (311), (400) and (511) crystal planes are broadened to some extent, which is mainly caused by the overlap of the characteristic diffraction peaks of titanium nitride at 36.9 °, 43.1 ° and 62.8 ° with the characteristic diffraction peaks of nickel cobaltate.
Example 5
The scanning electron microscope picture of the integrated flexible three-dimensional ordered hierarchical porous nickel cobaltate/titanium nitride array electrode material and the polystyrene microsphere is shown in figure 6 in detail. FIG. 6, section A-B, is a scanning electron micrograph of polystyrene microspheres, which are uniform in size and about 400nm in diameter, as can be seen from section A of FIG. 6; as can be seen from the part A-B of FIG. 6, the polystyrene templates are arranged layer by layer and present a hexagonal close-packed structure. And the part C-E in the figure 6 is a scanning electron microscope picture of the titanium nitride electrode material with the integrated three-dimensional ordered hierarchical pore structure. As can be seen from part C of FIG. 6, the sample has a three-dimensional ordered hierarchical pore structure, the pore diameter of the macropore is about 250nm, and the size of the macropore of the material is reduced compared with that of polystyrene microspheres, mainly due to the reduction of the pore diameter caused by calcination. The size of the pores mainly depends on the diameter of the polystyrene microspheres as templates, so that three-dimensional ordered multi-stage pore channel structures with different sizes can be obtained by adjusting the diameter of the polystyrene microspheres. And it can be seen from the figure that the pore wall thickness of the macropores composed of titanium nitride nanoparticles is substantially uniform. Six small holes can be seen in each big hole, the aperture of each small hole is about 60-80nm, three of the small holes are arranged at the bottom of the big hole, and three of the small holes are arranged on the side surface of the big hole, the appearance is consistent with the arrangement of a face-centered cube of a polystyrene template, and the appearance shows that the holes are open, transparent and completely connected. The porous structure has good permeability and is more beneficial to the transmission of electrolyte ions. In the part D of the graph 6, the sample appearance is neat and ordered, a multilayer structure arranged layer by layer is presented, a large-area three-dimensional ordered macroporous structure is presented, and the multistage pore channel structure and a large number of open pore channels are beneficial to the diffusion and transportation of electrons and electrolyte ions in the reaction process, so that the electrode reaction efficiency and the utilization rate of an electrode material are improved, and the activity of the electrode material is enhanced. Part E of the graph 6 is the three-dimensional ordered macroporous titanium nitride prepared by soaking the polystyrene template in the methanol bath in the preparation process, and it can be seen from the graph that although the sample presents a three-dimensional ordered macroporous structure, the pore wall is rough and partially incomplete, which is mainly caused by that the organic titanium mother liquor can not be completely filled into the polystyrene template gap due to the interface effect on the surface of the polystyrene microsphere. Therefore, the polystyrene template plays an important role in preparing the three-dimensional ordered macroporous structure with excellent morphology through methanol infiltration. Part F of the graph in FIG. 6 is a scanning electron microscope image of the integrated flexible three-dimensional ordered hierarchical porous nickel cobaltate/titanium nitride array electrode material, and it can be seen from the image that nickel cobaltate nanosheets uniformly cover the surface of the integrated three-dimensional ordered hierarchical porous titanium nitride, the surface presents a thin lamellar structure with a thickness of about 30nm, and macroporous channels which are beneficial to diffusion and transportation of electrons and electrolyte ions are reserved.
Example 6
The cyclic voltammetry curve of the integrated flexible three-dimensional ordered hierarchical porous nickel cobaltate/titanium nitride array electrode material is shown in figure 5 in detail. From FIG. 5, a pair of redox peaks is clearly observed, due to the reversible redox reaction of M-O/M-O-OH (M stands for cobalt and nickel ions), as shown in the following equation:
MxOy+OH-→MOOH+H2O+e-
and the increase of the area surrounded by the cyclic voltammetry curve is basically in direct proportion to the increase of the scanning rate, which means that the integrated flexible three-dimensional ordered hierarchical porous nickel cobaltate/titanium nitride array electrode material has better reversibility and still has faster ion transmission and exchange capacity at higher scanning rate.
Example 7
The cyclic voltammetry curve and the charging and discharging curve of the integrated flexible three-dimensional ordered multi-stage pore nickel cobaltate/titanium nitride array electrode material are shown in figure 7 in detail. As shown in part A of the drawing 7, when the current density is small (1-8A/g), almost no potential drop is observed, indicating that the sample has good conductivity. According to the calculation of the constant current charge-discharge curve, when the current density is 1, 2, 3, 4, 5, 6 and 8A/g, the corresponding mass specific capacitance is 1652, 1618, 1572, 1516, 1481, 1424 and 1396F/g respectively. Part B of fig. 7 is a charge-discharge curve at a high current density, and it can be found from calculation of the constant current charge-discharge curve that the corresponding mass-specific capacitances are 1381, 1292, 1201, 1172 and 1128F/g at current densities of 10, 20, 30, 40 and 50A/g, respectively, and show higher mass-specific capacitances. As the current density increased from 1A/g to 10A/g, the capacity retention was 83.6% of the initial capacity. It is noteworthy that the capacity retention also reached 68.3% of the initial capacitance when the current density was increased from 1A/g to a higher current density of 50A/g, demonstrating excellent rate performance.
The sample has higher specific capacitance and excellent rate performance, and is mainly attributed to the following aspects:
(1) the three-dimensional ordered hierarchical porous titanium nitride in the sample has higher conductivity, can effectively improve the conductivity of nickel cobaltate, and improves the charge transfer efficiency of the composite material, thereby improving the redox reaction efficiency and improving the electrochemical performance of the material.
(2) The three-dimensional ordered hierarchical pore structure can provide a larger specific surface area, increase reactive sites to adsorb electrolyte ions, shorten diffusion paths of reaction ions and electron transfer paths, minimize ion transport resistance and show excellent rate performance even under high current density.
(3) The sample is an integrated electrode material, so that the use of a binder is avoided, the defects of few reactive active sites and high interface impedance caused by the use of the binder are effectively reduced, and the specific capacitance and the rate capability are improved.
Example 8
As shown in FIG. 8, the invention adopts an integrated flexible three-dimensional ordered hierarchical porous nickel cobaltate/titanium nitride array electrode material as a positive electrode, an integrated flexible three-dimensional ordered hierarchical porous titanium nitride array as a negative electrode, and potassium hydroxide-polyvinyl alcohol as a gel electrolyte to construct an asymmetric flexible supercapacitor. FIG. 9 shows the constant current charging and discharging test curve of the asymmetric all-solid-state supercapacitor with the output voltage range of 0-1.2V and the current density of 1-5A/g, in which there is almost no potential drop observed in the constant current charging and discharging test curve, and the specific capacitances are calculated according to the constant current charging and discharging curve to be 108.5, 96.4, 81.3, 76.5 and 69.2F/g, respectively. With the current density increased from 1A/g to 10A/g, the capacity retention rate is 63.8% of the initial capacitance, and a good rate performance is shown, so that the asymmetric supercapacitor is mainly benefited from the fact that an integrated flexible three-dimensional ordered multi-level pore nickel cobaltate/titanium nitride array electrode material with a high rate performance is adopted. The power density and energy density of the asymmetric supercapacitor can be calculated according to the following formulas (1-2):
according to calculation, when the power density is 600, 1200, 1800, 2400 and 3000W/kg, the energy density of the asymmetric supercapacitor is 21.7, 19.3, 16.3, 15.3 and 13.8W h/kg respectively, and the higher energy density is shown, which means that the integrated flexible three-dimensional ordered hierarchical porous nickel cobaltate/titanium nitride array electrode material has better application prospect.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (8)
1. A nickel cobaltate/titanium nitride array electrode material is characterized in that: comprises a flexible substrate (1), a titanium nitride nanowire array inner core (2) and a nickel cobaltate shell layer (3); the nickel cobaltate shell layer (3) is completely wrapped on the surface of the titanium nitride nanowire array core (2); the titanium nitride nanowire array inner core (2) is internally provided with macroporous channels which are communicated with each other; the hole wall of the macroporous channel consists of titanium nitride nano particles with a mesoporous or microporous structure;
the preparation method of the nickel cobaltate/titanium nitride array electrode material is characterized by comprising the following steps of: comprises the following steps of (a) carrying out,
step (A), preparing monodisperse polystyrene microspheres;
step (B), adopting a centrifugal self-assembly combined heating sedimentation method to obtain a hexagonal tightly-stacked colloidal template which is formed by assembling monodisperse colloidal microspheres on a flexible substrate and is arranged in order;
step (C), preparing an integrated three-dimensional ordered titanium nitride inner core with a hierarchical porous structure growing on a flexible substrate by adopting a vacuum impregnation combined calcination post-treatment method;
growing a nickel cobaltate shell layer on the surface of the titanium nitride with the three-dimensional ordered multi-level pore channel structure by adopting a solvothermal method or an electrochemical deposition method, and finally preparing the nickel cobaltate/titanium nitride array electrode material;
in the step (C), any one of polystyrene microspheres (PS) and polymethyl methacrylate (PMMA) is adopted as a macroporous template; the surfactant adopts P123 or F127 nonionic surfactant as a mesoporous template; adopting isopropanol solution of tetrabutyl titanate and isopropyl titanate as mother solution;
n-butyl alcohol is used as a solvent to infiltrate the macroporous template, and the surface contact angle of the macroporous template is improved by the surface tension of the n-butyl alcohol, so that the surface infiltration is improved, and the isopropanol mother liquor of tetrabutyl titanate or isopropyl titanate can be more fully filled into the gaps of the macroporous template; the dipping time is 0.2 to 0.5 hour; carrying out suction filtration after dipping; repeating the steps for 2-5 times to finally obtain the surface modified PS template;
when an isopropanol solution of tetrabutyl titanate is used as a mother solution, the volume ratio of tetrabutyl titanate to isopropanol is 1 (4-8), and the addition amount of P123 or F127 is 3-8 mmol;
dipping the mother solution and the suspension of the PS template in a vacuum drying oven, and fully soaking the mother solution into the PS template by utilizing a vacuum environment so as to synthesize a three-dimensional ordered multi-stage pore channel structure with regular appearance and complete pore wall connection; wherein, the vacuum pressure is controlled to be 0.04-0.08MPa, the dipping time is controlled to be 6-12 hours, and then the suction filtration is carried out to remove the redundant residual mother liquor; repeating the above process for 2-4 times;
the calcination treatment is divided into two steps; the first step, calcining to obtain titanium dioxide with a three-dimensional ordered multilevel pore channel structure, wherein the process adopts inert gas protection, and the heating rate is as follows: the room temperature is 5 ℃/min at-200 ℃, 3 ℃/min at 350 ℃ and 200 ℃ and 550 ℃ are 2 ℃/min, and the temperature is kept for 1.5-3 hours at 550 ℃; secondly, obtaining the titanium nitride with the three-dimensional ordered hierarchical pore structure through high-temperature nitridation treatment, wherein the reaction conditions are as follows: the ammonia concentration is more than 99.7 percent, and the ammonia flow is 40-70 mL/min; the heating rate is as follows: 5 ℃/min from room temperature to 300 ℃, 2 ℃/min from 300 ℃ to 700 ℃, 1 ℃/min from 700 ℃ to 900 ℃, heat preservation for 1 hour at 900 ℃, and then naturally cooling to room temperature.
2. The nickel cobaltate/titanium nitride array electrode material as claimed in claim 1, wherein: the flexible substrate (1) comprises any one of carbon fiber, flexible carbon cloth, flexible carbon paper and flexible foam carbon.
3. The nickel cobaltate/titanium nitride array electrode material as claimed in claim 1, wherein: the thickness of the nickel cobaltate shell layer (3) is 10-40 nm; the nickel cobaltate shell layer (3) is in any one shape structure of a nanowire, a nanosheet, a nanoflower and a sea urchin.
4. The nickel cobaltate/titanium nitride array electrode material as claimed in claim 1, wherein: the pore diameter of the macroporous channel is 150-400 nm; 3-6 small holes which are communicated with each other are arranged in each large hole channel; the aperture of the small hole is 40-120 nm; the wall thickness of the macroporous channel is 20-80 nm.
5. The method for preparing the nickel cobaltate/titanium nitride array electrode material according to claim 1, wherein the method comprises the following steps: in the step (A), an emulsion polymerization method without an emulsifier is used, potassium persulfate is used as an initiator in the reaction process, and purified styrene and secondary distilled water are used as raw materials; wherein, the mol ratio of the styrene to the potassium persulfate to the secondary distilled water is as follows: 1: (1.0-1.7): (45-60); the reaction temperature is strictly controlled at 70 +/-0.5 ℃; the stirring speed is 400-1000 r/min; the reaction time is 7-24 hours; the whole reaction process is protected by nitrogen, the nitrogen flow rate initiation stage is controlled to be 40-60L/min, and the emulsification stage is controlled to be 20-40L/min;
before the styrene raw material is used, the polymerization inhibitor in the styrene is removed by alkali washing, water washing and reduced pressure distillation, and the specific operation is as follows: the alkaline washing adopts any one of sodium hydroxide and potassium hydroxide, the concentration is controlled to be 0.5-2M, and the volume ratio of styrene to sodium hydroxide solution is 1: (1.5-3); the number of alkaline washing times is 3-5; then washing with secondary distilled water for 4-6 times until the solution is neutral; finally, carrying out reduced pressure distillation treatment to obtain purified styrene;
in the preparation process, after the secondary distilled water is heated to 70 plus or minus 0.5 ℃, nitrogen is introduced for deoxidation for 20 to 40 minutes, the nitrogen flow rate is controlled to be 40 to 60L/min, then purified styrene and potassium persulfate are sequentially added, the purified styrene and the potassium persulfate are heated to 70 plus or minus 0.5 ℃ before the addition, the nitrogen is introduced for 20 to 40 minutes after the addition, and the nitrogen flow rate is controlled to be 40 to 60L/min.
6. The method for preparing the nickel cobaltate/titanium nitride array electrode material according to claim 1, wherein the method comprises the following steps: in the step (B), the centrifugal rotation speed of the centrifugal self-assembly method is controlled at 8000-15000r/min, and the centrifugal time is controlled at 24-48 hours; after removing supernatant liquid, uniformly coating the polystyrene microsphere suspension on the surface of the flexible substrate (1), and then heating and settling for 12-36 hours at 50-100 ℃ by a heating and settling method; finally, the hexagonal close-packed polystyrene microsphere (PS) template growing on the flexible carbon substrate is obtained.
7. The method for preparing the nickel cobaltate/titanium nitride array electrode material according to claim 1, wherein the method comprises the following steps: the solvent thermal method in the step (D) comprises the following specific operation steps: the mother liquor adopts 0.4-0.7mmol of nickel salt, 0.8-1.5mmol of cobalt salt and 1.8-2.8mmol of urea in ethanol water solution, wherein the molar ratio of the nickel salt to the cobalt salt is 1: 2; the volume ratio of ethanol to water is 1: (3-7); the solvothermal reaction temperature is as follows: at the temperature of 100 ℃ and 160 ℃, the reaction time is 4-10 hours; then washing the electrode material by deionized water and ethanol for a plurality of times, calcining the electrode material under the protection of inert gas at the calcining temperature of 300-500 ℃ for 2-4 hours to finally prepare the integrated flexible three-dimensional ordered hierarchical porous nickel cobaltate/titanium nitride array electrode material;
the specific operation steps of the electrochemical deposition method in the step (D) are as follows: in a standard three-electrode system, titanium nitride of an integrated three-dimensional ordered multi-level pore channel structure growing on a flexible substrate is used as a working electrode, a platinum sheet electrode is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode; the electrolyte adopts 0.02-0.06mmol of nickel salt and 0.08-0.15mmol of cobalt salt in ethanol water solution, wherein the molar ratio of the nickel salt to the cobalt salt is 1: 2; the volume ratio of the ethanol to the water is 1: (3-7); the electrochemical deposition adopts a constant potential method, the set potential is-0.07-1.0V (vs SCE), the deposition time is set to be 30-100 seconds, the prepared sample is carefully washed by absolute ethyl alcohol and deionized water for a plurality of times after the electrodeposition is finished, then the sample is placed in a vacuum oven to be dried at 60 ℃, and calcined under the protection of inert gas, the calcination temperature is 300-500 ℃, and the calcination time is 2-4 hours, and finally the integrated flexible three-dimensional ordered hierarchical porous nickel cobaltate/titanium nitride array electrode material is prepared.
8. A supercapacitor, characterized by: the electrode material is the nickel cobaltate/titanium nitride array electrode material in claim 1.
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