CN108183039B - Preparation method of carbon-modified titanium niobate material, lithium ion capacitor and negative electrode slurry thereof - Google Patents

Preparation method of carbon-modified titanium niobate material, lithium ion capacitor and negative electrode slurry thereof Download PDF

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CN108183039B
CN108183039B CN201711309732.9A CN201711309732A CN108183039B CN 108183039 B CN108183039 B CN 108183039B CN 201711309732 A CN201711309732 A CN 201711309732A CN 108183039 B CN108183039 B CN 108183039B
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titanium niobate
lithium ion
ion capacitor
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CN108183039A (en
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张海涛
刘奥
张锁江
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Institute of Process Engineering of CAS
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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
    • 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
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • 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
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • 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
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • 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
    • 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 discloses a preparation method of a carbon-modified titanium niobate material and application of the carbon-modified titanium niobate material in a lithium ion capacitor. The invention adopts a solvothermal method to prepare the titanium niobate and modified porous graphene composite electrode material. The titanium niobate composite material has excellent performances of high energy density, high power density, high multiplying power and the like in the ionic liquid gel electrolyte, and the ionic liquid gel electrolyte effectively widens the electrochemical window of a lithium ion capacitor, thereby improving the energy density and the high pressure resistance of a lithium ion battery. The method has the advantages of simple process, convenient operation, low cost, low raw material price, low production cost and easy amplification.

Description

Preparation method of carbon-modified titanium niobate material, lithium ion capacitor and negative electrode slurry thereof
Technical Field
The invention belongs to the technical field of energy storage materials, and relates to a preparation method of a high-performance carbon-modified titanium niobate material, the carbon-modified titanium niobate material, a lithium ion capacitor and a negative electrode slurry of the lithium ion capacitor.
Background
Despite the significant advances made in lithium ion capacitors in recent years, the development of supercapacitors with high safety performance, high energy density, high power density and low cost remains a hot spot of research. Particularly, in recent years, titanium niobate is widely used as an energy storage material in super capacitors and lithium ion batteries. The titanium niobate used as the negative electrode material of the lithium ion capacitor has relatively high oxidation-reduction potential, effectively avoids the formation of lithium dendrite, improves the safety performance of the lithium ion capacitor, and has the theoretical specific capacity up to 387mAh g-1Much greater than lithium titanate (175mAh g)-1) And has better application foundation. And the titanium niobate also has better high-rate charge-discharge performance and cycle performance, and is an ideal lithium ion capacitor cathode material. The excellent electrochemical performance of the titanium niobate has been obtained by famous researchers at home and abroadThere are some problems to be solved, such as poor conductivity.
The graphene has high conductivity, can adsorb static electricity and be used for a super capacitor, can be used as a lithium battery cathode by being embedded with lithium ions, and is widely applied to various energy storage devices. Therefore, the graphene and the titanium niobate are compounded, so that the electronic conductivity of the composite material can be improved, the high-speed diffusion of electrolyte ions in an electrode is facilitated, a part of battery capacity can be provided, and the energy density and the power density of the composite material are greatly improved. The modified graphene can effectively improve the conductivity of the material, increase the active sites of the material, and increase the specific surface junction of the material, thereby improving the cycle performance and the rate capability of the material. And the titanium niobate composite material has a porous structure, and is easy for the transmission of electrons and ions, so that the overall performance of the titanium niobate composite material can be improved. Therefore, the research on how to improve the conductivity of the titanium niobate so as to improve the performance of the material has important significance for expanding the application of the titanium niobate material.
Disclosure of Invention
The invention aims to provide a preparation method of a high-performance carbon-modified titanium niobate material and a novel high-performance carbon-modified titanium niobate material.
The invention firstly provides a preparation method of a carbon-modified titanium niobate material, which comprises the following steps:
1) dissolving a titanium source and a niobium source in an organic solvent at an equal molar ratio, adding oxalic acid, and fully stirring to obtain a mixed solution;
2) adding graphene oxide powder or a solution thereof into the mixed solution obtained in the step 1), and fully and uniformly mixing to obtain a uniform turbid liquid;
3) heating the turbid liquid obtained in the step 2), naturally cooling to room temperature to obtain a precipitate, and washing and drying the obtained precipitate to obtain a composite precursor of titanium niobate and graphene;
4) dispersing the composite precursor obtained in the step 3) into water, adding hydrogen peroxide, and performing hydrothermal reaction after uniform dispersion to obtain a modified graphene-coated titanium niobate composite precursor;
5) carrying out heat treatment on the precursor obtained in the step 4) to obtain the carbon-modified titanium niobate material.
As a better alternative to the above process, the titanium source and the niobium source are preferably added in equal molar ratios.
As a more preferable alternative to the above method, the concentration of the titanium source and the niobium source in the mixed solution obtained in step 1) is 0.1mmol to 10 mol/L.
As a better alternative to the above method, the organic solvent in step 1) comprises one or more of ethanol, ethylene glycol and isopropanol.
As a better alternative of the method, the niobium source in the step 1) comprises one or more of niobium fluoride, niobium ethoxide, niobium pentachloride, niobium oxalate and niobium ammonium oxalate.
As a better choice of the method, the titanium source in the step 1) is one or a mixture of more of titanium tetraisopropoxide, titanium tetrachloride, titanium sulfate and butyl titanate.
As a better choice of the above method, step 2) further includes adding a surfactant to a mixture obtained by mixing the graphene oxide powder or the solution thereof with the mixed solution obtained in step 1), where the surfactant includes one or more of cetyl trimethyl ammonium bromide, alkylphenol ethoxylates, octylphenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, polyethylene pyrrolidone, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, and polyoxyethylene-polyoxypropylene-polyoxyethylene.
As a better alternative of the above method, the concentration of the surfactant in the step 2) is 0.1mmol/L-10 mol/L.
As a better choice of the method, the preset heating temperature in the step 3) is 150-200 ℃, and the reaction time is 6-48 h.
As a better choice of the method, the concentration of the hydrogen peroxide (30 w%) in the reaction system in the step 4) is 0.1mmol/L-1 mol/L.
As a better choice of the method, the heat treatment temperature in the step 5) is 500-1200 ℃, the treatment time is 2-12h, and the protective atmosphere is nitrogen or argon.
A typical preparation method for preparing a high-performance carbon-modified titanium niobate material is as follows:
1) dissolving a titanium source and a niobium source in an organic solvent at an equal molar ratio, adding a proper amount of oxalic acid, and fully stirring to obtain a mixed solution;
2) adding a certain amount of graphene oxide powder or solution into the mixed solution obtained in the step 1), fully stirring and ultrasonically dispersing, and then adding a proper amount of surfactant to obtain a uniform suspension;
3) transferring the suspension obtained in the step 2) into a reaction kettle, heating and reacting in a constant-temperature drying oven at a preset heating temperature, naturally cooling to room temperature to obtain a precipitate, washing the precipitate with deionized water and ethanol for several times respectively, and freeze-drying to obtain a composite precursor of titanium niobate and graphene;
4) dispersing the composite precursor obtained by freeze drying in the step 3) into water, adding a proper amount of hydrogen peroxide, fully stirring and ultrasonically dispersing, performing hydrothermal reaction in a constant-temperature drying oven, and then performing vacuum drying to obtain a carbon-modified titanium niobate material precursor;
5) carrying out heat treatment on the precursor obtained in the step 4).
The invention provides a carbon-modified titanium niobate material prepared by any one of the methods.
As a more preferable alternative to the above-mentioned titanium niobate material modified with carbon, the titanium niobate material modified with carbon has a size of not more than 50nm and the content of carbon in the titanium niobate material modified with carbon is 0.5 to 20 wt%.
The invention provides a novel carbon-modified titanium niobate material, which comprises CxTiNb2O7The carbon-modified titanium niobate material has a size of not more than 50nm, and the value range of x is 0.05-0.2.
As a better choice of the carbon-modified titanium niobate material, the carbon-modified titanium niobate material has the capacity of not less than 213.6mAh/g at 50 ℃.
The invention also provides a lithium ion capacitor which comprises a positive electrode material, a negative electrode material and a solid gel electrolyte.
As a better alternative of the above lithium ion capacitor, the housing of the lithium ion capacitor is an aluminum housing or an aluminum-plastic film.
As a better alternative of the above lithium ion capacitor, the negative electrode sheet comprises a copper foil and a negative electrode slurry, and is characterized in that: the negative electrode slurry contains 70 wt% -95 wt% of titanium niobate composite material, 1.5 wt% -15 wt% of conductive agent and 1.5 wt% -15 wt% of binder. The titanium niobate composite material can be a composite material prepared according to the method, and can also be a composite material for forming the material.
As a better alternative to the above lithium ion capacitor, the positive electrode material includes at least one of activated carbon, graphene, or carbon nanotubes.
As a more preferable alternative of the above lithium ion capacitor, the positive electrode material layer includes: 80-90 wt% of double-layer energy storage carbon material, 1.5-15 wt% of conductive agent and 1.5-10 wt% of binder.
As a better choice of the lithium ion capacitor, the conductive agent is one or a mixture of several of acetylene black, ketjen black, carbon nanotubes, graphene or Super-P.
As a better alternative to the above lithium ion capacitor, the gelling agent in the solid gel electrolyte comprises one or more of polyacrylonitrile, polymethyl methacrylate, polyethylene oxide, polypropylene oxide, polyvinyl pyridine, and a copolymer of vinylidene fluoride and hexafluoropropylene.
As a more preferable alternative to the above lithium ion capacitor, the solid gel electrolyte ionic liquid includes 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, N-methyl-N-propylpiperidine bis (trifluoromethylsulfonyl) imide, N, N-butyl-N-ethylpyrrolidine-N, N-bis (trifluoromethylsulfonyl) imide, N-methyl-N-butylpyrrolidine bis (trifluoromethylsulfonyl) imide, 1-methyl-3-ethylimidazolium bis (trifluoromethylsulfonyl) imide, 1-methyl-3-propylimidazolium tetrafluoroborate, 1-methyl-3-ethylimidazolium tetrafluoroborate, 1-methyl-3-hexylimidazolium tetrafluoroborate, tetrafluoroborate, One or more of 2, 3-dimethyl-1-octylimidazole trifluoromethanesulfonate, 2, 3-dimethyl-1-octylimidazole tetrafluoroborate, N-methyl-N-propylpyrrolidine bis (trifluoromethylsulfonyl) imide, and N-methyl-N-propylpyrrole-bis (trifluoromethylsulfonyl) imide.
As a better choice of the lithium ion capacitor, the addition amount of the ionic liquid accounts for 5-50% of the total weight of the mixed solvent.
As a more preferable alternative to the above lithium ion capacitor, the lithium salt electrolyte is lithium bis (trifluoromethyl) sulfonimide (LiTFSI), lithium bis (fluoroxanthimide) (LiFSI), lithium difluorooxalato borate (LiFOB, liddoob, LiODFB), lithium hexafluorophosphate (LiPF)6) Or lithium tetrafluoroborate (LiBF)6) At least one of (1).
As a better choice of the lithium ion capacitor, the addition amount of the lithium salt electrolyte is 1 to 50 percent of the total weight of the mixed solvent.
As a better alternative to the above lithium ion capacitor, the solid gel electrolyte is prepared by directly blending an ionic liquid and a polymer to form a film.
The invention also provides negative electrode slurry of the lithium ion capacitor, which contains 70 wt% -95 wt% of the titanium niobate composite material, 1.5 wt% -15 wt% of the conductive agent and 1.5 wt% -15 wt% of the binder.
Compared with the prior art, the invention has the following beneficial effects:
1) the titanium niobate/graphene composite material obtained by the method is processed, so that the conductivity of the electrode material is increased; in addition, the interlayer spacing of the graphene is widened in the pyrolysis process of adding the surfactant, so that the titanium niobate particles are uniformly loaded on the graphene; moreover, hydrogen peroxide is added and graphene is modified, so that the conductivity of the material is further improved, and the specific surface area is increased, so that the electrochemical performance of the material is improved.
2) The crystallite size of the prepared titanium niobate is generally less than 50nm, transmission of lithium ions and electrons is facilitated, the rate capability of the material is improved, and the titanium niobate has a capacity of 213.6mAh/g at 50 ℃.
3) According to the invention, in the process of assembling the solid lithium ion capacitor, the titanium niobate/graphene composite material is used as a negative electrode, the activated carbon material is used as a positive electrode, and the electrolyte is an ionic liquid gel solid electrolyte, so that the assembled lithium ion super capacitor has excellent performance, high working voltage and good cycle performance, and the energy density and power density are far higher than those of a common electrochemical capacitor, can reach 114Wh/kg, and has high use value.
Drawings
FIG. 1: example a scanning electron microscope photograph of the titanium niobate/graphene composite material prepared in fig. 1, the material is uniformly supported on graphene nano-sheets, and the majority of the particle size is less than 50 nm;
FIG. 2: example case fig. 2 shows that the modified graphene sheet layer has a good pore structure in a transmission electron microscope photograph of the titanium niobate/graphene composite material;
FIG. 3: according to the titanium niobate/graphene composite material prepared by the embodiment I of the invention, the material has a capacity of 213.6mAh/g at 50 ℃ in a half-cell.
FIG. 4: the energy density curve of the lithium ion super capacitor prepared by the embodiment I of the invention at different temperatures is that the energy density of the material in the solid state lithium ion capacitor test is as high as 114 Wh/Kg.
FIG. 5: the energy density curve at room temperature of the lithium ion super capacitor prepared by the second embodiment of the invention can be seen from the graph, and the energy density of the material in the solid state lithium ion capacitor test is as high as 92 Wh/Kg.
FIG. 6: the energy density curve at room temperature of the lithium ion super capacitor prepared by the third embodiment of the invention is that the energy density of the material in the solid state lithium ion capacitor test is as high as 84 Wh/Kg.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings.
Example one
(a) Weighing niobium chloride and n-butyl titanate, dissolving the niobium chloride and the n-butyl titanate in an ethanol solution of 220ml according to an equal molar ratio, adding 3.6g of oxalic acid to prevent hydrolysis, fully stirring to uniformly mix, adding 300mg of graphene oxide powder and 2.1g of hexadecyl trimethyl ammonium bromide into the solution, continuously stirring for 3 hours, transferring the mixture into a reaction kettle, reacting for 10-24 hours at 180 ℃, washing the obtained precipitate for multiple times, and freeze-drying.
(b) Adding a certain amount of precipitate powder into a proper amount of pure water and a certain amount of hydrogen peroxide, continuously stirring, transferring the mixture into a reaction kettle, reacting for 10 hours at 100 ℃, washing precipitates for multiple times, and drying in vacuum to obtain a precursor;
(c) carrying out heat treatment on the precursor obtained in the step (b) at 800 ℃ for 3 hours.
The positive electrode comprises 80 wt% of activated carbon as an active substance, 10 wt% of acetylene black as a conductive agent and 10 wt% of PVDF as a binder.
The negative electrode takes 80 wt% of titanium niobate/graphene composite material as an active substance, 10 wt% of acetylene black as a conductive agent and 10 wt% of PVDF as a binder.
The ionic liquid polymer gel electrolyte takes PVDF-HFP as a gelling agent, the ionic liquid adopts EMIMBF4, and the preparation method adopts the mode of directly blending the ionic liquid and the polymer to form a film; the lithium ion capacitor works in 0-4V working voltage.
Example two
Weighing niobium ethoxide and n-butyl titanate, dissolving the niobium ethoxide and the n-butyl titanate in 220ml of ethanol solution according to an equal molar ratio, adding 3.6g of oxalic acid to prevent hydrolysis, fully stirring to uniformly mix, then adding 300mg of graphene oxide powder and 4.4g of sodium dodecyl sulfate into the solution, continuously stirring for 3 hours, transferring the mixture into a reaction kettle, reacting for 10-24 hours at 180 ℃, washing the obtained precipitate for multiple times, and freeze-drying.
EXAMPLE III
Weighing niobium ethoxide and isopropyl titanate, dissolving the niobium ethoxide and the isopropyl titanate in 220ml of ethanol solution according to an equal molar ratio, adding 3.6g of oxalic acid to prevent hydrolysis, fully stirring to uniformly mix, adding 300mg of graphene oxide powder and 2.1g of hexadecyl trimethyl ammonium bromide into the solution, continuously stirring for 3 hours, transferring the mixture into a reaction kettle, reacting for 10-24 hours at 180 ℃, washing the obtained precipitate for multiple times, and freeze-drying.
Example four
Weighing ammonium niobium oxalate and isopropyl titanate, dissolving in 220ml ethanol solution according to an equal molar ratio, adding 3.6g of oxalic acid to prevent hydrolysis, fully stirring to mix uniformly, adding 300mg of graphene oxide powder and 4.4g of octylphenol polyoxyethylene ether into the solution, continuously stirring for 3 hours, transferring the mixture into a reaction kettle, reacting for 10-24 hours at 180 ℃, washing the obtained precipitate for multiple times, and freeze-drying.
EXAMPLE five
Weighing niobium chloride and titanium tetraisopropoxide, dissolving the niobium chloride and the titanium tetraisopropoxide in an ethanol solution of 220ml according to an equal molar ratio, adding 3.6g of oxalic acid to prevent hydrolysis, fully stirring to uniformly mix, adding 300mg of graphene oxide powder and 2.1g of hexadecyl trimethyl ammonium bromide into the solution, continuously stirring for 3 hours, transferring the mixture into a reaction kettle, reacting for 10-24 hours at 180 ℃, washing the obtained precipitate for multiple times, and freeze-drying.
Examples two to five the obtained materials were treated in the same manner as in example one to obtain a negative electrode slurry.
Figure BDA0001502729530000061
Figure BDA0001502729530000071
The lithium battery may be provided according to the related art or in the following manner, corresponding to the above-described negative electrode slurry.
The positive electrode material of the lithium battery is at least one of activated carbon, graphene or carbon nano tubes.
A positive electrode material layer of a lithium battery includes: 80-90 wt% of double-layer energy storage carbon material, 1.5-15 wt% of conductive agent and 1.5-10 wt% of binder.
Wherein the conductive agent is one or a mixture of acetylene black, Ketjen black, carbon nanotube, graphene or Super-P
The gel-forming agent in the solid gel electrolyte comprises one or more of polyacrylonitrile, polymethyl methacrylate, polyethylene oxide, polypropylene oxide, polyvinyl pyridine and a copolymer of vinylidene fluoride and hexafluoropropylene;
the solid gel electrolyte ionic liquid comprises 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, N-methyl-N-propylpiperidine bis (trifluoromethylsulfonyl) imide, N, N-butyl-N-ethylpyrrolidine-N, N-bis (trifluoromethylsulfonyl) imide, N-methyl-N-butylpyrrolidine bis (trifluoromethylsulfonyl) imide, 1-methyl-3-ethylimidazolium bis (trifluoromethylsulfonyl) imide, 1-methyl-3-propylimidazolium tetrafluoroborate, 1-methyl-3-ethylimidazolium tetrafluoroborate, 1-methyl-3-hexylimidazolium tetrafluoroborate, 2, 3-dimethyl-1-octylimidazolium trifluoromethanesulfonate, 2-methyl-3-butylimidazolium tetrafluoroborate, sodium chloride, sodium, One or more of 2, 3-dimethyl-1-octylimidazolium tetrafluoroborate, N-methyl-N-propylpyrrolidine bis (trifluoromethylsulfonyl) imide, and N-methyl-N-propylpyrrole-bis (trifluoromethylsulfonyl) imide;
the adding amount of the ionic liquid accounts for 1 to 50 percent of the total weight of the mixed solvent
The lithium salt electrolyte comprises at least one of lithium bis (trifluoromethyl) sulfonimide, lithium bis-fluoroxanthimide, lithium difluorooxalato borate, lithium hexafluorophosphate or lithium tetrafluoroborate
The adding amount of the lithium salt electrolyte is 1 to 50 percent of the total weight of the mixed solvent;
the solid gel electrolyte is prepared by directly blending an ionic liquid and a polymer into a film.
The steps not related to the steps can adopt the operation of the prior art.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (18)

1. A preparation method of a carbon-modified titanium niobate material comprises the following steps:
1) dissolving a titanium source and a niobium source in an organic solvent, adding oxalic acid, and fully stirring to obtain a mixed solution, wherein the organic solvent comprises one or more of ethanol, ethylene glycol and isopropanol;
2) adding a surfactant and graphene oxide powder or a solution thereof into the mixed solution obtained in the step 1), and fully and uniformly mixing to obtain a uniform turbid liquid;
3) heating the turbid liquid obtained in the step 2) at a preset heating temperature for reaction, naturally cooling to room temperature to obtain a precipitate, and washing and drying the obtained precipitate to obtain a composite precursor of titanium niobate and graphene;
4) dispersing the composite precursor obtained in the step 3) into water, adding hydrogen peroxide, and performing hydrothermal reaction after uniform dispersion to obtain a modified graphene-coated titanium niobate composite precursor;
5) carrying out heat treatment on the modified graphene-coated titanium niobate composite material precursor obtained in the step 4) to obtain the carbon-modified titanium niobate material.
2. The method for preparing a carbon-modified titanium niobate material according to claim 1, wherein the niobium source in step 1) comprises a mixture of one or more of niobium fluoride, niobium ethoxide, niobium pentachloride, niobium oxalate, niobium ammonium oxalate.
3. The method for preparing a carbon-modified titanium niobate material according to claim 1, wherein the titanium source in the step 1) is one or a mixture of titanium tetraisopropoxide, titanium tetrachloride, titanium sulfate, butyl titanate, and isopropyl titanate.
4. The method for preparing a carbon-modified titanium niobate material according to claim 1, wherein the step 2) further comprises adding a surfactant to a mixture obtained by mixing the graphene oxide powder or the solution thereof with the mixed solution obtained in the step 1), wherein the surfactant comprises one or more of cetyltrimethylammonium bromide, alkylphenol ethoxylates, octylphenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, polyvinylpyrrolidone, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, and polyoxyethylene-polyoxypropylene-polyoxyethylene.
5. The method for producing a carbon-modified titanium niobate material according to claim 4, wherein the concentration of the surfactant in the step 2) is 0.1 to 10 mol/L.
6. The method for preparing a carbon-modified titanium niobate material as claimed in claim 1, wherein the heating temperature in step 3) is 150-200 ℃ and the reaction time is 6-48 h.
7. The method for preparing a carbon-modified titanium niobate material according to claim 1, wherein the concentration of hydrogen peroxide in the hydrothermal reaction system in the step 4) is 0.1mmol/L to 1 mol/L.
8. The method for preparing a carbon-modified titanium niobate material as claimed in claim 1, wherein the heat treatment temperature in step 5) is 500-1200 ℃, the treatment time is 2-12h, and nitrogen or argon is used as a protective atmosphere.
9. The carbon-modified titanium niobate material obtained by the method according to any one of claims 1 to 8.
10. The carbon-modified titanium niobate material according to claim 9, wherein: the carbon-modified titanium niobate material comprises CxTiNb2O7The carbon-modified titanium niobate material has a size of not more than 50nm, and the value range of x is 0.005-0.2.
11. The utility model provides a lithium ion capacitor, lithium ion capacitor comprises positive plate, negative pole piece, solid-state gel electrolyte, aluminium system shell or plastic-aluminum membrane, the negative pole piece contains copper foil and negative electrode material layer, its characterized in that: the negative electrode material layer contains 70 to 95 wt% of the titanium niobate composite material according to claim 9, 1.5 to 15 wt% of a conductive agent, and 1.5 to 15 wt% of a binder.
12. The lithium ion capacitor according to claim 11, wherein: the positive electrode sheet includes a positive electrode substance layer including: 80-90 wt% of double-layer energy storage carbon material, 1.5-15 wt% of conductive agent and 1.5-10 wt% of binder.
13. The lithium ion capacitor according to claim 11, wherein: the conductive agent is one or a mixture of several of acetylene black, Ketjen black, carbon nanotubes, graphene or Super-P.
14. The lithium ion capacitor according to claim 11, wherein: the gelling agent in the solid gel electrolyte comprises one or more of polyacrylonitrile, polymethyl methacrylate, polyethylene oxide, polypropylene oxide, polyvinyl pyridine and a copolymer of vinylidene fluoride and hexafluoropropylene.
15. The lithium ion capacitor according to claim 14, wherein: the solid gel electrolyte ionic liquid comprises 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, N-methyl-N-propylpiperidine bis (trifluoromethylsulfonyl) imide, N, N-butyl-N-ethylpyrrolidine-N, N-bis (trifluoromethylsulfonyl) imide, N-methyl-N-butylpyrrolidine bis (trifluoromethylsulfonyl) imide, 1-methyl-3-ethylimidazolium bis (trifluoromethylsulfonyl) imide, 1-methyl-3-propylimidazolium tetrafluoroborate, 1-methyl-3-ethylimidazolium tetrafluoroborate, 1-methyl-3-hexylimidazolium tetrafluoroborate, 2, 3-dimethyl-1-octylimidazolium trifluoromethanesulfonate, 2-methyl-3-butylimidazolium tetrafluoroborate, sodium hydrogen fluoride, sodium chloride, 2, 3-dimethyl-1-octylimidazolium tetrafluoroborate, N-methyl-N-propylpyrrolidinedi (trifluoromethylsulfonyl) imide and N-methyl-N-propylpyrroledi (trifluoromethylsulfonyl) imide.
16. The lithium ion capacitor according to claim 15, wherein: the addition amount of the solid gel electrolyte ionic liquid accounts for 1-50% of the total weight of the mixed solvent.
17. The lithium ion capacitor according to claim 16, wherein: the lithium salt electrolyte includes at least one of lithium bis (trifluoromethyl) sulfonimide, lithium bis fluorosulfonimide, lithium difluorooxalato borate, lithium hexafluorophosphate, or lithium tetrafluoroborate.
18. The lithium ion capacitor according to claim 17, wherein: the adding amount of the lithium salt electrolyte is 1-50% of the total weight of the mixed solvent.
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