CN113224293B - Preparation method and application of titanium carbide/carbon nano-film material - Google Patents

Preparation method and application of titanium carbide/carbon nano-film material Download PDF

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CN113224293B
CN113224293B CN202110361320.XA CN202110361320A CN113224293B CN 113224293 B CN113224293 B CN 113224293B CN 202110361320 A CN202110361320 A CN 202110361320A CN 113224293 B CN113224293 B CN 113224293B
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film material
titanium
carbon nano
titanium carbide
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CN113224293A (en
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余佳阁
杨宇航
丁瑜
张贤
王�锋
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Hubei Changjie New Materials Co ltd
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Hubei Engineering University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative 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
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a preparation method and application of a titanium carbide/carbon nano-film material, wherein the nano-film material is prepared by reacting polyacrylonitrile, polyethylene oxide, polybenzimidazole and a titanium source in DMF according to a limited concentration to prepare a spinning precursor solution, carrying out electrostatic spinning on the spinning precursor solution to obtain a precursor film, drying the precursor film, pre-oxidizing the precursor film in the air, and then carrying out two-step high-temperature calcination in an inert gas atmosphere to obtain the titanium carbide/carbon nano-film material with a three-dimensional network structure. The titanium carbide/carbon nano-film material is used as a lithium ion battery cathode self-supporting material, has the advantages of good conductivity, high strength, excellent rate performance and excellent cycling stability, can ensure that the lithium ion battery does not use rigid current collectors, binders, conductive agents and other inactive materials, and greatly improves the overall energy density of the battery.

Description

Preparation method and application of titanium carbide/carbon nano-film material
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a preparation method of a titanium carbide/carbon nano-film material and the material used as a self-supporting cathode material of a lithium ion battery
Background
At present, copper foil is required to be adopted as a current collector for the cathode material of the commercialized lithium ion battery, so that the conductivity of the material is enhanced, and the mechanical strength of the material is improved. However, the copper foil has a large mass ratio in the entire battery system and cannot provide capacity. Under the large background that the development of negative electrode materials is mature, the thickness of copper foil is reduced by various methods in industry, so that the overall energy density of the battery is improved. Therefore, there is a need to develop self-supporting materials that completely eliminate the current collector and thereby greatly increase the overall energy density of the battery. Most of the self-supporting materials reported at present have the problems of insufficient mechanical strength and poor conductivity. Titanium carbide (TiC) is one of the carbides widely studied, has a high melting point, high hardness, a high young's modulus, good electrical conductivity, and good chemical and thermal stability, and is widely used as a catalyst carrier, a gas phase reaction catalyst, an electrochemical catalyst, a capacitor electrode, and the like. Because the lithium ion battery anode material does not have lithium storage capacity, only a few studies exist at present for applying the lithium ion battery anode material as a conductive component.
CN107732170A discloses a high-efficiency lithium metal composite material and a preparation method thereof, wherein a TiC/C three-dimensional porous skeleton layer is synthesized by a chemical vapor deposition method, and the high-efficiency lithium metal composite material is prepared by taking the TiC/C three-dimensional porous skeleton layer as a carrier and adopting a molten lithium infiltration method.
CN108649189A discloses a preparation method of a titanium carbide/carbon core shell nanowire array loaded nitrogen-doped lithium titanate composite material, which utilizes an atomic layer deposition technology to grow aluminum oxide on a titanium mesh; growing a titanium carbide/carbon core shell nanowire array composite material on a titanium mesh by using a chemical vapor deposition method; and then placing the titanium carbide/carbon core-shell nanowire array composite material in a solution for hydrothermal reaction, and washing, drying and calcining a product to obtain the LTO @ TiC/C material.
The prior art needs to dope a lithium metal compound in the TiC/C composite material, and reports that the flexible TiC/C nano-film material without doping the metal lithium compound prepared by the prior art is used as a lithium ion self-supporting electrode material are not found at present.
Disclosure of Invention
In order to prepare the flexible TiC/C nano-film material, the invention adopts an electrostatic spinning method and a two-step calcination carbonization method in sequence to realize uniform film formation of titanium carbide and obtain the TiC/C nano-film material with a three-dimensional network structure. The film material is a three-dimensional network structure obtained by in-situ calcination, so that the grain growth of titanium carbide can be well controlled, the whole film material has high mechanical strength and excellent conductivity, and the material has excellent electrochemical performance when being applied as a self-supporting lithium battery cathode material.
In order to realize the purpose, the invention provides a preparation method of a titanium carbide/carbon nano-film material, which is realized by adopting the following technical scheme:
s1, adding polyacrylonitrile, polyethylene oxide, polybenzimidazole and a titanium source into N, N-dimethylformamide according to the mass ratio of (0.1-1): 3, (0.1-0.5): 3, (0.1-1): 3 and (0.1-1): 3 at the temperature of 50-80 ℃ and stirring for 6-24 hours to form a spinning precursor solution; carrying out electrostatic spinning on the spinning precursor solution to obtain a precursor film, and carrying out vacuum drying for 12 hours at the temperature of 55-65 ℃ for later use;
s2, heating the spinning precursor film obtained in the S1 to 100-300 ℃ at the speed of 1-10 ℃/min in the air atmosphere, and preserving the heat for 1-5 h; then heating to 550-650 ℃ at the speed of 2 ℃/min and preserving heat for 2h under the nitrogen atmosphere to obtain TiO2a/C nano-film material;
s3 preparation of TiO 2 in Ar atmosphere2Heating the/C nano-film material to 1000-1800 ℃ at the speed of 5-20 ℃/min, and preserving the heat for 2-10 h to obtain the titanium carbide/carbon nano-film material.
Because the flexible self-supporting electrode has high requirement on mechanical strength, three polymers of polyacrylonitrile, polyethylene oxide and polybenzimidazole are selected for combination, so that the viscosity of the polymer is increased, the material structure is more compact, and the effect of synergistically enhancing the mechanical strength is achieved. And S2, performing heat preservation and solidification on the spinning precursor film in the air atmosphere to evaporate the organic solvent to dryness, and discharging free water and adsorbed water in the polymer to make the material structure more compact. When the temperature is lower than 100 ℃, water cannot be effectively removed, and when the temperature is higher than 300 ℃, the polymer is easy to degrade and cannot achieve the curing effect. The invention adopts a two-step calcination method, and three polymers are firstly converted into carbon materials to obtain TiO2a/C nano-film material; then a part of the carbon material is mixed with TiO2The TiC/C nano-film material is obtained by reaction at a higher temperature, and the compactness of the material can be greatly improved, so that the TiC/C nano-film material with smooth surface, uniform thickness, good flexibility and better mechanical strength is obtained.
Preferably, the titanium source is nano titanium dioxide, tetrabutyl titanate, titanyl sulfate, titanium tetrachloride or titanium trichloride.
More preferably, when the titanium source is nano titanium dioxide, the mass ratio of the nano titanium dioxide to the N, N-dimethylformamide is (0.2-0.5): 3; when the titanium source is tetrabutyl titanate, the mass ratio of the tetrabutyl titanate to the N, N-dimethylformamide is (0.5-1) to 3; when the titanium source is titanyl sulfate, the mass ratio of the titanyl sulfate to the N, N-dimethylformamide is (0.6-1): 3; when the titanium source is titanium tetrachloride, the mass ratio of the titanium tetrachloride to the N, N-dimethylformamide is (0.3-0.6): 3; when the titanium source is titanium trichloride, the mass ratio of the titanium trichloride to the N, N-dimethylformamide is (0.2-0.6): 3.
Preferably, the titanium source in step S1 is titanyl sulfate, and the mass ratio of polyacrylonitrile, polyethylene oxide, polybenzimidazole, titanyl sulfate and N, N-dimethylformamide is 3:1:1:6: 30.
Preferably, in the step S2, the spinning precursor film is heated to 280-300 ℃ at a heating rate of 1-2 ℃/min, and the temperature is maintained for 1-2 h.
More preferably, in step S2, the spinning precursor film is heated to 280 ℃ at a heating rate of 1 ℃/min, and is kept warm for 2 h.
Preferably, TiO is mixed in step S32The temperature of the/C nano-film material is raised to 1200-1500 ℃ at the speed of 5-10 ℃/min, and the temperature is kept for 4-8 h.
More preferably, TiO is treated in step S32The temperature of the/C nano-membrane material is raised to 1400 ℃ at the speed of 5 ℃/min, and the temperature is kept for 6 h.
Preferably, the polyacrylonitrile, the titanium source and the N, N-dimethylformamide are not less pure than chemically pure.
Preferably, the titanium carbide/carbon nano-film material prepared by the preparation method of the titanium carbide/carbon nano-film material is used as a self-supporting negative electrode material of a lithium ion battery.
The invention has the beneficial effects that:
(1) the titanium carbide/carbon nano-film material prepared by the invention belongs to a flexible self-supporting material in the field of lithium ion batteries, and can completely eliminate the use of inactive materials such as rigid current collectors, binders, conductive agents and the like, thereby greatly improving the overall energy density of the battery;
(2) the titanium carbide/carbon nano-film material with the three-dimensional network structure prepared by the invention has the advantages of good conductivity, high strength, excellent rate capability and cycle stability and the like, and can be widely applied to catalyst carrier capacitor electrodes and lithium ion battery electrode materials.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a titanium carbide/carbon nano-film material prepared in example 1 of the present invention;
fig. 2 is a graph showing the cycle rate performance of the titanium carbide/carbon nano-film material prepared in example 1 of the present invention at different current densities.
Detailed Description
The technical solution of the present invention is described in detail and fully with reference to the following examples, it is obvious that the described examples are only a part of the examples of the present invention, and not all of the examples. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention. Any equivalent changes or substitutions by those skilled in the art according to the following embodiments are within the scope of the present invention.
Example 1
The method for preparing the titanium carbide/carbon nano-film material comprises the following steps:
s1, mixing Polyacrylonitrile (PAN), polyethylene oxide (PEO), Polybenzimidazole (PBI), titanyl sulfate and N, N-Dimethylformamide (DMF) according to the mass ratio of 3:1:1:6:30 at 70 ℃, and uniformly stirring for 12 hours to form a spinning precursor solution; performing electrostatic spinning on the spinning precursor solution to obtain a precursor film, and performing vacuum drying for 12 hours at the temperature of 60 +/-5 ℃ for later use;
s2, heating the spinning precursor film to 280 ℃ at the speed of 1 ℃/min under the air atmosphere, and preserving the heat for 2 h; heating to 600 +/-50 ℃ at the speed of 2 ℃/min under the nitrogen atmosphere, and preserving the heat for 2 hours to obtain TiO2a/C nano-film material;
s3, in argon atmosphere, adding TiO2Heating the/C nano-film material to 1400 ℃ at the speed of 5 ℃/min, and preserving the heat for 6h to obtain the titanium carbide/carbon nano-film material.
Fig. 1 is a Scanning Electron Microscope (SEM) image of the titanium carbide/carbon nano-film material prepared in this example, and it can be seen that the titanium carbide/carbon nano-film material has a three-dimensional network structure.
The titanium carbide/carbon nano-film material is assembled into a lithium ion half-cell in a glove box according to the following method:
sequentially stacking the positive electrode shell, the titanium carbide/carbon nano-film material, the diaphragm, the lithium sheet, the foamed nickel and the negative electrode shell, adding a proper amount of electrolyte, and packaging; the battery case used therein was of the CR2016 type, the separator was Celgard2400, and the electrolyte was 1mol/L LiPF6/EC-DMC (volume ratio of EC to DMC was 1: 1). The prepared battery is circulated under different current densities, the obtained circulation performance diagram is shown in figure 2, the capacity of 520mAh/g is still remained after 200 cycles of circulation under the current density of 0.1A/g, and the capacity of 182mAh/g can be reached under the current density of 2A/g; the battery has excellent cycle performance under high current density, which shows that the electrode material structure is very stable.
Example 2
The method for preparing the titanium carbide/carbon nano-film material in this example is substantially the same as that in example 1, except that the mass ratio of PAN, PEO, PBI, titanyl sulfate to DMF in step S1 is 1:1:1:6: 30.
The prepared titanium carbide/carbon nano-film material is assembled into a lithium ion half-cell in a glove box according to the method of example 1, the electrical property of the lithium ion half-cell is measured, and the capacity of 490mAh/g is still remained after 200 cycles under the current density of 0.1A/g.
Example 3
The method for preparing the titanium carbide/carbon nano-film material in this example is substantially the same as that in example 1, except that the mass ratio of PAN, PEO, PBI, titanyl sulfate to DMF in step S1 is 10:5:5:6: 30.
The prepared titanium carbide/carbon nano-film material is assembled into a lithium ion half-cell in a glove box according to the method of example 1, the electrical property of the lithium ion half-cell is measured, and the capacity of 502mAh/g is still remained after 200 cycles under the current density of 0.1A/g.
Example 4
The method for preparing the titanium carbide/carbon nano-film material in this example is substantially the same as in example 1, except that step S2:
s2, heating the spinning precursor film to 300 ℃ at the speed of 2 ℃/min under the air condition, and preserving heat for 1 h; under nitrogen atmosphereHeating to 600 +/-50 ℃ at the speed of 2 ℃/min and preserving the temperature for 2 hours to obtain TiO2a/C nano-film material.
The prepared titanium carbide/carbon nano-film material is assembled into a lithium ion half-cell in a glove box according to the method of example 1, the electrical property of the lithium ion half-cell is measured, and the capacity of 511mAh/g is still remained after 200 cycles under the current density of 0.1A/g.
Example 5
The method for preparing the titanium carbide/carbon nano-film material in this example is substantially the same as in example 1, except that step S3:
s3, under the condition of argon, adding TiO2Heating the/C nano-film material to 1500 ℃ at the speed of 10 ℃/min, and preserving the heat for 4h to obtain the titanium carbide/carbon nano-film material.
The titanium carbide/carbon nano-film material is assembled into a lithium ion half-cell in a glove box according to the method of example 1, the electrical property of the lithium ion half-cell is measured, and the capacity of 516mAh/g is still remained after 200 cycles under the current density of 0.1A/g.
Example 6
The method for preparing the titanium carbide/carbon nano-film material in this example is substantially the same as in example 1, except that step S3:
s3, under the condition of argon, adding TiO2Heating the/C nano-film material to 1200 ℃ at the speed of 7 ℃/min, and preserving the heat for 8h to obtain the titanium carbide/carbon nano-film material.
The titanium carbide/carbon nano-film material is assembled into a lithium ion half-cell in a glove box according to the method of example 1, the electrical property of the lithium ion half-cell is measured, and the capacity of 513mAh/g is still remained after 200 cycles under the current density of 0.1A/g.
Example 7
The method for preparing the titanium carbide/carbon nano-film material in this embodiment is substantially the same as that in embodiment 1, except that PAN, PEO, PBI, tetrabutyl titanate and DMF are uniformly mixed at a mass ratio of 3:1:1:5:30 at 50 ℃ in step S1, and stirred for 24 hours to form a spinning precursor solution.
The prepared titanium carbide/carbon nano-film material is assembled into a lithium ion half-cell in a glove box according to the method of example 1, the electrical property of the lithium ion half-cell is measured, and the capacity of 506mAh/g is still remained after 200 cycles under the current density of 0.1A/g.
Example 8
The method for preparing the titanium carbide/carbon nano-film material in this example is substantially the same as that in example 1, except that in step S1, PAN, PEO, PBI, titanium tetrachloride and DMF are uniformly mixed at a mass ratio of 3:1:1:4:30, and stirred for 6 hours to form a spinning precursor solution.
The prepared titanium carbide/carbon nano-film material is assembled into a lithium ion half-cell in a glove box according to the method of example 1, the electrical property of the lithium ion half-cell is measured, and the capacity of 498mAh/g is still remained after 200 cycles under the current density of 0.1A/g.
Comparative example 1
The method for preparing the titanium carbide/carbon nano-film material in the comparative example is basically the same as that in example 1, except that PAN, PEO, titanyl sulfate and DMF were mixed in a mass ratio of 3:1:6:30 in step S1, and were uniformly stirred for 12 hours to form a spinning precursor solution.
The prepared titanium carbide/carbon nano-film material was assembled into a lithium ion half-cell in a glove box according to the method of example 1, and the electrical properties of the lithium ion half-cell were measured, and the capacity after 200 cycles at a current density of 0.1A/g was 415 mAh/g.
Comparative example 2
The method for preparing the titanium carbide/carbon nano-film material in the comparative example is basically the same as that in example 1, except that in step S1, PAN, PBI, titanyl sulfate and DMF are mixed according to the mass ratio of 3:1:6:30, and are uniformly stirred for 12 hours to form a spinning precursor solution.
The prepared titanium carbide/carbon nano-film material was assembled into a lithium ion half-cell in a glove box according to the method of example 1, and the electrical properties of the lithium ion half-cell were measured, and the capacity after 200 cycles at a current density of 0.1A/g was 407 mAh/g.
Comparative example 3
The method for preparing the titanium carbide/carbon nano-film material in the comparative example is substantially the same as that in example 1, except that in step S1, PEO, PBI, titanyl sulfate and DMF were mixed in a mass ratio of 1:1:6:30, and were uniformly stirred for 12 hours to form a spinning precursor solution.
The prepared titanium carbide/carbon nano-film material was assembled into a lithium ion half cell in a glove box according to the method of example 1, and the electrical properties of the lithium ion half cell were measured, and the capacity after 200 cycles at a current density of 0.1A/g was 395 mAh/g.
Comparative example 4
The method for preparing the titanium carbide/carbon nano-film material in the comparative example is basically the same as that in example 1, except that in step S1, PAN, titanyl sulfate and DMF are mixed according to the mass ratio of 3:6:30, and are uniformly stirred for 12 hours to form a spinning precursor solution.
The prepared titanium carbide/carbon nano-film material was assembled into a lithium ion half-cell in a glove box according to the method of example 1, and the electrical properties of the lithium ion half-cell were measured, and the capacity after 200 cycles at a current density of 0.1A/g was 380 mAh/g.
Comparative example 5
The method for preparing the titanium carbide/carbon nano-film material in the comparative example comprises the following steps:
s1, mixing Polyacrylonitrile (PAN), polyethylene oxide (PEO), Polybenzimidazole (PBI), titanyl sulfate and N, N-Dimethylformamide (DMF) according to the mass ratio of 3:1:1:6:10 at 70 ℃, and uniformly stirring for 12 hours to form a spinning precursor solution; performing electrostatic spinning on the spinning precursor solution to obtain a precursor film, and performing vacuum drying for 12 hours at the temperature of 60 +/-5 ℃ for later use;
s2, heating the spinning precursor film to 280 ℃ at the speed of 1 ℃/min under the air atmosphere, and preserving the heat for 2 h; and under the argon atmosphere, heating to 1400 ℃ at the speed of 5 ℃/min, and preserving the heat for 8 hours to obtain the TiC/C nano-film material.
The prepared titanium carbide/carbon nano-film material was assembled into a lithium ion half-cell in a glove box according to the method of example 1, and the electrical properties of the lithium ion half-cell were measured, and the capacity after 200 cycles at a current density of 0.1A/g was 440 mAh/g.
Comparative example 6
The comparative example prepared a titanium carbide/carbon nano-film material in substantially the same manner as in example 1, except that the mass ratio of PAN, PEO, PBI, titanyl sulfate to DMF in step S1 was 0.8:0.8:0.8:6: 30.
The prepared titanium carbide/carbon nano-film material was assembled into a lithium ion half-cell in a glove box according to the method of example 1, and the electrical properties of the lithium ion half-cell were measured, and the capacity after 200 cycles at a current density of 0.1A/g was 420 mAh/g.
Comparative example 7
The method of preparing a titanium carbide/carbon nano-film material according to this comparative example is substantially the same as that of example 1, except that the mass ratio of PAN, PEO, PBI, titanyl sulfate to DMF in step S1 is 11:6:6:6: 30.
The prepared titanium carbide/carbon nano-film material was assembled into a lithium ion half-cell in a glove box according to the method of example 1, and the electrical properties of the lithium ion half-cell were measured, and the capacity after 200 cycles at a current density of 0.1A/g was 320 mAh/g.
In conclusion, according to the preparation method provided by the invention, the TiC/C nano-film material prepared by using three polymers, namely polyacrylonitrile, polyethylene oxide and polybenzimidazole together in a limited concentration range and adopting a two-step calcination method has more excellent electrical properties when being used as the negative electrode of the lithium ion battery. The performance of the TiC/C nano-film material prepared by the two-step calcination method is remarkably reduced by only using one or two polymers; or the performance of the TiC/C nano-film material prepared by the three polymers by adopting a one-step calcination method is also obviously reduced.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. The present invention may be subject to various modifications and changes by any person skilled in the art. Any simple equivalent changes and modifications made in accordance with the protection scope of the present application and the content of the specification are intended to be included within the protection scope of the present invention.

Claims (10)

1. A preparation method of a titanium carbide/carbon nano-film material is characterized by comprising the following steps:
s1, adding polyacrylonitrile, polyethylene oxide, polybenzimidazole and a titanium source into N, N-dimethylformamide according to the mass ratio of (0.1-1): 3, (0.1-0.5): 3, (0.1-1): 3 and (0.1-1): 3 at the temperature of 50-80 ℃ and stirring for 6-24 hours to form a spinning precursor solution; carrying out electrostatic spinning on the spinning precursor solution to obtain a spinning precursor film, and carrying out vacuum drying for 12 hours at the temperature of 55-65 ℃ for later use;
s2, heating the spinning precursor film obtained in the S1 to 100-300 ℃ at the speed of 1-10 ℃/min in the air atmosphere, and preserving the heat for 1-5 h; then heating to 550-650 ℃ at the speed of 2 ℃/min and preserving heat for 2h under the nitrogen atmosphere to obtain TiO2a/C nano-film material;
s3 preparation of TiO 2 in Ar atmosphere2Heating the/C nano-film material to 1000-1800 ℃ at the speed of 5-20 ℃/min, and preserving the heat for 2-10 h to obtain the titanium carbide/carbon nano-film material.
2. The method for preparing a titanium carbide/carbon nano-film material according to claim 1, wherein the titanium source is nano-titanium dioxide, tetrabutyl titanate, titanyl sulfate, titanium tetrachloride or titanium trichloride.
3. The method for preparing titanium carbide/carbon nano-film material according to claim 2, characterized in that:
when the titanium source is nano titanium dioxide, the mass ratio of the nano titanium dioxide to the N, N-dimethylformamide is (0.2-0.5): 3;
when the titanium source is tetrabutyl titanate, the mass ratio of the tetrabutyl titanate to the N, N-dimethylformamide is (0.5-1) to 3;
when the titanium source is titanyl sulfate, the mass ratio of the titanyl sulfate to the N, N-dimethylformamide is (0.6-1): 3;
when the titanium source is titanium tetrachloride, the mass ratio of the titanium tetrachloride to the N, N-dimethylformamide is (0.3-0.6): 3;
when the titanium source is titanium trichloride, the mass ratio of the titanium trichloride to the N, N-dimethylformamide is (0.2-0.6): 3.
4. The method for preparing a titanium carbide/carbon nano-film material according to claim 1, wherein the titanium source in step S1 is titanyl sulfate, and the mass ratio of polyacrylonitrile, polyethylene oxide, polybenzimidazole, titanyl sulfate, and N, N-dimethylformamide is 3:1:1:6: 30.
5. The method for preparing a titanium carbide/carbon nano-film material according to claim 1, wherein in step S2, the spinning precursor film is heated to 280-300 ℃ at a heating rate of 1-2 ℃/min, and the temperature is maintained for 1-2 h.
6. The method for preparing titanium carbide/carbon nano-film material according to claim 5, wherein the spinning precursor film is heated to 280 ℃ at a heating rate of 1 ℃/min in step S2, and the temperature is kept for 2 h.
7. The method for preparing titanium carbide/carbon nano-film material according to claim 1, wherein in step S3, TiO is added2The temperature of the/C nano-film material is raised to 1200-1500 ℃ at the temperature raising rate of 5-10 ℃/min, and the temperature is kept for 4-8 h.
8. The method for preparing titanium carbide/carbon nano-film material according to claim 7, wherein TiO 32The temperature of the/C nano-membrane material is raised to 1400 ℃ at the temperature raising rate of 5 ℃/min, and the temperature is kept for 6 h.
9. The method for preparing titanium carbide/carbon nano-film material according to claim 1, wherein the purities of the polyacrylonitrile, the titanium source and the N, N-dimethylformamide are not lower than chemical purity.
10. The titanium carbide/carbon nano-film material prepared by the preparation method of the titanium carbide/carbon nano-film material according to any one of claims 1 to 9, wherein the titanium carbide/carbon nano-film material is used as a self-supporting negative electrode material of a lithium ion battery.
CN202110361320.XA 2021-04-02 2021-04-02 Preparation method and application of titanium carbide/carbon nano-film material Active CN113224293B (en)

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