CN113948691B - Titanium dioxide composite material and application thereof as energy storage material - Google Patents

Titanium dioxide composite material and application thereof as energy storage material Download PDF

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CN113948691B
CN113948691B CN202111201883.9A CN202111201883A CN113948691B CN 113948691 B CN113948691 B CN 113948691B CN 202111201883 A CN202111201883 A CN 202111201883A CN 113948691 B CN113948691 B CN 113948691B
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titanium dioxide
graphene
composite material
dioxide composite
melamine
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CN113948691A (en
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熊帮云
郭家进
范振荣
李静静
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Foshan University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/366Composites as layered products
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/054Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M2004/021Physical characteristics, e.g. porosity, surface area
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M2004/026Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027Negative electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention relates to the technical field of titanium dioxide composite materials, in particular to a titanium dioxide composite material and application thereof as an energy storage material. The material is compounded by taking graphene as a core material and titanium dioxide containing a pore structure as a shell material; the preparation method comprises the steps of reacting melamine with formaldehyde to obtain prepolymer methyl melamine, and then transferring the prepolymer methyl melamine into an acidic polyvinyl alcohol aqueous solution dispersed with graphene for heating reaction to obtain graphene/melamine formaldehyde composite particles; uniformly mixing the graphene/melamine formaldehyde composite particles and a surfactant in a solvent, and adjusting the pH value to be alkaline to obtain a mixed solution; adding a titanium source solution into the mixed solution under the stirring condition, stirring, centrifuging and drying to obtain a product; and calcining the product in an inert atmosphere to obtain the titanium dioxide composite material. The invention utilizes the characteristics of high temperature resistance, oxidation resistance, high strength, good electric conduction and heat conduction of graphene to solve the defects of poor electric conduction performance and low specific capacity of titanium dioxide.

Description

Titanium dioxide composite material and application thereof as energy storage material
Technical Field
The invention relates to the technical field of titanium dioxide composite materials, in particular to a titanium dioxide composite material and application thereof as an energy storage material.
Background
With a series of problems of climate warming, environmental pollution and the like caused by the development of large-scale fossil energy, the utilization of new renewable energy sources, such as solar energy, wind energy, tidal energy and the like, has received attention from many researchers. The common method is to convert corresponding energy into electric energy through some comprehensive conversion facilities to serve the human society, however, the method is limited by natural laws and limitations of the human society on electric energy use, even in an area with optimal natural conditions, the utilization of the novel energy is limited by some factors, such as season and climate influence, so that the serious problems of large fluctuation range, uncontrollable and discontinuous working time and the like exist when the energy is converted into the electric energy; accordingly, devices and equipment with energy storage regulation function are used to regulate and improve the working efficiency of these renewable energy sources, so that such energy sources can be finally converted into electric energy sources suitable for human society. Among various energy storage resources, the application of battery energy storage is most flexible, various use scenes are compatible, meanwhile, the development of battery technology also has better development prospects, the battery energy storage system in the prior art is developed rapidly, and the main types of the battery energy storage system in the prior art are lithium ion batteries, sodium ion batteries, lead-acid batteries, sodium-sulfur batteries, flow batteries, nickel-cadmium batteries, nickel-hydrogen batteries and the like. The basic composition of a battery generally comprises a positive electrode material, a negative electrode material, a diaphragm and an electrolyte; among them, the negative electrode materials are mainly researched carbon-based materials, titanium-based materials, alloy materials, metal oxide materials, transition metal sulfide materials and the like; in the cathode material, tiO is compared with other electrode materials 2 TiO has its own advantages, whether as a lithium-storage electrode material or a sodium-storage electrode material 2 The titanium dioxide electrode material has the advantages of small structural change and small volume expansion in the charging and discharging process, can be considered as zero distortion, stable charging and discharging platform and short insertion and extraction path, and the advantages of long cycle life and safety of the titanium dioxide electrode materialThe performance is good; but TiO is not limited to 2 Meanwhile, the defects of wide band gap, poor conductivity, low specific capacity and the like exist, and the defects limit the application of the lithium ion battery in the field of battery energy storage.
Disclosure of Invention
Based on the above, the present invention provides a titanium dioxide composite material and its application as an energy storage material. The conductivity and specific capacity of the titanium dioxide are improved by preparing the titanium dioxide composite material which takes the graphene as a core material and takes the titanium dioxide containing a reticular pore structure as a shell material.
According to one technical scheme, the titanium dioxide composite material is compounded by taking graphene as a core material and titanium dioxide containing a pore structure as a shell material.
The second technical scheme of the invention is that the preparation method of the titanium dioxide composite material comprises the following steps:
(1) Mixing melamine and formaldehyde, carrying out primary heating reaction to obtain a prepolymer methyl melamine, then transferring the prepolymer methyl melamine into an acidic polyvinyl alcohol aqueous solution dispersed with graphene, carrying out secondary heating reaction, drying and crushing to obtain graphene/melamine formaldehyde composite particles;
(2) Placing the graphene/melamine formaldehyde composite particles and a surfactant in a solvent, uniformly mixing, and adjusting the pH value to be alkaline to obtain a mixed solution;
(3) Adding a titanium source solution into the mixed solution under the stirring condition, stirring, centrifuging and drying to obtain a product;
(4) And calcining the product in an inert atmosphere to obtain the titanium dioxide composite material.
Further, in the step (1):
the mixing ratio of melamine and formaldehyde is (1-2) g: (3-5) mL, wherein the reaction temperature is 60-70 ℃ in one heating, and the reaction time is 20-30min;
the pH value of the acidic polyvinyl alcohol aqueous solution dispersed with the graphene is 3-5, wherein the concentration of the graphene is 5-10wt%, the concentration of the polyvinyl alcohol is 5-10wt%, and the volume ratio of the prepolymer methyl melamine to the acidic polyvinyl alcohol aqueous solution dispersed with the graphene is 10 (50-80);
the secondary heating reaction temperature is 60-70 ℃, the reaction time is 30-50min, and the secondary heating reaction is carried out under the ultrasonic condition.
Further, in the step (2): the graphene/melamine formaldehyde composite particles in the mixed solution are 3-5wt% in concentration, the surfactant is 0.05-0.1wt% in concentration, ammonia water is used for adjusting the pH value of the mixed solution to 8-10, the solvent of the mixed solution is ethanol, and the surfactant is cetyl trimethyl ammonium bromide.
Further, in the step (3): the titanium source in the titanium source solution is tetraethyl titanate, tetrapropyl titanate or tetrabutyl titanate, the solvent of the titanium source solution is ethanol, and the concentration of the titanium source in the titanium source solution is 10-20wt%; the mixing volume ratio of the titanium source solution to the mixed solution is 10: (5-10).
Further, in the step (3): the dropping process is carried out at 50-60 deg.C, and the drying is freeze drying.
Further, in the step (4), the calcining temperature is 500-600 ℃, the calcining time is 5-10h, and the heating rate is 5-10 ℃/min.
According to the third technical scheme, the titanium dioxide composite material is applied as an energy storage material.
Further, the titanium dioxide composite material is used as a negative electrode material of an ion battery.
Further, the ion battery is specifically a lithium ion battery or a sodium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
the graphene has the advantages of high temperature resistance, oxidation resistance, high strength, good electric conduction and heat conduction performance and the like, the titanium dioxide composite material disclosed by the invention takes the graphene as a core material, and takes the titanium dioxide containing a net-shaped pore structure as a shell material, and the pore structure on the surface of the titanium dioxide enables the specific surface area of the material to be larger so as to have more active sites, and on the other hand, the titanium dioxide composite material is beneficial to more effectively carrying out electron transfer on the core graphene material and a contact medium so as to exert the electric conduction function to a greater extent, and the graphene and the titanium dioxide material are synergistic, so that the electric conduction and the specific capacity of the composite titanium dioxide can be remarkably improved. Meanwhile, the graphene is wrapped by the titanium dioxide serving as the shell material, and the stress generated in the charging and discharging process can be reduced based on the advantages of small structural change and small volume expansion in the charging and discharging process, so that the problem that the service life of the battery is influenced due to the generation of cracks in the material is solved.
The preparation method comprises the steps of mixing graphene/melamine formaldehyde nano composite particles serving as a template agent and a surfactant to prepare an alkaline mixed solution, then dropwise adding a titanium source solution into the alkaline mixed solution to form a suspension of graphene/melamine formaldehyde composite particles @ titanium dioxide sol, then centrifugally washing and drying a product, and calcining the product in an inert atmosphere to remove melamine formaldehyde copolymer in a core material, wherein in the calcining process, gas generated by the melamine formaldehyde copolymer in the core material gradually volatilizes to break through a surface shell layer so as to leave a net-shaped pore structure on the surface of titanium dioxide, and meanwhile, the remaining graphene material in the core also forms a spatial net-shaped structure. In the preparation method, the concentration of the graphene/melamine formaldehyde nano composite particles in the mixed solution is not suitable to be too high, and agglomeration phenomenon can be caused if the concentration is too high, so that the formation of a shell-core structure is influenced. The heating rate in the calcining process is not too slow or too fast, the too slow can result in the too slow volatilization and decomposition rate of the melamine formaldehyde copolymer, and the too fast can result in the decomposition reaction of the melamine formaldehyde copolymer before the formation of the titanium dioxide shell layer, which is not beneficial to the formation of a net-shaped pore structure.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the documents are cited. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
(1) Dissolving 8g of polyvinyl alcohol in 100mL of water to prepare a polyvinyl alcohol aqueous solution, adjusting the pH of the solution to 4.5 by using acetic acid, and adding 8g of graphene under an ultrasonic condition to obtain an acidic polyvinyl alcohol aqueous solution in which the graphene is dispersed;
(2) Weighing 5g of melamine and 10mL of formaldehyde, mixing, heating and reacting at 60 ℃ for 30min to obtain prepolymer methyl melamine, transferring into 80mL of acidic polyvinyl alcohol aqueous solution dispersed with graphene in the step (1), heating and reacting at 65 ℃ for 30min, drying and crushing to obtain graphene/melamine formaldehyde composite particles;
(3) Placing 4g of graphene/melamine formaldehyde composite particles and 0.08g of hexadecyl trimethyl ammonium bromide in 100mL of ethanol solution, ultrasonically mixing uniformly, and adding ammonia water to adjust the pH value to 9 to obtain a mixed solution;
(4) Under the stirring condition, 20mL of tetraethyl titanate ethanol solution (15 wt%) is dropwise added into 20mL of mixed solution preheated to 60 ℃ in advance, after dropwise addition is finished, vigorous stirring is continued for 24h, and centrifugation and freeze drying are carried out to obtain a product precursor;
(5) And (3) placing the product precursor in an argon atmosphere, heating to 550 ℃ at the heating rate of 10 ℃/min, and calcining for 8 hours to obtain the titanium dioxide composite material.
The scanning electron microscope observation is carried out on the prepared product, and the result shows that the outer shell of the material is in a network pore structure, and the inner material is in a graphene three-dimensional space network structure.
Example 2
(1) Dissolving 10g of polyvinyl alcohol in 100mL of water to prepare a polyvinyl alcohol aqueous solution, adjusting the pH of the solution to 5 by using acetic acid, and adding 10g of graphene under an ultrasonic condition to obtain an acidic polyvinyl alcohol aqueous solution in which the graphene is dispersed;
(2) Weighing 5g of melamine and 10mL of formaldehyde, mixing, heating and reacting for 30min at 65 ℃ to obtain prepolymer methyl melamine, then transferring into 60mL of acidic polyvinyl alcohol aqueous solution dispersed with graphene in the step (1), carrying out secondary heating and reacting for 30min at 70 ℃, drying and crushing to obtain graphene/melamine formaldehyde composite particles;
(3) Placing 5g of graphene/melamine formaldehyde composite particles and 0.1g of hexadecyl trimethyl ammonium bromide in 100mL of ethanol solution, ultrasonically mixing uniformly, and adding ammonia water to adjust the pH value to 8 to obtain a mixed solution;
(4) Dropwise adding 10mL of tetraethyl titanate ethanol solution (20 wt%) into 20mL of mixed solution preheated to 50 ℃ in advance under the stirring condition, after dropwise adding is finished, continuously and violently stirring for 24h, centrifuging, and freeze-drying to obtain a product precursor;
(5) And (3) placing the product precursor in an argon atmosphere, heating to 600 ℃ at the heating rate of 5 ℃/min, and calcining for 5 hours to obtain the titanium dioxide composite material.
Scanning electron microscope observation is carried out on the prepared product, and the result shows that the outer shell of the material is in a network pore structure, and the inner material is in a graphene three-dimensional space network structure.
Example 3
The difference from example 1 is that the preparation process of the graphene/melamine formaldehyde composite particles in step (1) and step (2) is omitted, and the titanium dioxide composite material compounded by taking graphene as the core material and titanium dioxide as the shell material is prepared by directly taking graphene as the raw material in step (3).
Example 4
The method is the same as example 1, except that the graphene in step (2) is omitted, and the melamine formaldehyde composite particles are used as the raw material in step (3) to prepare the hollow titanium dioxide material using titanium dioxide as the shell material.
Example 5
The difference from example 1 is that the temperature increase rate in step (5) is 20 ℃/min, and the result shows that the prepared product is a graphene-doped titanium dioxide composite material and does not have a shell-core structure.
Example 6
The difference from example 1 is that the temperature increase rate in step (5) is 1 ℃/min, and the prepared product is a graphene-doped titanium dioxide composite material and does not have a shell-core structure.
Example of Effect verification
Conductivity measurements of the titanium dioxide composites prepared in examples 1-6 were performed using a multifunctional resistivity tester, and the results are shown in table 1;
TABLE 1
Figure BDA0003305291720000061
A negative electrode was prepared by mixing the titanium dioxide composite materials prepared in examples 1 to 6 with acetylene black and a binder (PVDF) in a mass ratio of 8 6 (EC: DEC: DMC = 1.
And performing cyclic voltammetry test on the assembled electrons by using an electrochemical workstation, wherein the reference electrode and the reference electrode are both metal lithium sheets, the current density is 100mA/g, the voltage range is 1.0-3.0V, and the scanning rate is 1.0mV/s. The results are shown in Table 2.
TABLE 2
Figure BDA0003305291720000062
As can be seen from the data in tables 1 and 2, the titanium dioxide composite materials prepared in examples 1-2 of the present invention have higher electrical conductivity and charge-discharge specific capacity. Meanwhile, the charge-discharge specific capacity attenuation rate of the product obtained in the embodiment 1-2 after 50 cycles is far lower than that obtained in the embodiment 3-6, and the reason is that the mesh structure in the material prevents the electrolyte from forming a passivation layer on the surface of the negative electrode material, so that more reaction channels are provided for lithium ions, and the cycling stability of the battery is improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.

Claims (8)

1. The preparation method of the titanium dioxide composite material is characterized by comprising the following steps:
(1) Mixing melamine and formaldehyde, carrying out primary heating reaction to obtain a prepolymer methyl melamine, then transferring the prepolymer methyl melamine into an acidic polyvinyl alcohol aqueous solution dispersed with graphene, carrying out secondary heating reaction, drying and crushing to obtain graphene/melamine formaldehyde composite particles;
(2) Placing the graphene/melamine formaldehyde composite particles and a surfactant in a solvent, uniformly mixing, and adjusting the pH value to be alkaline to obtain a mixed solution;
(3) Adding a titanium source solution into the mixed solution under the stirring condition, stirring, centrifuging and drying to obtain a product;
(4) Calcining the product in an inert atmosphere to obtain a titanium dioxide composite material;
the titanium dioxide composite material takes graphene as a core material and takes titanium dioxide containing a pore structure as a shell material;
in the step (4), the calcining temperature is 500-600 ℃, the calcining time is 5-10h, and the heating rate is 5-10 ℃/min.
2. The method for producing a titanium dioxide composite material according to claim 1, wherein in the step (1): the mixing ratio of melamine and formaldehyde is (1-2) g: (3-5) mL, wherein the reaction temperature is 60-70 ℃ in one heating, and the reaction time is 20-30min;
the pH value of the acidic polyvinyl alcohol aqueous solution dispersed with the graphene is 3-5, wherein the concentration of the graphene is 5-10wt%, the concentration of the polyvinyl alcohol is 5-10wt%, and the volume ratio of the prepolymer methyl melamine to the acidic polyvinyl alcohol aqueous solution dispersed with the graphene is 10 (50-80);
the secondary heating reaction temperature is 60-70 ℃, the reaction time is 30-50min, and the secondary heating reaction is carried out under the ultrasonic condition.
3. The method for producing the titanium dioxide composite material according to claim 1, wherein in the step (2): the graphene/melamine formaldehyde composite particles in the mixed solution are 3-5wt% in concentration, the surfactant is 0.05-0.1wt% in concentration, ammonia water is used for adjusting the pH value of the mixed solution to 8-10, the solvent of the mixed solution is ethanol, and the surfactant is cetyl trimethyl ammonium bromide.
4. The method for producing a titanium dioxide composite material according to claim 1, wherein in the step (3): the titanium source in the titanium source solution is tetraethyl titanate, tetrapropyl titanate or tetrabutyl titanate, the solvent of the titanium source solution is ethanol, and the concentration of the titanium source in the titanium source solution is 10-20wt%; the mixing volume ratio of the titanium source solution to the mixed solution is 10: (5-10).
5. The method for producing the titanium dioxide composite material as claimed in claim 1, wherein in the step (3): the dripping process is carried out at 50-60 ℃, and the drying is freeze drying.
6. Use of the titanium dioxide composite material prepared by the preparation method according to claim 1 as an energy storage material.
7. The use of the titanium dioxide composite material according to claim 6 as an energy storage material, wherein the titanium dioxide composite material is used as a negative electrode material for an ion battery.
8. Use of the titanium dioxide composite material according to claim 7 as an energy storage material, characterized in that the ion battery is in particular a lithium ion battery or a sodium ion battery.
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