CN112591790A - Modulation of MOF-derived TiO2Preparation method and application of @ C morphology particle size - Google Patents
Modulation of MOF-derived TiO2Preparation method and application of @ C morphology particle size Download PDFInfo
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 29
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- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
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Abstract
The invention belongs to the technical field of lithium ion battery application, and discloses a method for regulating and controlling MIL-125(Ti) -derived TiO2The preparation method and application of the @ C morphology particle size are characterized in that absolute methanol and N-N dimethylformamide are used as solvents, terephthalic acid and tetrabutyl titanate are used as an organic carbon source and a titanium source respectively, and different types of surfactants PVP (K23-27), F127 and the like are added to regulate and control TiO2The shape and the particle size of @ C are mixed, then the mixture is transferred into a high-pressure reaction kettle, and the mixture is naturally cooled after heat preservation; sequentially centrifugally washing the mixture by using absolute methanol and N-N dimethylformamide, drying the mixture in vacuum to obtain a white precursor product,finally calcining the mixture in argon atmosphere to obtain the MIL-125(Ti) -derived TiO with the shape and the particle size regulated and controlled2@ C. The invention obtains the active material which has different shape grain diameters, controllable and adjustable pore channel structure, excellent performance, low cost and can meet various electrochemical applications.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery application, and particularly relates to a method for regulating and controlling MIL-125(Ti) -derived TiO2A preparation method and application of the @ C morphology particle size.
Background
Currently, in lithium ion battery applications, TiO2Is considered one of the most promising transition metal materials because of its relatively low density and molar mass, which provides the advantages of excellent volume, mass energy density, low cost, high safety, etc. In addition, TiO relative to other materials2The structure is easier to control, and a solid electrolyte membrane (SEI) is not easy to generate in the working process of the battery. However, TiO2The ionic conductivity is poor and the volume change is generated in the charging and discharging processes of the lithium ion battery, so that the multiplying power performance is poor, and further TiO is provided2The application prospect of (2) brings limitations. Thus, the control of the preparation of different TiO2The porous structure is necessary for improving the electrochemical performance and optimizing the application prospect. In the charging and discharging process of the battery, the cavity position in the porous structure can buffer the volume change and release the internal pressure, so that the performance of the battery is improved; close contact between the active material and the electrolyte can also be promoted, thereby enhancing Li+Diffusion capacity and rate capability. Although this solution has been proposed to improve its performance, porous TiO produced by conventional synthesis methods, such as self-assembly, templating, are used2The application of high-performance batteries still cannot be met, and other methods which are more efficient and more beneficial to performance improvement need to be adopted to optimize TiO2The application prospect of (1).
Metal-organic framework Materials (MOFs) are mixed functional materials composed of metal ions and inorganic linking units, and their high porosity and adjustable pore structure make them widely used in the fields of gas adsorption/separation, catalysis, biomedicine, electrochemistry and photochemistry. Because metal and oxygen atoms are arranged at a periodic atomic level in the MOFs crystal, the MOFs can be completely converted into a transition metal oxide without long-range atom migration, and has stable porosity, so that in order to better utilize nano holes and channels in the MOFs as an ion transport path, the MOFs is often used as a precursor for preparing porous transition metals, and the method replaces the traditional synthesis method.
Through the above analysis, the problems and defects of the prior art are as follows: preparation of TiO by derivation of existing MOFs2The @ C material is single in shape and large in size, so that the application of the @ C material in the lithium ion battery is limited.
The difficulty in solving the above problems and defects is: the appearance is regulated and controlled by the surfactant by adsorbing different crystal faces of the material by amphiphilic molecules of the surfactant, so that different crystal faces are passivated by different surface inhibitors. The difficulty is that the surfactants with different concentrations are combined with different crystal faces, and the different concentrations are difficult to accurately determine in the experimental process.
The significance of solving the problems and the defects is as follows: preparing MIL-125(Ti) -derived TiO with different shapes and particle sizes2The @ C can optimize the performance of the material, so that the prepared active material can meet electrochemical applications with different requirements.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for regulating MOF-derived TiO2A preparation method and application of the @ C morphology particle size.
The invention is realized by that the MOF derived TiO is regulated and controlled2Method for preparing @ C morphology and particle size for regulating MOF-derived TiO2The preparation method of the @ C morphology particle size comprises the following steps: anhydrous methanol and N-N dimethylformamide are taken as solvents, terephthalic acid and tetrabutyl titanate are respectively taken as an organic carbon source and a titanium source, and different types of surfactants are added to regulate TiO2The shape and the particle size of @ C are mixed, then the mixture is transferred into a high-pressure reaction kettle, and the mixture is naturally cooled after being kept warm for a period of time; sequentially centrifugally washing with anhydrous methanol and N-N dimethylformamide, and vacuum drying to obtainObtaining a white product, and finally calcining the white product in an argon atmosphere to obtain TiO with the regulated morphology and particle size2@C。
Further, the modulating MOF-derived TiO2The preparation method of the @ C morphology particle size comprises the following steps:
step one, preparing a mixed solution of anhydrous methanol and N-N dimethylformamide as a solvent, adding terephthalic acid and PVP (K23-27)/(F127), stirring, and ultrasonically dissolving until the solution is transparent;
the ultrasonic treatment can make the raw materials fully dissolved in the organic solvent, and provide uniform precursor reaction solution for the next reaction.
Step two, adding tetrabutyl titanate by times; firstly, adding a small part of tetrabutyl titanate as seed crystal, fully stirring, and then adding the rest tetrabutyl titanate to obtain a mixed solution;
the purpose of the fractional addition of the inorganic titanium source was to reduce the particle size of the MIL-125(Ti) precursor.
And step three, transferring the mixed solution into a high-pressure reaction kettle, cooling the high-pressure reaction kettle to room temperature, centrifugally washing the mixture to obtain a white precipitate, and collecting a product to obtain the material with the regulated morphology and the regulated particle size.
Further, in the first step and the second step, in the mixing of the reactant ratios, assuming that the mixing ratio of the mass of terephthalic acid, the mass of PVP (K23-27)/(F127), the volume of tetrabutyl titanate and the volume of organic solvent is a: b: c: d; wherein a is more than or equal to 0 and less than or equal to 10; b is more than or equal to 0 and less than or equal to 10; c is more than or equal to 0 and less than or equal to 5; d is more than or equal to 10 and less than or equal to 60.
Further, in step three, the centrifugation conditions are as follows: the centrifugation speed was set at 12000 rpm and the centrifugation time was set at 10 minutes. This parameter was set in order to centrifuge the sample sufficiently to ensure that the impurities were washed clean.
Further, in the third step, after the product is collected, the product is dried in vacuum, and the drying time is 6-8 hours.
Further, the modulating MOF-derived TiO2The preparation method of the @ C morphology particle size further comprises the following steps:
(1) preparing a mixed solution of 6ml of anhydrous methanol and 54ml of N-N dimethylformamide as a solvent, adding 6g of terephthalic acid and 3g of PVP (K23-27)/(F127), stirring, and ultrasonically dissolving until the solution is transparent;
(2) adding tetrabutyl titanate by times; adding 0.32ml of tetrabutyl titanate serving as seed crystal, fully stirring for 50min, and then adding 1.24ml of tetrabutyl titanate to obtain a mixed solution;
(3) transferring the mixed solution into a high-pressure reaction kettle, and putting the high-pressure reaction kettle into a 150 ℃ oven to keep for 24 hours; cooling the high-pressure reaction kettle to room temperature, and centrifugally washing the mixture to obtain a white precipitate;
(4) and (3) carrying out ultrasonic dispersion treatment on the white precipitate, alternately washing the white precipitate for a plurality of times by adopting absolute methanol and N-N dimethylformamide, finally carrying out centrifugal collection, and collecting the product to obtain the precursor material with the regulated morphology and particle size.
Another object of the present invention is to provide a method for modulating MOF-derived TiO using the same2TiO with different shapes and different particle sizes prepared by the preparation method of @ C shape and particle size2@C。
Another objective of the invention is to provide a method for regulating and controlling the TiO based on a solvothermal synthesis method2The preparation method of the shape and the particle size of @ C.
The invention also aims to provide the TiO with different morphologies and different particle sizes2The application of @ C as a negative electrode material in a lithium ion battery.
The invention also aims to provide the TiO with different morphologies and different particle sizes2The application of @ C as an active material in electrochemistry.
By combining all the technical schemes, the invention has the advantages and positive effects that: the invention provides a method for regulating MOF-derived TiO2The preparation method of the @ C morphology particle size is characterized in that on the basis of original solvothermal synthesis, organic solvent is used as solvent, different types of surfactants and the dosage of the surfactants are added by regulation and control, and the obtained TiO is subjected to2The shape and the particle size of the @ C material are correspondingly regulated, the required raw materials are simple and easy to obtain, and the active material which has different shape particle sizes, controllable and adjustable pore channel structure, excellent performance and low cost and can meet various electrochemical applications is prepared.
Compared with the prior art, the method prepares TiO with different shapes and particle sizes by adjusting the type and the dosage of the surfactant2@ C active materials are used in lithium ion batteries; modulating TiO2The @ C active material does not change a mesoporous channel and increase a plurality of crystal faces while being converted from a round cake-shaped structure to a polyhedral structure, so that TiO is reduced2The @ C active material has a particle size that further improves its electrochemical performance.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments of the present invention will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic representation of the modulation of MOF-derived TiO provided by embodiments of the invention2A flow chart of a preparation method of the @ C morphology particle size.
FIGS. 2(a), (b) and (c) are schematic diagrams of the synthesis of TiO based on the solvothermal method according to the embodiment of the present invention2SEM images of the morphology and particle size before and after @ C (PVP/F127).
FIG. 3 is a schematic diagram of an XRD (X-ray diffraction) spectrum for regulating and controlling the morphology and the particle size of MIL-125(Ti) based on solvothermal synthesis provided by the embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Aiming at the problems in the prior art, the invention provides a method for regulating MOF-derived TiO2The invention discloses a preparation method and application of the @ C morphology particle size, and is described in detail below with reference to the accompanying drawings.
As shown in FIG. 1, embodiments of the invention provide for modulating MOF-derived TiO2The preparation method of the @ C morphology particle size comprises the following steps:
s101, preparing a mixed solution of anhydrous methanol and N-N dimethylformamide as a solvent, adding terephthalic acid and PVP (K23-27)/(F127), stirring, and ultrasonically dissolving until the solution is transparent;
s102, adding tetrabutyl titanate in batches; firstly, adding a small part of tetrabutyl titanate as seed crystal, fully stirring, and then adding the rest tetrabutyl titanate to obtain a mixed solution;
s103, transferring the mixed solution into a high-pressure reaction kettle, cooling the temperature of the high-pressure reaction kettle to room temperature, centrifugally washing the mixture to obtain a white precipitate, and collecting a product to obtain the precursor material with the regulated morphology and particle size.
The invention provides a method for regulating MOF-derived TiO2The preparation method of the morphology and particle size of @ C can also be implemented by other steps by a person of ordinary skill in the art, and the method for regulating and controlling MOF-derived TiO provided by the invention in figure 12The method of preparation of the particle size of the @ C morphology is only one specific example.
The technical solution of the present invention is further described with reference to the following examples.
The invention provides TiO regulated and controlled based on solvothermal synthesis2The preparation method of the shape and the particle size of @ C can be implemented by other steps by a person of ordinary skill in the art, and TiO is regulated and controlled based on solvothermal synthesis provided by the invention shown in figure 12The preparation of the morphology and particle size of @ C is only one specific example.
Example 1
The invention provides TiO regulated and controlled based on solvothermal synthesis2The preparation method of the @ C morphology and particle size comprises the following steps: a mixed solution of 6ml of anhydrous methanol and 54ml of N-N dimethylformamide is prepared as a solvent, 6g of terephthalic acid and 3g of PVP (K23-27)/(F127) are added, and the mixture is stirred and ultrasonically treated to dissolve the mixture, so that the solution is transparent. Adding tetrabutyl titanate by times; adding 0.32ml of tetrabutyl titanate as seed crystal, fully stirring for 50min, and then adding 1.24ml of tetrabutyl titanate to meet the requirement of a titanium source required by MIL-125(Ti) crystal growth. And transferring the mixed solution into a high-pressure reaction kettle, and putting the high-pressure reaction kettle into a 150 ℃ oven to keep the temperature for 24 hours. Cooling the autoclave to room temperature, centrifugally washing the mixture to obtain a white precipitate, and subjecting the white precipitate to precipitationAnd (3) performing ultrasonic dispersion treatment, alternately washing the mixture for a plurality of times by adopting absolute methanol and N-N dimethylformamide, finally performing centrifugal collection, and collecting a product to obtain the material with the regulated morphology and the regulated particle size.
Example 2
The invention provides TiO regulated and controlled based on solvothermal synthesis2The preparation method of the @ C morphology and particle size comprises the following steps: a mixed solution of 6ml of anhydrous methanol and 54ml of N-N dimethylformamide is prepared as a solvent, 6g of terephthalic acid and 6g of PVP (K23-27)/(F127) are added, and the mixture is stirred and ultrasonically treated to dissolve the mixture, so that the solution is transparent. Adding tetrabutyl titanate by times; adding 0.32ml of tetrabutyl titanate as seed crystal, fully stirring for 50min, and then adding 1.24ml of tetrabutyl titanate to meet the requirement of a titanium source required by MIL-125(Ti) crystal growth. And transferring the mixed solution into a high-pressure reaction kettle, and putting the high-pressure reaction kettle into a 150 ℃ oven to keep the temperature for 24 hours. And cooling the high-pressure reaction kettle to room temperature, centrifugally washing the mixture to obtain a white precipitate, ultrasonically dispersing the white precipitate, alternately washing the white precipitate for several times by adopting anhydrous methanol and N-N dimethylformamide, centrifugally collecting the white precipitate, and collecting the product to obtain the material with the regulated morphology and the regulated particle size.
Example 3
The invention provides TiO regulated and controlled based on solvothermal synthesis2The preparation method of the @ C morphology and particle size comprises the following steps: a mixed solution of 6ml of anhydrous methanol and 54ml of N-N dimethylformamide is prepared as a solvent, 6g of terephthalic acid and 12g of PVP (K23-27)/(F127) are added, and the mixture is stirred and ultrasonically treated to dissolve the mixture, so that the solution is transparent. Adding tetrabutyl titanate by times; adding 0.32ml of tetrabutyl titanate as seed crystal, fully stirring for 50min, and then adding 1.24ml of tetrabutyl titanate to meet the requirement of a titanium source required by MIL-125(Ti) crystal growth. And transferring the mixed solution into a high-pressure reaction kettle, and putting the high-pressure reaction kettle into a 150 ℃ oven to keep the temperature for 24 hours. And cooling the high-pressure reaction kettle to room temperature, centrifugally washing the mixture to obtain a white precipitate, ultrasonically dispersing the white precipitate, alternately washing the white precipitate for several times by adopting anhydrous methanol and N-N dimethylformamide, centrifugally collecting the white precipitate, and collecting the product to obtain the material with the regulated morphology and the regulated particle size.
The above description is only for the purpose of illustrating the present invention and the appended claims are not to be construed as limiting the scope of the invention, which is intended to cover all modifications, equivalents and improvements that are within the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. MOF-derived TiO regulation and control method2The preparation method of the morphology and particle size of @ C is characterized in that the MOF-derived TiO is regulated and controlled2The preparation method of the @ C morphology particle size comprises the following steps: anhydrous methanol and N-N dimethylformamide are taken as solvents, phthalic acid and tetrabutyl titanate are respectively taken as an organic carbon source and a titanium source, and different types of surfactants are added to regulate TiO2The shape and the particle size of @ C are mixed, then the mixture is transferred into a high-pressure reaction kettle, and the mixture is naturally cooled after being kept warm for a period of time; sequentially centrifugally washing with anhydrous methanol and N-N dimethylformamide, vacuum drying to obtain a white product, and calcining in an argon atmosphere to obtain TiO with controlled morphology and particle size2@C。
2. The modulated MOF derived TiO of claim 12The preparation method of the morphology and particle size of @ C is characterized in that the MOF-derived TiO is regulated and controlled2The preparation method of the @ C morphology particle size comprises the following steps:
step one, preparing a mixed solution of anhydrous methanol and N-N dimethylformamide as a solvent, adding terephthalic acid and PVP/(F127), stirring, and ultrasonically dissolving until the solution is transparent;
step two, adding tetrabutyl titanate by times; firstly, adding a small part of tetrabutyl titanate as seed crystal, fully stirring, and then adding the rest tetrabutyl titanate to obtain a mixed solution;
and step three, transferring the mixed solution into a high-pressure reaction kettle, cooling the high-pressure reaction kettle to room temperature, centrifugally washing the mixture to obtain a white precipitate, and collecting a product to obtain the material with the regulated morphology and the regulated particle size.
3. The modulated MOF derived TiO of claim 22@ C morphologyThe preparation method of the particle size is characterized in that in the first step and the second step, in the reactant proportion mixing, the mixing proportion of the mass of terephthalic acid, the mass of PVP, the volume of tetrabutyl titanate and the volume of an organic solvent is a: b: c: d; wherein a is more than or equal to 0 and less than or equal to 10; b is more than or equal to 0 and less than or equal to 10; c is more than or equal to 0 and less than or equal to 5; d is more than or equal to 10 and less than or equal to 60.
4. The modulated MOF derived TiO of claim 22The preparation method of the morphology particle size of @ C is characterized in that in the third step, the centrifugation conditions are as follows: the centrifugation speed was set at 12000 rpm and the centrifugation time was set at 10 minutes.
5. The modulated MOF derived TiO of claim 22The preparation method of the shape particle size of @ C is characterized in that in the third step, after the product is collected, the product is dried in vacuum for 6-8 hours.
6. The modulated MOF derived TiO of claim 22The preparation method of the morphology and particle size of @ C is characterized in that the MOF-derived TiO is regulated and controlled2The preparation method of the @ C morphology particle size further comprises the following steps:
(1) preparing a mixed solution of 6ml of anhydrous methanol and 54ml of N-N dimethylformamide as a solvent, adding 6g of terephthalic acid and 3g of PVP/(F127), stirring, and ultrasonically dissolving until the solution is transparent;
(2) adding tetrabutyl titanate by times; adding 0.32ml of tetrabutyl titanate serving as seed crystal, fully stirring for 50min, and then adding 1.24ml of tetrabutyl titanate to obtain a mixed solution;
(3) transferring the mixed solution into a high-pressure reaction kettle, and putting the high-pressure reaction kettle into a 150 ℃ oven to keep for 24 hours; cooling the high-pressure reaction kettle to room temperature, and centrifugally washing the mixture to obtain a white precipitate;
(4) and (3) carrying out ultrasonic dispersion treatment on the white precipitate, alternately washing the white precipitate for a plurality of times by adopting absolute methanol and N-N dimethylformamide, finally carrying out centrifugal collection, and collecting a product to obtain the material with the regulated morphology and the regulated particle size.
7. Use of the MOF-derived TiO of any one of claims 1 to 6 for modulating MOF2TiO with different shapes and different particle sizes prepared by the preparation method of @ C shape and particle size2@C。
8. The method for controlling TiO of claim 7 based on solvothermal synthesis2The preparation method of the shape and the particle size of @ C.
9. The TiO of claim 7 with different morphologies and different particle sizes2The application of @ C as a negative electrode material in a lithium ion battery.
10. The TiO of claim 7 with different morphologies and different particle sizes2The application of @ C as an active material in electrochemistry.
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