CN109950502B - TiO 22Preparation method and application of domain structure regulated titanium lithium silicate material - Google Patents

TiO 22Preparation method and application of domain structure regulated titanium lithium silicate material Download PDF

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CN109950502B
CN109950502B CN201910258331.8A CN201910258331A CN109950502B CN 109950502 B CN109950502 B CN 109950502B CN 201910258331 A CN201910258331 A CN 201910258331A CN 109950502 B CN109950502 B CN 109950502B
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tio
domain structure
tisio
lithium titanium
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尉海军
何迪
吴天昊
苏恒
王博亚
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Beijing University of Technology
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Abstract

TiO 22A preparation method and application of a domain structure regulated titanium lithium silicate material belong to the technical field of batteries. The composite structure has a main body of lithium titanium silicate and a structural chemical formula of Li2TiSiO5While the lithium titanium silicate is compounded with TiO2The domain structure can be used as a lithium ion battery cathode material. By TiO2Introduction of domain structure in original pure Li2TiSiO5On the basis, the composite structure shows good cycling stability and high specific capacity. On the basis, the surface carbon layer is introduced at the same time, so that the electronic conductivity of the composite structure is further enhanced, and the rate capability of the material is improved. The method discloses a preparation method of the composite structure.

Description

TiO 22Preparation method and application of domain structure regulated titanium lithium silicate material
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to TiO capable of serving as a negative electrode of a lithium ion battery2The preparation and application of the lithium titanium silicate composite material are regulated and controlled by the domain structure.
Background
As an environment-friendly chemical energy storage device, a lithium ion battery has been widely used in the fields of vehicles, electronic devices, smart grids, and the like. The basic components of the lithium ion battery mainly comprise a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the positive electrode and the negative electrode are main influencing factors determining the performance of the battery. Since the first successful commercialization of lithium batteries, graphite-based materials have occupied the major market for lithium battery cathodes due to their wide reserves, low cost, high energy density, and the like. The graphite-based material is an intercalation-type negative electrode material, and intercalation/deintercalation of lithium ions mainly occurs between layers. However, the charge and discharge potential of graphite is close to the deposition potential of metallic lithium, which causes the formation of lithium dendrite, thus puncturing the diaphragm to cause the internal short circuit of the battery, and causing the safety accidents such as fire. The embedded negative electrode material has the advantage of small volume change, but has a relative capacityLower. Another commercially available intercalation-type negative electrode material is Li4Ti5O12The theoretical capacity of the material is 175mAh/g, and the potential is about 1.5V. The material has long cycle life and excellent rate performance, and has a zero strain effect so that the material has good stability. The high potential avoids the formation of lithium dendrites, but also makes the material less energy dense. The search for new negative electrode materials with high specific capacity and lower potential has led to extensive research. Wangxing et al prepared a series of lithium titanium silicate materials (patent publication Nos.: CN 105024070A, CN 104810513A, CN 105152177A, CN 105140516A) by different methods and applied them to the negative electrode of lithium ion battery. Then, the material was subjected to carbon coating and doping studies by Yao et al (patent publication No.: CN 105226281A). The experimental result shows that the material has lower charge-discharge potential (about 0.28V) and high specific capacity (about 308mAh/g), but the material has poor conductivity, so the material has lower specific capacity and poor cycling stability under the condition of no carbon coating.
The invention obtains TiO by introducing a micro-domain structure on a lithium titanium silicate matrix material2The lithium titanium silicate material with the regulated and controlled domain structure shows excellent cycling stability without further modification, and shows excellent rate performance and better cycling stability under the condition of large current.
Disclosure of Invention
The invention provides a TiO2The preparation method of the titanium lithium silicate material with the domain structure regulated and controlled further introduces TiO on the basis of the titanium lithium silicate2The domain structure improves the cycle stability and discharge capacity of the material.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
TiO 22The lithium titanium silicate negative electrode material with the regulated domain structure is characterized in that the negative electrode material main body is lithium titanium silicate Li2TiSiO5While the lithium titanium silicate is compounded with TiO2The domain structure regulates and controls the cathode material, and the lithium titanium silicate Li2TiSiO5In mass percent ofFrom 90% to 100% (excluding 100%).
The lithium titanium silicate Li2TiSiO5Is pure or modified lithium titanium silicate, and the TiO2The domains form a composite structure, preferably TiO2The domain structure is located in lithium titanium silicate Li2TiSiO5Surface, lithium titanium disilicate Li2TiSiO5In the form of a sheet, then TiO2The domain structure is distributed in lithium titanium silicate Li2TiSiO5The periphery of the sheet structure forms a ring structure, or the TiO coated with carbon on the surface is also included2The domain structure regulates and controls the lithium titanium silicate cathode material.
The modified lithium titanium silicate material comprises one or more of a carbon-coated lithium titanium silicate material, a doped lithium titanium silicate material and a doped and coated lithium titanium silicate material. The negative electrode material is particles, and the particle size can be micron or nanometer. Doped lithium titanosilicate, the doping element of which comprises a metal cation and a non-metal anion. Wherein the metal cation is Na+、K+、Cs+、Mg2+、Ca2+、Ba2+、Al3+、Bi3+、Ge2+/4+、 Sn2+/4+、Zr4+、V3+/5+、Nb5+、Ta5+、Cr3 +、Mo4+/6+、W3+/4+/6+、Mn3+/4+/7+、Fe3+/4+、Co3+/4+、Ni2+/3+/4+、 Cu+/2+、Zn2+(ii) a Wherein the non-metal anions include B, C, N, F, P, S, Cl, Br, I. The percentage range of the doped impurities is 0.001% -10%. The doping element species may be one or more of the above doping elements.
In the present invention, the TiO is2The domain structure may be present in the composite material in the form of crystals including anatase structure, TiO2One or more of-B structure and rutile structure, wherein TiO2The characteristic peak position of the domain structure in X-ray powder diffraction preferably appears at 24-28 degrees (copper target); TiO 22Can also be in an amorphous state, and the composite material of the composite material has no obvious peak in an X-ray powder diffraction spectrum(ii) occurs;
the preparation method of the micro-domain structure regulating material mainly comprises a chemical hydrothermal method, a chemical vapor deposition method, a solution method and an atomic layer deposition method.
First method, hydrothermal method, of mono-pure or modified Li2TiSiO5Adding into saccharide (preferably glucose, sucrose, chitosan (concentration preferably 0.05-1mol/L) water solution, controlling hydrothermal time and temperature, and further sintering to obtain TiO2Domain structure modulated Li2TiSiO5/TiO2A composite structural material. Wherein the hydrothermal temperature is 120-200 ℃, and the hydrothermal time is 1-24 h; the sintering temperature is 600-800 ℃, the time is 2-4 h, and the atmosphere is air, nitrogen, argon or argon/hydrogen mixed gas.
The second method, chemical vapor deposition, is to use pure or modified Li2TiSiO5Fixing in a reaction chamber, introducing Ti-containing organic precursor titanium source vapor (preferably titanium isopropoxide and titanium isopropoxide) in an inert atmosphere, and introducing water/oxygen as a catalyst to promote hydrolysis of the titanium source to obtain micro-region amorphous TiO2Domain structure modulated Li2TiSiO5/TiO2A composite structural material. Further sintering to obtain crystalline TiO2Domain structure modulated Li2TiSiO5/TiO2A composite structural material. The sintering temperature is 400-800 ℃, the time is 2-8h, and the atmosphere is air, nitrogen, argon or argon/hydrogen mixed gas.
The third method, the solution method, is to use pure or modified Li2TiSiO5Adding the mixture into an organic solution containing a titanium source, uniformly stirring, adding a precipitator, drying and grinding to obtain amorphous TiO2Domain structure modulated Li2TiSiO5 /TiO2Composite structural material of TiO2No obvious XRD peak. The organic solvent is preferably ethanol or ethylene glycol, and the precipitant can be water or ammonia water.
A fourth method, atomic layer deposition, is to deposit pure or modified Li2TiSiO5Fixed in a reaction chamber and carried by argonQi in H2O and titanium isopropoxide as reactants at a temperature of 110-300 ℃, nitrogen as a carrier gas and a gas flow of 20-200 sccm. Depositing a certain thickness and drying to obtain amorphous TiO2Domain structure modulated Li2TiSiO5/TiO2Composite structural material of TiO2No obvious XRD peak. Can be further sintered to obtain crystalline TiO2Domain structure modulated Li2TiSiO5/TiO2A composite structural material. The sintering temperature is 400-800 ℃, the time is 2-8h, and the atmosphere is air, nitrogen, argon or argon/hydrogen mixed gas. The deposition thickness is 1-10 nm.
In the invention, the titanium source is one or more of tetrabutyl titanate, titanium isopropoxide, titanium trichloride, titanium tetrachloride, titanium sulfate, titanyl sulfate, titanium boride, titanium fluoride, titanium nitride and titanium oxide.
The preparation method of the carbon-coated micro-domain structure regulating material mainly comprises a solvothermal method, a chemical vapor deposition method and a ball milling method.
The first method, the solvothermal method, is to take the prepared TiO2The domain structure is regulated and controlled, lithium titanium silicate is dispersed in water, ultrasonically dispersed and stirred, and then graphene oxide solution (preferably 0.1mg/ml) with certain concentration is gradually added into TiO2In the aqueous solution of the lithium titanium silicate regulated and controlled by the domain structure, the pH value of the solution can be selectively regulated or a certain amount of polyethyleneimine solution is added, so that TiO2The domain structure regulates and controls titanium lithium silicate and graphene oxide to generate copolymerization so as to form a precipitate, then the precipitate is centrifuged to obtain a solid, the solid is placed in an ethanol solution to react for 12-24h at the temperature of 150 ℃, the obtained solid is centrifugally washed by ethanol and dried, and the solid is sintered for 2-10h in a muffle furnace or a tubular furnace at the temperature of 800 ℃ at 300 ℃ in the atmosphere of air, nitrogen, argon or argon/hydrogen mixed gas.
The second method, chemical vapor deposition, is to prepare the prepared TiO2The domain structure regulates and controls the titanium lithium silicate to be fixed in a reaction chamber, an organic carbon source (preferably hydrocarbon gas) is introduced, argon or nitrogen is taken as carrier gas, the heating temperature is 600-800 ℃, the time is 1-4h, and the thickness of a carbon layer is 1-10 nm.
The third method is to take the prepared TiO by ball milling2The domain structure regulates and controls titanium lithium silicate and a carbon source (preferably graphene, carbon nano tubes, glucose and sucrose) to be placed in a ball milling tank, a certain amount of grinding balls with different gradations are added, the rotating speed is regulated to be 100-400 r/min, and the time is 2-8 h. The sintering treatment can also be properly carried out to improve the bonding force among the materials, wherein the sintering temperature is 300-800 ℃, the time is 1-4h, and the atmosphere is nitrogen, argon or argon/hydrogen mixed gas.
The invention introduces micro-TiO2Domain structure, improved pure Li2TiSiO5Conductivity and cycling stability of the conductive layer; by introducing the surface carbon layer, the electronic conductivity of the material is improved, so that the rate capability of the material is further improved. Compared with the traditional graphite material, the charge-discharge potential and the capacity of the composite structure material are between those of lithium titanate and the graphite material, so that the formation of a large number of lithium dendrites is avoided, and the composite structure material has higher capacity and excellent rate capability. The preparation method is simple and easy to implement, and has good application prospect.
Drawings
Figure 1 XRD spectrum of example 1
FIG. 2 Raman spectra in example 1
FIG. 3 Transmission Electron microscopy of example 1
FIG. 4 second to fourth circles of Charge-discharge curves in example 1
FIG. 5 Long cycling curves for assembled batteries tested in example 1
Figure 6 XRD spectrum of example 2
Fig. 7 long cycle curves for assembled cells tested in example 2.
Detailed Description
The present invention will be better understood from the following examples, but the present invention is not limited to only the following examples.
Example 1: 0.5g of prepared flaky Li was taken2TiSiO5Dispersed in 40ml of glucose solution with a concentration of 0.05 mol/L. Stirring thoroughly for 30min, transferring the mixed solution into a reaction kettle, and performing hydrothermal treatment at 180 deg.C for 5 h. Completion of the reactionThe obtained solid is subjected to centrifugal water washing and drying, and then is sintered for 2 hours in a tube furnace under the atmosphere of argon/hydrogen at the temperature of 700 ℃. To obtain TiO2Domain structure modulated Li2TiSiO5/TiO2A composite structural material. The XRD structure is shown in figure 1, and obvious TiO appears between 24 and 28 DEG2And (4) characteristic structure. The TiO was analyzed by further Raman analysis (FIG. 2)2From anatase structure with TiO2-B structure composition. In addition, transmission electron microscopy results show that in Li2TiSiO5The peripheral edge of the sheet structure forms TiO in situ2Nano-crystalline domains, as shown in fig. 3.
Mixing the lithium titanium silicate composite material, acetylene black and PTFE solution at a ratio of 70:20:10 to prepare a pole piece with the diameter of 6mm, and drying in an oven at 120 ℃ for 12 hours. The pole pieces were then weighed and pressed onto a copper mesh current collector and compacted under a pressure of 10 MPa. Assembling a 2032 type button cell in a glove box according to the assembly sequence of the prepared electrode material, the diaphragm and the lithium metal wafer with the diameter of 10mm, wherein the electrolyte adopts 1M LiPF6(EC: DEC ═ 1:1vol), 2 to 3 drops were added dropwise. And (3) carrying out charge and discharge tests on the mixture after standing for 12 hours, wherein the voltage range is 3-0.1V, and the test current density adopts 100 mA/g. The second to fourth circles of the charge-discharge curve are shown in FIG. 4, and the charge-discharge capacity is about 310 mAh/g. Fig. 5 is a graph showing long-cycle charge and discharge.
Example 2: 0.5g of prepared Li was taken2TiSiO5Dispersing in 40ml water, stirring thoroughly for 30min, transferring the mixed solution to a reaction kettle, and heating at 180 deg.C for 5 h. After the reaction is finished, the obtained solid is subjected to centrifugal washing and drying, and then is sintered for 2 hours in a tubular furnace under the atmosphere of argon/hydrogen at the temperature of 700 ℃. To obtain TiO2Domain structure modulated Li2TiSiO5/TiO2A composite structural material. The XRD structure is shown in figure 6, and obvious TiO appears between 24 and 28 DEG2And (4) characteristic structure.
Mixing the lithium titanium silicate composite material, acetylene black and PTFE solution at a ratio of 70:20:10 to prepare a pole piece with the diameter of 6mm, and drying in a 120 ℃ ovenAnd (4) 12 h. The pole pieces were then weighed and pressed onto a copper mesh current collector and compacted under a pressure of 10 MPa. Assembling a 2032 type button cell in a glove box according to the assembly sequence of the prepared electrode material, the diaphragm and the lithium metal wafer with the diameter of 10mm, wherein the electrolyte adopts 1M LiPF6(EC: DEC ═ 1:1vol), 2 to 3 drops were added dropwise. And (3) carrying out charge and discharge tests on the mixture after standing for 12 hours, wherein the voltage range is 3-0.1V, and the test current density adopts 10 mA/g. The cycle test is shown in FIG. 7, and the charge/discharge capacity is about 250 mAh/g.
Example 3: 0.5g of prepared Li2TiSiO5Dispersing in 20ml ethanol solution, and marking as solution A; 0.1ml of TBT solution was dispersed in 20ml of ethanol solution and recorded as solution B. And dropwise adding the solution A into the solution B, fully stirring for 1h, dropwise adding 2ml of ammonia water solution, continuously stirring for 24h, and drying. By further analysis, the TiO2In an amorphous state.
The negative electrode material prepared above was treated and tested according to the method in example 2, and the initial discharge capacity was found to be lower than that in example 2.
Example 4: 0.5g of prepared Li was taken2TiSiO5Dispersed in 40ml of ethylene glycol solution and subsequently 0.1ml of TiCl was added4The solution was thoroughly stirred, 2ml of ammonia water was added, and the mixture was stirred at 150 ℃ for 12 hours and then centrifuged. Then sintering for 2h at 380 ℃ under the air condition. By further analysis, the TiO2From TiO2-B structure composition.
The prepared negative electrode material is treated and tested according to the method in the embodiment 2, and the initial discharge capacity of the prepared negative electrode material is about 260mAh/g and is slightly higher than that of the prepared negative electrode material in the embodiment 2.
Example 5: the TiO obtained in example 2 was2Domain structure modulated Li2TiSiO5/TiO2The composite structure material is placed in a CVD deposition furnace, toluene is used as a carbon source, and the toluene and carrier gas are introduced into a reaction chamber together, wherein the heating temperature is 700 ℃, and the time is 1 h. To obtain carbon-coated TiO2Domain structure modulated Li2TiSiO5/TiO2A composite structural material.
The obtained negative electrode material is processed and tested according to the method in the embodiment 2, and the initial discharge capacity of the negative electrode material is higher than that of the negative electrode material in the embodiment 2.
Example 6: 0.5g of prepared Li was taken2TiSiO5Placing in an atomic layer deposition device, taking titanium isopropoxide as a titanium source, and H2O is used as catalyst to control TiO2The deposition thickness is 5nm to obtain amorphous TiO2Domain structure modulated Li2TiSiO5/TiO2A composite structural material.
The prepared negative electrode material is processed and tested according to the method in the embodiment 2, and the initial discharge capacity of the negative electrode material is slightly higher than that of the negative electrode material in the embodiment 3.

Claims (11)

1. TiO 22The lithium titanium silicate negative electrode material with the regulated domain structure is characterized in that the negative electrode material main body is lithium titanium silicate Li2TiSiO5While the lithium titanium silicate is compounded with TiO2The domain structure regulates and controls the cathode material, and the lithium titanium silicate Li2TiSiO5The mass percent of (A) is 90-100%, not including 100%; or also surface carbon-coated TiO2The domain structure regulates and controls the lithium titanium silicate cathode material.
2. A TiO compound according to claim 12The lithium titanium silicate cathode material with regulated domain structure is characterized in that TiO2The domain structure is located in lithium titanium silicate Li2TiSiO5A surface.
3. A TiO compound according to claim 22The lithium titanium silicate cathode material with regulated domain structure is characterized in that lithium titanium silicate Li2TiSiO5In the form of a sheet, then TiO2The domain structure is distributed in lithium titanium silicate Li2TiSiO5The peripheral edges of the sheet-like structure form a ring-shaped structure.
4. A TiO compound according to claim 12The lithium titanium silicate cathode material is characterized in that the cathode material is particles, and the particle size is micron or nanometer; the silicic acidTitanium lithium Li2TiSiO5Is pure or modified lithium titanium silicate, and the TiO2The domain structure forms a composite structure.
5. A TiO compound according to claim 42The lithium titanium silicate cathode material is characterized in that the modified lithium titanium silicate material comprises one or more of a carbon-coated lithium titanium silicate material, a doped lithium titanium silicate material and a doped and coated lithium titanium silicate material.
6. A TiO compound according to claim 52The negative electrode material of the lithium titanium silicate is regulated and controlled by a domain structure, and is characterized in that doping elements of the doped lithium titanium silicate comprise metal cations and non-metal anions; wherein the metal cation is Na+、K+、Cs+、Mg2 +、Ca2+、Ba2+、Al3+、Bi3+、Ge2+/4+、Sn2+/4+、Zr4+、V3+/5+、Nb5+、Ta5+、Cr3+、Mo4+/6+、W3+/4+/6+、Mn3+/4+/7+、Fe3+/4+、Co3+/4+、Ni2+/3+/4+、Cu+/2+、Zn2+(ii) a Wherein the non-metal anions comprise B, C, N, F, P, S, Cl, Br and I; the percentage range of the doped impurities is 0.001% -10%; the doping element species is one or more of the above doping elements.
7. A TiO compound according to claim 12The lithium titanium silicate cathode material with the regulated domain structure is characterized in that the TiO is2The domain structure exists in the composite material in the form of crystal including anatase structure, TiO2One or more of-B structure and rutile structure, wherein TiO2The characteristic peak position of the domain structure in X-ray powder diffraction is 24-28 degrees; TiO 22Or in an amorphous state, and the composite material has no obvious peak in an X-ray powder diffraction spectrum.
8. The TiO of any one of claims 1 to 72The preparation method of the lithium titanium silicate cathode material with the domain structure regulated and controlled is characterized by mainly comprising a hydrothermal method, a chemical vapor deposition method, a solution method and an atomic layer deposition method;
first method, hydrothermal method, of mono-pure or modified Li2TiSiO5Adding into saccharide aqueous solution, controlling hydrothermal time and temperature, and further sintering to obtain TiO2Domain structure modulated Li2TiSiO5/TiO2A composite structural material; wherein the hydrothermal temperature is 120-200 ℃, and the hydrothermal time is 1-24 h; the sintering temperature is 600-800 ℃, the time is 2-4 h, and the atmosphere is air, nitrogen, argon or argon/hydrogen mixed gas;
the second method, chemical vapor deposition, is to use pure or modified Li2TiSiO5Fixing in a reaction chamber, introducing Ti-containing precursor titanium source steam in inert atmosphere, and introducing water/oxygen as catalyst to promote hydrolysis of the titanium source to obtain micro-region amorphous TiO2Domain structure modulated Li2TiSiO5/TiO2A composite structural material; or further sintering to obtain crystalline TiO2Domain structure modulated Li2TiSiO5/TiO2A composite structural material; the sintering temperature is 400-800 ℃, the time is 2-8h, and the atmosphere is air, nitrogen, argon or argon/hydrogen mixed gas;
the third method, the solution method, is to use pure or modified Li2TiSiO5Adding the mixture into an organic solution containing a titanium source, uniformly stirring, adding a precipitator, drying and grinding to obtain amorphous TiO2Domain structure modulated Li2TiSiO5/TiO2Composite structural material of TiO2No obvious XRD peak exists; the organic solvent is ethanol or glycol, and the precipitator is water or ammonia water;
a fourth method, atomic layer deposition, is to deposit pure or modified Li2TiSiO5Fixed in a reaction chamber, taking argon or nitrogen as a carrier gas and H2O and titanium isopropoxide as reactants at a temperature of 110 ℃ to 300 ℃, and carrier gas flow rate20-200 sccm; depositing a certain thickness and drying to obtain amorphous TiO2Domain structure modulated Li2TiSiO5/TiO2Composite structural material of TiO2No obvious XRD peak; or further sintering to obtain crystalline TiO2Domain structure modulated Li2TiSiO5/TiO2The composite structure material is sintered at the temperature of 400-800 ℃ for 2-8h in the atmosphere of air, nitrogen, argon or argon/hydrogen mixed gas; the deposition thickness is 1-10 nm;
the titanium source is one or more of tetrabutyl titanate, titanium isopropoxide, titanium trichloride, titanium tetrachloride, titanium sulfate, titanyl sulfate, titanium boride, titanium fluoride, titanium nitride and titanium oxide.
9. The method according to claim 8, wherein the saccharide in the first method comprises a monosaccharide, disaccharide or polysaccharide, at a concentration of 0.05-1 mol/L; the second method is that the organic precursor titanium source vapor is titanium isopropoxide.
10. A TiO compound according to claim 12The lithium titanium silicate cathode material with the regulated domain structure is characterized in that TiO coated with carbon on the surface2The preparation method of the lithium titanium silicate cathode material with a domain structure regulated and controlled comprises the following steps of (1) preparing a carbon coating material, wherein the carbon coating material comprises 0.5-30% of carbon, and the carbon coating method comprises a solvothermal method, a chemical vapor deposition method and a ball milling method;
the first method, the solvothermal method, is to take the prepared TiO2Dispersing lithium titanium silicate in water by regulating domain structure, ultrasonically dispersing and stirring, and then dropwise adding a graphene oxide solution with the concentration of 0.1mg/ml into TiO2Regulating and controlling the pH value of the solution in the aqueous solution of the lithium titanium silicate by the domain structure or adding a polyethyleneimine solution to ensure that the TiO is2The domain structure is used for regulating and controlling the copolymerization between the lithium titanium silicate and the graphene oxide to form a precipitate, then the precipitate is centrifuged to obtain a solid, the solid is placed in an ethanol solution to react for 12-24h at the temperature of 100 ℃ and 150 ℃, the obtained solid is centrifuged, washed by ethanol and dried, and sintered for 2-10h in a muffle furnace or a tubular furnace at the temperature of 300 ℃ and 800 ℃ under the atmosphereAir, nitrogen, argon or argon/hydrogen mixed gas;
the second method, chemical vapor deposition, is to prepare the prepared TiO2The domain structure regulates and controls the titanium lithium silicate to be fixed in a reaction chamber, a hydrocarbon gas organic carbon source is introduced, argon or nitrogen is used as carrier gas, the heating temperature is 600-800 ℃, the time is 1-4h, and the thickness of a carbon layer is 1-10 nm;
the third method, ball milling, is to obtain the prepared TiO2Adjusting and controlling the titanium lithium silicate and a carbon source in a ball milling tank by a domain structure, wherein the carbon source is selected from graphene, carbon nano tubes, glucose and sucrose, adding a certain amount of grinding balls with different gradations, and adjusting the rotating speed to be 100-400 r/min for 2-8 h; and sintering to improve the binding force between the materials, wherein the sintering temperature is 300-800 ℃, the time is 1-4h, and the atmosphere is nitrogen, argon or argon/hydrogen mixed gas.
11. The TiO of any one of claims 1 to 72The application of the lithium titanium silicate cathode material is regulated and controlled by a domain structure, and the lithium titanium silicate cathode material is applied to lithium ion batteries.
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