CN114702065A - Oxygen-enriched defective TiO2Carbon composite material, preparation method and application thereof - Google Patents
Oxygen-enriched defective TiO2Carbon composite material, preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000001301 oxygen Substances 0.000 title claims abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 27
- 230000002950 deficient Effects 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 12
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 10
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 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 6
- 230000007547 defect Effects 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 7
- 239000010406 cathode material Substances 0.000 abstract description 6
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 6
- 150000004706 metal oxides Chemical class 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000012983 electrochemical energy storage Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 30
- 239000000243 solution Substances 0.000 description 8
- 239000004408 titanium dioxide Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 239000012702 metal oxide precursor Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000005298 paramagnetic effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007040 multi-step synthesis reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- -1 nickel metal hydride Chemical class 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/14—Pore volume
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/40—Electric properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
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- 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 scheme relates to oxygen-enriched defective TiO2The carbon composite material, the preparation method and the application thereof are characterized in that firstly, a carbon material, tetrabutyl titanate and ethanol are ultrasonically mixed, then are steamed in a rotating way, and are calcined at the temperature of between 200 and 400 ℃ in a segmented temperature rise manner under the protection of nitrogen, so that the oxygen-enriched defect type TiO is obtained2A carbon composite material. The invention uses porous carbon material as template, metal oxide as precursor, and then uses rotary evaporation solvent volatilization method to obtain goldBelongs to oxide carbon composite materials; in N2Under the protection, the oxygen-enriched defective TiO is formed by sectional calcination from room temperature to 200-400 ℃ and then to 400-800 DEG C2@ NMC composite. The method is adopted to prepare the lithium ion battery cathode material with controllable particle size, high specific surface and oxygen enrichment on the surface, has good electrochemical energy storage performance and is an excellent lithium ion battery cathode material.
Description
Technical Field
The invention relates to the technical field of battery cathode materials, in particular to oxygen-rich defective TiO2Carbon composite material, preparation method and application thereof.
Background
In the current times of rapid development of economy and continuous updating of science and technology, global environmental pollution and large consumption of non-renewable energy sources become social problems concerned by the public. The current situation is changed by the discovery and large-scale application of clean energy such as electric energy, solar energy and the like. In modern China, the main sources of electric energy are thermal power generation, hydroelectric power generation, wind power generation and the like; the battery energy storage under high power is mainly used for storing surplus energy of emergency power supplies, battery cars and power plants; low power often uses rechargeable dry cells: such as nickel metal hydride batteries, lithium ion batteries, and the like.
The lithium ion battery is used as an environment-friendly pollution-free mode in battery energy storage, and has the advantages of high specific capacity, no memory effect, high voltage platform, good cycle performance and the like, so the lithium ion battery has extremely good development prospect in the future electric vehicle power battery. However, the current technical methods for practical development of electrode materials and mass production of components limit the mass application of lithium ion batteries; graphite is currently one of the most common commercial negative electrode materials, but is still deficient in cycle performance, specific capacity, safety performance and the like. Metal oxide materials (SnO)2；Fe2O3；TiO2) Because of its low volume expansion, environmental friendliness and low priceThe lithium ion battery has the advantages of low cost and the like, is widely researched, and is applied to the direction of electrode materials of lithium ion batteries. However, the metal oxide itself is a semiconductor, and has problems of poor conductivity, low ion diffusion coefficient, and the like, thereby limiting the commercial large-scale application.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to design and synthesize a high-capacity-density lithium ion battery cathode material based on a titanium dioxide material, and the high-capacity-density lithium ion battery cathode material has the performances of large capacity density, stable circulation, excellent rate performance and the like.
In order to achieve the purpose, the invention provides the following technical scheme:
oxygen-enriched defective TiO2The preparation method of the carbon composite material comprises the following steps:
1) ultrasonically mixing a carbon material, tetrabutyl titanate and ethanol to obtain a mixed solution;
2) carrying out rotary evaporation on the mixed solution to obtain a precursor of the carbon composite material;
3) placing a carbon composite material precursor in a crucible, and performing segmented temperature rise calcination at the temperature of between 200 and 400 ℃ to 800 ℃ under the protection of nitrogen to obtain the oxygen-enriched defective TiO2A carbon composite material.
Preferably, the feeding ratio of the carbon material to tetrabutyl titanate is 1mg: 2-8 muL. The addition of the metal oxide precursor (tetrabutyl titanate) is less, so that oxygen-rich defective materials cannot be formed, and the addition of the metal oxide precursor can influence the electrochemical performance.
Preferably, the reaction temperature of the step 1) and the step 2) is accurately controlled to be between 20 and 50 ℃. The temperature of the mixed environment condition should not be too high, and the shorter air contact time can be helpful for synthesizing TiO with uniform particle size and content due to the special physicochemical property of the metal oxide precursor2A carbon composite material. The ultrasonic treatment is to enable the carbon material and metal ions in the precursor to be uniformly dispersed in ethanol so that the subsequent reaction can be carried out to form a specific shape. And in the rotary evaporation process, when the solvent is volatilized, the metal ions can be prevented from being coated on the outer layer of the carbon material due to high temperature.
The invention further provides a preparation method prepared by the preparation methodOxygen-enriched defective TiO2A carbon composite material.
The present invention further provides oxygen-rich deficient TiO as described above2The carbon composite material is applied to the negative electrode material of the lithium ion battery.
The TiO provided by the invention2The carbon composite material is different from the traditional multistep synthesis method, the particle size of titanium dioxide in the calcination process is controlled by a carbon hard template method synthesized before in the synthesis process, so that the titanium dioxide has uniform particle spherical appearance and simultaneously has a connected channel for facilitating ion transmission, and the composite material has good electrochemical performance due to the generation of oxygen vacancy, the success of synthesizing the oxygen vacancy of the titanium dioxide at the calcination temperature of 400-800 ℃ is verified in the scheme, the calcination condition of simultaneously having an anatase tetragonal crystal form and higher oxygen vacancy concentration is selected, and the tests prove that the oxygen-rich defect type titanium dioxide carbon composite material synthesized by the method is a battery cathode material with good cycle performance.
The invention has the beneficial effects that: according to the invention, a porous carbon material is used as a template, a metal oxide is used as a precursor, and then a method of rotary evaporation of a solvent is utilized to obtain a metal oxide carbon composite material; at N2Under protection, the oxygen-rich defective TiO is formed by sectional calcination from room temperature to 200-400 ℃ and then to 400-800 DEG C2@ NMC composite. The oxygen-enriched defect type metal oxide carbon composite material with controllable particle size, high specific surface and good electrochemical performance is prepared by adopting the method.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is TiO2TEM image of @ NMC-L material.
FIG. 2 isTiO2TEM image of @ NMC-M material.
FIG. 3 is TiO2TEM image of @ NMC-O material.
FIG. 4 is TiO2TEM images of the material.
FIG. 5 is TiO2@NMC-L、TiO2@ NMC-M and TiO2XRD pattern of @ NMC-O material.
FIG. 6 is a graph of electron paramagnetic measurements of materials made in examples 1-4 at room temperature.
FIG. 7 shows TiO at different calcination temperatures2The electron paramagnetic test pattern of @ NMC material.
FIG. 8 is a graph of cycle performance for electrochemical performance tests using examples 1-4 or carbon template materials.
FIG. 9 is a graph of rate performance for electrochemical performance tests using examples 1-4 or carbon template materials.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1:
dissolving 50mg of porous carbon template material (NMC) in 15ml of ethanol solution, adding 100 mu L of TBOT, performing ultrasonic treatment, performing rotary evaporation at 45 ℃ for 2h, placing in a crucible, heating from room temperature to 350 ℃ in nitrogen atmosphere, and calcining at 600 ℃ for 2h to obtain TiO2@ NMC-L material.
Example 2:
dissolving 50mg of porous carbon template material (NMC) in 15ml of ethanol solution, adding 200 mu L of TBOT, performing ultrasonic treatment, performing rotary evaporation at 45 ℃ for 2h, placing in a crucible, heating from room temperature to 350 ℃ in nitrogen atmosphere, and calcining at 600 ℃ for 2h to obtain TiO2@ NMC-M material.
Example 3:
dissolving 50mg of porous carbon template material (NMC) in 15ml of ethanol solution, adding 400 mu L of TBOT, performing ultrasonic treatment, performing rotary evaporation at 45 ℃ for 2h, placing in a crucible, heating from room temperature to 350 ℃ in nitrogen atmosphere, and calcining at 600 ℃ for 2h to obtain TiO2@ NMC-O material.
Example 4:
dissolving 50mg of porous carbon template material (NMC) in 15ml of ethanol solution, adding 100 mu L of TBOT, performing ultrasonic treatment, performing rotary evaporation at 45 ℃ for 2h, placing in a crucible, heating from room temperature to 350 ℃ in air atmosphere, and calcining at 600 ℃ for 2h to obtain TiO2A material.
Referring to the SEM images of the materials obtained in examples 1 to 4 in FIGS. 1 to 4, respectively, it can be seen from FIG. 4 that titanium dioxide is agglomerated and dispersed in a random particle size, while FIGS. 1 to 3 show uniform particles, indicating that titanium dioxide tends to be uniformly distributed due to the restriction of the carbon material.
As can be seen from the XRD patterns of the different materials (fig. 5), at 2 θ, 25.281 °; 37.8 degrees; 48.049 degrees; 53.89 degrees; 55.06 °; 62.688 degrees; 68.76 degrees; 70.309 degrees; 75.029 degrees; 80.725 degrees; 82.136 DEG has corresponding characteristic peaks, which proves the success of synthesizing anatase type titanium dioxide (PDF NO.).
In addition, from the data in Table 1, it is clear that TiO produced herein2The @ NMC material has a large specific surface area and pore volume.
TABLE 1
| Sample (I) | Specific surface area (m)2/g) | Pore volume (ml/g) |
| NMC | 369.9600 | 1.9741 |
| TiO2@NMC-L | 314.1410 | 1.3412 |
| TiO2@NMC-M | 264.5875 | 1.1398 |
| TiO2@NMC-O | 178.7573 | 1.1060 |
The EPR test is carried out on the materials, as shown in figure 6, the enhancement of peak positions can be seen from the figure, and the generation of oxygen enrichment defects of the composite material is proved compared with that of a single material. Among them, NMC-L has the highest concentration of oxygen vacancies.
Example 5:
dissolving 50mg of porous carbon template material (NMC) in 15ml of ethanol solution, adding 100 mu L of TBOT, performing ultrasonic treatment, performing rotary evaporation at 45 ℃ for 2h, placing in a crucible, heating from room temperature to 350 ℃ in nitrogen atmosphere, and calcining at 400, 500, 700 and 800 ℃ for 2h to obtain TiO at different calcining temperatures2The @ NMC material, subjected to an EPR test, as shown in FIG. 7, from which an enhancement in peak position can be seen, demonstrates the success of the synthesis of oxygen vacancies of titanium dioxide at 400 ℃ -800 ℃.
Application and effect verification:
80% of the sample (examples 1-4 or carbon template material), 10% conductive carbon black was dispersed in a 10% PVDF solution in NMP. Evenly coating on an aluminum foil, drying for 12h in a vacuum oven, and punching into a circular electrode plate with the diameter of 14 mm. And taking the electrode plate loaded with the active substances as a working electrode and taking the copper foil as a counter electrode to form the button cell. The electrolyte is1M LiPF6EC + PC (EC to PC volume ratio 3:7), the cell assembly was performed in a glove box filled with argon. The charging and discharging tests of the battery are carried out on an ARBIN test system.
From FIGS. 8 and 9, it can be seen that TiO2@ NMC compared to pure TiO2The specific capacity is increased, which shows that the electrochemical performance of the composite material is better than that of a single material. The increase of oxygen vacancies also improves the electrochemical performance of the same material, wherein TiO2Electrochemical performance of @ NMC-M is optimal, TiO2The electrochemical performance of @ NMC-L is relatively inferior.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.
Claims (5)
1. Oxygen-enriched defective TiO2The preparation method of the carbon composite material is characterized by comprising the following steps:
1) ultrasonically mixing a carbon material, tetrabutyl titanate and ethanol to obtain a mixed solution;
2) carrying out rotary evaporation on the mixed solution to obtain a precursor of the carbon composite material;
3) placing the carbon composite material precursor in a crucible, and carrying out sectional heating calcination at 400-800 ℃ under the protection of nitrogen to obtain the oxygen-rich defect type TiO2A carbon composite material.
2. The oxygen-rich deficient TiO of claim 12The preparation method of the carbon composite material is characterized in that the feeding ratio of the carbon material to tetrabutyl titanate is 1mg: 2-8 mu L.
3. The oxygen-rich deficient TiO of claim 12A method for producing a carbon composite material, characterized by the steps of1) And the reaction temperature of the step 2) is between 20 and 50 ℃.
4. Oxygen-rich defective TiO produced by the production method according to any one of claims 1 to 32A carbon composite material.
5. The oxygen-rich deficient TiO according to claim 42The carbon composite material is applied to the negative electrode material of the lithium ion battery.
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| CN102324511A (en) * | 2011-10-09 | 2012-01-18 | 北京科技大学 | Preparation method for lithium ion battery composite cathode material |
| JP2017016853A (en) * | 2015-06-30 | 2017-01-19 | 堺化学工業株式会社 | Carrier material for electrode and production method therefor |
| CN110937628A (en) * | 2019-12-09 | 2020-03-31 | 浙江工业大学 | TiO with oxygen vacancy2Method for producing a material |
| CN113896186A (en) * | 2021-09-10 | 2022-01-07 | 山东建筑大学 | Preparation method of defective graphene |
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| CN101422726A (en) * | 2008-12-11 | 2009-05-06 | 浙江富来森竹炭有限公司 | Manufacture method of oxygen defect visible light type titanium dioxide photo-catalyst |
| CN102324511A (en) * | 2011-10-09 | 2012-01-18 | 北京科技大学 | Preparation method for lithium ion battery composite cathode material |
| JP2017016853A (en) * | 2015-06-30 | 2017-01-19 | 堺化学工業株式会社 | Carrier material for electrode and production method therefor |
| CN110937628A (en) * | 2019-12-09 | 2020-03-31 | 浙江工业大学 | TiO with oxygen vacancy2Method for producing a material |
| CN113896186A (en) * | 2021-09-10 | 2022-01-07 | 山东建筑大学 | Preparation method of defective graphene |
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