CN112563499B - TiO of lithium ion battery2Method for modifying negative electrode - Google Patents
TiO of lithium ion battery2Method for modifying negative electrode Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 55
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 50
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000843 powder Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- -1 fluorine ions Chemical class 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000002715 modification method Methods 0.000 claims abstract description 7
- 230000007935 neutral effect Effects 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000011737 fluorine Substances 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 239000007791 liquid phase Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 13
- 239000010453 quartz Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- 230000001788 irregular Effects 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052744 lithium Inorganic materials 0.000 abstract description 16
- 238000003860 storage Methods 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000003682 fluorination reaction Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LVYZJEPLMYTTGH-UHFFFAOYSA-H dialuminum chloride pentahydroxide dihydrate Chemical compound [Cl-].[Al+3].[OH-].[OH-].[Al+3].[OH-].[OH-].[OH-].O.O LVYZJEPLMYTTGH-UHFFFAOYSA-H 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical compound [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a TiO lithium ion battery2The modification method of the negative electrode specifically comprises the following steps: adding TiO into the mixture2Carrying out hydrogenation heat treatment on the powder in an atmosphere containing hydrogen, wherein the treatment temperature is 200-600 ℃, and obtaining hydrogenated TiO after complete reaction2Powder of hydrogenated TiO2Dispersing the powder in a solution containing fluorine ions, carrying out liquid phase reaction at 60-250 ℃, and reacting on hydrogenated TiO2Fluoridizing the powder, centrifugally collecting the product after the reaction is completed, washing the product to be neutral, and drying the product in vacuum to obtain the hydrofluoro-codoped TiO2A material. The invention prepares the hydrofluoric acid co-doped TiO through hydrogenation and fluorination treatment2The material has low requirement on process conditions, simple equipment and low cost, and is easy to popularize and carry out large-scale production; prepared hydrofluoro-codoped TiO2When the material is used as the negative electrode of the lithium ion battery, the material has higher specific capacity and better rate capability, and is more commercially available TiO than the raw material2The lithium storage negative electrode performance of the powder is greatly improved.
Description
Technical Field
The invention relates to a TiO lithium ion battery2A modification method of a negative electrode belongs to the technical field of medical analysis.
Background
Two problems of global warming and fossil energy depletion make energy conversion and storage face huge challenges, and the development of new materials plays a crucial role in solving the two problems. The lithium ion battery has the characteristics of high energy density, high power density, long cycle life, good safety, no pollution and the like, and becomes an ideal power supply for portable electronic equipment and future large-scale energy storage and vehicle power batteries. The key to improve the performance of the lithium ion battery is to develop a novel lithium storage material with high capacity, high rate and long service life, and the negative electrode material is one of the vital components in the lithium ion battery and determines the reversible capacity and rate performance of the whole battery system. Titanium dioxide (TiO)2) Has 335mAh g-1The theoretical capacity and good electrochemical stability, so the lithium ion battery has been widely concerned and researched in the field of lithium ion batteries. However, TiO2Limited by extremely low electronic conductivity and ion diffusion rate, the practical electrochemical lithium storage performance, especially rate performance, can not meet the requirements of practical application.
To improve TiO2The electrochemical performance of the electrochemical material is improved, and researchers have conducted a great deal of research and obtained some valuable research results. The main modification strategies include nanostructured to shorten the electron and ion transport distance, or to enhance the electron transport capability of the material by complexing with conductive agents. The invention patent with the patent application number of 201610608242.8 discloses TiO for preparing composite carbon and molybdenum sulfide2The performance of the nano material is improved but 170mA g-1Only 160mAh g is obtained at a current density of-1The specific capacity of (A). The invention patent with the patent application number of 201711320398.7 discloses TiO loaded with high-conductivity carbon cloth so as to improve the conductivity and lithium storage capacity of the material2Materials, however, other thanTiO, in addition to the lithium storage contribution of the carbon-removing cloth2The activity of the material itself is still to be improved. The methods of the nano-structuring and the compounding of the conductive agent can not improve the electron and ion transport performance of the material, so the improvement of the intrinsic electrochemical performance of the material is very limited.
Disclosure of Invention
The invention aims to solve the problem of TiO in the existing lithium ion battery2The above problems of the electrode material in the aspects of capacity and rate performance are solved by providing TiO of the lithium ion battery2The modification method of the cathode has simple modification process and convenient operation, and the prepared hydrofluoric acid co-doped TiO is2When the material is used as a lithium ion battery cathode, the material has higher specific capacity and good rate capability.
The technical solution of the invention is as follows: TiO of lithium ion battery2The modification method of the negative electrode specifically comprises the following steps:
(1) adding TiO into the mixture2Carrying out hydrogenation heat treatment on the powder in an atmosphere containing hydrogen, wherein the treatment temperature is 200-600 ℃, and obtaining hydrogenated TiO after complete reaction2Powder;
(2) hydrogenated TiO obtained in the step (1)2Dispersing the powder in solution containing fluorinion, carrying out liquid phase reaction at 60-250 ℃, and reacting on hydrogenated TiO2Fluoridizing the powder, centrifugally collecting the product after the reaction is completed, washing the product to be neutral, and drying the product in vacuum to obtain the hydrofluoro-codoped TiO2A material.
Further, TiO in the step (1)2The powder is sieved by a vibrating screen with 800 meshes, and the particle size of the powder is smaller than 800 meshes.
Further, the hydrogen-containing atmosphere in the step (1) is pure hydrogen, or a mixed gas containing hydrogen, such as argon-hydrogen mixed gas.
Further, the screened sample is placed in a quartz boat in the step (1), the quartz boat is placed in the middle of an atmosphere tube furnace, and hydrogenation heat treatment is carried out, wherein the reaction temperature is preferably 300-500 ℃, the reaction time is 0.1-24 hours, and preferably 0.5-6 hours.
Further, the solution containing fluoride ions in the step (2) comprises a mixed aqueous solution of one or more of hydrofluoric acid, ammonium fluoride, sodium fluoride and potassium fluoride.
Further, the fluorine ion concentration of the solution containing the fluorine ions in the step (2) is 0.01-1 mol/L; the fluoride ion is mixed with the hydrogenated TiO2The ratio of the amount of powder to the amount of substance is 0.1 or more.
Further, the liquid phase reaction vessel in the step (2) is a polytetrafluoroethylene reaction kettle, the reaction temperature is preferably 100-200 ℃, and the reaction time is preferably 0.1-24 hours, preferably 0.5-12 hours.
The hydrofluor co-doped TiO prepared by the modification method2The material is irregular granular, has uneven surface and has a grain diameter of 50-100 nm.
Compared with the prior art, the invention has the advantages that:
1) the invention adopts commercially available TiO2The powder is a raw material, and the material is easy to obtain; preparation of hydrofluoro-codoped TiO by hydrogenation and fluorination2Materials in which the heat treatment of hydrogenation accelerates the electron conduction in the bulk phase of the material, while the fluorination increases the TiO content2The lithium storage activity of (3) and the diffusion of lithium ions is promoted; the modification method has the advantages of low requirement on process conditions, simple equipment, low cost and easy popularization and large-scale production;
2) with the raw material commercially available TiO2Compared with powder, the prepared hydrofluoric acid co-doped TiO has the advantages of high purity, good corrosion resistance and the like2When the material is used as a lithium ion battery cathode, higher specific capacity and better rate capability are shown: the electrochemical test result shows that the prepared hydrofluoric acid co-doped TiO is doped with the fluorine2The material was at 1C (335mA · g)-1) The reversible capacity under multiplying power is 140 mAh.g-1Compared with the commercial TiO of the raw material2The lithium storage negative electrode performance of the powder is greatly improved.
Drawings
FIG. 1 shows the hydrofluoro-codoped TiO obtained in example 12TEM images of the material.
FIG. 2 shows the hydrofluoro-codoped TiO obtained in example 12XRD test result of the material.
FIG. 3 shows the hydrofluoro-codoped TiO obtained in example 12The material is prepared into a charge-discharge curve diagram of the electrode under different multiplying powers.
FIG. 4 is an unmodified TiO2The material is prepared into a charge-discharge curve diagram of the electrode under different multiplying powers.
FIG. 5 shows the hydrofluoro-codoped TiO obtained in example 22The material is prepared into a charge-discharge curve diagram of the electrode under different multiplying powers.
FIG. 6 shows the hydrofluoro-codoped TiO obtained in example 32The material is prepared into a charge-discharge curve diagram of the electrode under different multiplying powers.
FIG. 7 shows the hydrofluoro-codoped TiO obtained in example 42The material is prepared into a charge-discharge curve diagram of the electrode under different multiplying powers.
Detailed Description
The technical scheme of the invention is further explained by combining the drawings and the embodiment. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and should not be construed as limiting the invention.
In the following examples of the invention, hydrofluoro-codoped TiO2The lithium storage performance test steps of the material are as follows:
co-doping of hydrofluoric acid with TiO2The material, conductive agent carbon black and binder are mixed according to the mass ratio of 7: 2: 1 uniformly mixed composite electrode as working electrode, metal lithium sheet as counter electrode, and LiPF with concentration of 1M6(ED: DMC: EMC volume ratio 1:1:1) solution is used as electrolyte to assemble a lithium ion battery, and then a charge-discharge test is carried out between 1V and 3V.
Example 1
Will market TiO2Sieving the powder with a 800-mesh vibrating screen, placing the sieved sample in a quartz boat, placing the quartz boat in the middle of an atmosphere tube furnace, heating to 450 ℃ in the atmosphere of argon-hydrogen mixed gas (the volume ratio of argon to hydrogen is 95: 5), preserving heat for 6 hours, taking out the sample after the tube furnace is naturally cooled to obtain hydrogenated TiO2A material. Then, 0.2g of hydrogenated TiO2The material is placed in a 25mL polytetrafluoroethylene reaction kettle, and 15mL hydrofluoric acid solution with the concentration of 0.1mol/L is addedCarrying out hydrothermal reaction for 6h at 200 ℃. Centrifugally collecting a sample after reaction, fully washing the sample to be neutral by using water, and drying the sample in vacuum to obtain the hydrofluoro-codoped TiO2A material.
Hydrogen fluorine co-doped TiO2The microscopic morphology and crystal structure of the material are shown in fig. 1 and 2, respectively. As can be seen from FIG. 1, the material is irregular and has a particle size of 50-100 nm.
Testing of the hydrofluoro-codoped TiO according to the method described above2Lithium storage Properties of the materials, for comparison, a hydrofluoro-codoped TiO co-doped with TiO according to the method described above2Replacement of material with sieved commercial TiO2And (3) preparing powder into a working electrode, and testing the lithium storage performance of the working electrode. FIG. 3 shows hydrogen and fluorine-containing co-doped TiO2The lithium storage rate performance test result of the material shows that the sample can reach 148mAh g under the rate of 1C-1The specific capacity of the sample can reach 101 mAh.g under the multiplying power of 5C-1The specific capacity of (A). FIG. 4 shows unmodified TiO after sieving2The lithium storage rate performance test result of the material shows that the sample has only 75 mAh.g at the rate of 1C-1The specific capacity of the sample is only 45mAh g under the multiplying power of 5C-1The specific capacity of the sample of the embodiment 1 is obviously higher than that of screened TiO under the same multiplying power2And (3) sampling.
Example 2
Will market TiO2Sieving the powder by using a vibrating screen of 800 meshes, placing the sieved sample in a quartz boat, placing the quartz boat in the middle of an atmosphere tube furnace, heating to 250 ℃ in a hydrogen atmosphere, preserving the heat for 20 hours, and taking out the sample after the tube furnace is naturally cooled to obtain hydrogenated TiO2A material. Then, 0.2g of hydrogenated TiO2The material is placed in a 25mL polytetrafluoroethylene reaction kettle, 15mL hydrofluoric acid solution with the concentration of 0.2mol/L is added, and the hydrothermal reaction is carried out for 20h at the temperature of 80 ℃. Centrifugally collecting a sample after reaction, fully washing the sample to be neutral by using water, and drying the sample in vacuum to obtain the hydrofluoro-codoped TiO2A material. Testing of the hydrofluoro-codoped TiO according to the method described above2The lithium storage performance of the material can reach 104 mAh.g of a sample under the multiplying power of 1C-1The specific capacity of the sample can reach 55 mAh.g under the multiplying power of 5C-1Specific capacity of (2), as shown in FIG. 5Shown in the figure.
Example 3
Will market TiO2Sieving the powder with a 800-mesh vibrating screen, placing the sieved sample in a quartz boat, placing the quartz boat in the middle of an atmosphere tube furnace, heating to 500 ℃ in the atmosphere of argon-hydrogen mixed gas (the volume ratio of argon to hydrogen is 85: 15), preserving the temperature for 0.5h, taking out the sample after the tube furnace is naturally cooled to obtain hydrogenated TiO2A material. Then, 0.2g of hydrogenated TiO2The material is put into a 25mL polytetrafluoroethylene reaction kettle, 15mL of sodium fluoride solution with the concentration of 0.15mol/L is added, and hydrothermal reaction is carried out for 4h at 200 ℃. Centrifugally collecting a sample after reaction, fully washing the sample to be neutral by using water, and drying the sample in vacuum to obtain the hydrofluoro-codoped TiO2A material. Testing of the hydrofluoro-codoped TiO according to the method described above2The lithium storage performance of the material can reach 141mAh g under the multiplying power of 1C-1The specific capacity of the sample can reach 82mAh g under the multiplying power of 5C-1The specific capacity of (A) is shown in FIG. 6.
Example 4
Will market TiO2Sieving the powder with a 800-mesh vibrating screen, placing the sieved sample in a quartz boat, placing the quartz boat in the middle of an atmosphere tube furnace, heating to 400 ℃ in the atmosphere of nitrogen-hydrogen mixed gas (argon-hydrogen volume ratio is 90: 10), preserving heat for 4 hours, and taking out the sample after the tube furnace is naturally cooled to obtain hydrogenated TiO2A material. Then, 0.2g of hydrogenated TiO2The material is put into a 25mL polytetrafluoroethylene reaction kettle, 15mL ammonium fluoride solution with the concentration of 0.06mol/L is added, and the hydrothermal reaction is carried out for 10h at 150 ℃. Centrifugally collecting a sample after reaction, fully washing the sample to be neutral by using water, and drying the sample in vacuum to obtain the hydrofluoro-codoped TiO2A material. Testing of the hydrofluoro-codoped TiO according to the method described above2The lithium storage performance of the material can reach 131mAh g of a sample under the multiplying power of 1C-1The specific capacity of the sample can reach 87 mAh.g under the multiplying power of 5C-1The specific capacity of (A) is shown in FIG. 7.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. TiO of lithium ion battery2The method for modifying the negative electrode is characterized by comprising the following steps:
(1) adding TiO into the mixture2The powder is subjected to hydrogenation heat treatment in hydrogen-containing atmosphere, and hydrogenated TiO is obtained after the reaction is completed2Powder;
(2) hydrogenated TiO obtained in the step (1)2Dispersing the powder in solution containing fluorinion, liquid phase reaction, and reacting on hydrogenated TiO2Fluoridizing the powder, centrifugally collecting the product after the reaction is completed, washing the product to be neutral, and drying the product in vacuum to obtain the hydrofluoro-codoped TiO2A material;
TiO in the step (1)2Sieving the powder by a vibrating screen with 800 meshes, wherein the particle size of the powder is less than 800 meshes;
in the step (1), the screened TiO is treated2Placing the powder in a quartz boat, placing the quartz boat in the middle of an atmosphere tube furnace, and carrying out hydrogenation heat treatment, wherein the reaction temperature is 300-500 ℃, and the reaction time is 0.1-24 hours;
and (3) the liquid phase reaction in the step (2) is carried out in a polytetrafluoroethylene reaction kettle at the reaction temperature of 100-200 ℃ for 0.1-24 hours.
2. The TiO lithium ion battery of claim 12The method for modifying the negative electrode is characterized in that the hydrogen-containing atmosphere in the step (1) is pure hydrogen or a mixed gas containing hydrogen.
3. The TiO lithium ion battery of claim 12The method for modifying the negative electrode is characterized in that the reaction time in the step (1) is 0.5-6 hours.
4. A method as claimed in claim 1Lithium ion battery TiO2The method for modifying the negative electrode is characterized in that the solution containing the fluoride ions in the step (2) comprises a mixed aqueous solution of one or more of hydrofluoric acid, ammonium fluoride, sodium fluoride and potassium fluoride.
5. The TiO lithium ion battery of claim 12The method for modifying the negative electrode is characterized in that the fluorine ion concentration of the solution containing the fluorine ions in the step (2) is 0.01-1 mol/L; the fluoride ion is mixed with the hydrogenated TiO2The ratio of the mass of the powder is 0.1 or more.
6. The TiO lithium ion battery of claim 12The method for modifying the negative electrode is characterized in that the reaction time in the step (2) is 0.5-12 hours.
7. The TiO lithium ion battery of any one of claims 1-62Hydrofluoride co-doped TiO prepared by negative electrode modification method2The material is characterized in that the material is irregular particles, the surface of the material is uneven, and the particle size of the material is 50-100 nm.
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