CN114634200A - Preparation method of lithium titanate negative electrode material - Google Patents
Preparation method of lithium titanate negative electrode material Download PDFInfo
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- CN114634200A CN114634200A CN202210171963.2A CN202210171963A CN114634200A CN 114634200 A CN114634200 A CN 114634200A CN 202210171963 A CN202210171963 A CN 202210171963A CN 114634200 A CN114634200 A CN 114634200A
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- lithium
- lithium titanate
- negative electrode
- electrode material
- titanate negative
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 87
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002699 waste material Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 29
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000002441 X-ray diffraction Methods 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 4
- 229940039790 sodium oxalate Drugs 0.000 claims description 4
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 22
- 229910009866 Ti5O12 Inorganic materials 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000009831 deintercalation Methods 0.000 abstract description 3
- 230000002687 intercalation Effects 0.000 abstract description 3
- 238000009830 intercalation Methods 0.000 abstract description 3
- -1 compound lithium hydroxide Chemical class 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- 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
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01—INORGANIC CHEMISTRY
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- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The invention belongs to the technical field of lithium batteries, and particularly relates to a preparation method of a lithium titanate negative electrode material, which comprises the following steps: 1) taking a negative plate of a waste lithium titanate battery as a cathode, and carrying out water electrolysis reaction in an alkaline aqueous solution to separate a current collector in the negative plate from a film containing active powder; 2) placing the film containing the active powder obtained in the step 1), a lithium source compound and deionized water in a hydrothermal reaction kettle, and reacting at 160-220 ℃ for 8-16 hours to obtain a reaction precursor; 3) roasting the reaction precursor obtained in the step 2) for 3-8 hours in an air atmosphere at the temperature of 500-700 ℃ to obtain a powdery lithium titanate negative electrode material. The invention has simple synthesis process and high synthesis temperatureLow degree of Li produced4Ti5O12The material has the advantages of stable structure, fine and uniform particles, good crystallinity, good reversibility of lithium intercalation and deintercalation and excellent performance.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a preparation method of a lithium titanate negative electrode material.
Background
Lithium titanate (Li) of spinel structure4Ti5O12) The lithium-doped lithium iron phosphate is a zero-strain negative electrode material, has stable discharge voltage, high lithium intercalation potential, difficult precipitation of metal lithium and good cycle stability. The battery using lithium titanate as the cathode has excellent cycle life and is widely applied to the fields of new energy automobiles and energy storage.
With the development of new energy industry, the retirement of various new energy automobile batteries and energy storage batteries, the number of waste batteries increases year by year, and the generated environmental problems become more serious. Meanwhile, because metal substances in the lithium ion battery are all non-renewable resources, the metal substances are comprehensively recycled, the cost can be saved, the cyclic utilization of the resources can be achieved, and the power is contributed to the establishment of a resource ecological society and an environment-friendly society.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides lithium titanate Li4Ti5O12A preparation process of the cathode material. The method utilizes the characteristic of stable structure of the lithium titanate material in the lithium titanate battery cathode, recycles the cathode material of the waste lithium titanate battery, realizes the recycling of the lithium titanate material, and saves lithium resources and titanium resources.
The technical scheme provided by the invention is as follows:
a preparation method of a lithium titanate negative electrode material comprises the following steps:
1) taking a negative plate of a waste lithium titanate battery as a cathode, and carrying out water electrolysis reaction in an alkaline aqueous solution to separate a current collector in the negative plate from a film containing active powder;
2) placing the film containing the active powder obtained in the step 1), a lithium source compound and deionized water in a hydrothermal reaction kettle, and reacting at 160-220 ℃ for 8-16 hours to obtain a reaction precursor;
3) roasting the reaction precursor obtained in the step 2) for 3-8 hours in an air atmosphere at the temperature of 500-700 ℃ to obtain a powdery lithium titanate negative electrode material.
In the prior art, a binder adopted by a cathode of a general lithium titanate battery is an oil-based binder. Based on the technical scheme, the bonding strength of the binder can be damaged by utilizing hydrogen generated when residual lithium ions in the negative lithium titanate material are subjected to deintercalation in an alkaline aqueous solution, so that the separation efficiency of the current collector and the film containing the active powder is improved.
Specifically, in step 1):
taking a graphite plate or a lead plate as an anode;
carrying out an electrolytic reaction of water in an alkaline electrolyte with a pH of 8-12.
Specifically, the waste lithium titanate battery is disassembled after being discharged to 0-0.5V, and the negative plate is taken out.
Specifically, in the step 2): the active powder-containing film and the lithium source compound are mixed according to the mass ratio of the active powder-containing film to lithium being 100 (1-5).
Specifically, in step 3): and roasting the reaction precursor for 3-6 hours in an air atmosphere at the temperature of 450-600 ℃ to obtain the powdery lithium titanate negative electrode material.
Specifically, in the step 1), the alkaline aqueous solution is selected from any one of sodium carbonate, sodium oxalate, sodium hydroxide and ammonia water.
Based on the technical scheme, sodium carbonate, sodium oxalate, sodium hydroxide or ammonia provides a proper alkaline condition for electroevolution of hydrogen. And the sodium carbonate, the sodium oxalate, the sodium hydroxide and the ammonia have the obvious advantages of no toxicity, environmental protection and the like.
Specifically, in step 2), the lithium source compound is selected from any one of lithium sulfate, lithium oxalate, lithium phosphate, lithium dihydrogen phosphate, lithium chloride, lithium nitrate, and lithium hydroxide.
Specifically, in step 3):
the average particle diameter of the obtained lithium titanate negative electrode material is within the range of 200-1000 nm;
the intensity ratio of a main impure phase peak to a main lithium titanate peak in an X-ray diffraction peak of the lithium titanate negative electrode material is less than 2%.
The invention has the advantages that: simple synthesis process, low synthesis temperature, and prepared Li4Ti5O12The material has the advantages of stable structure, fine and uniform particles, good crystallinity, good reversibility of lithium intercalation and deintercalation and excellent performance.
Drawings
FIG. 1 is Li prepared in example 14Ti5O12SEM photograph of the material.
FIG. 2 is Li prepared in example 14Ti5O12XRD pattern of material.
FIG. 3 is Li prepared in example 14Ti5O12Charge and discharge test curve of the material. The test conditions were: the performance of the prepared lithium titanate material is tested by adopting a half-cell, the positive active substance is the lithium titanate material, the negative electrode is a metal lithium sheet, the electrolyte is common commercial electrolyte (the solvent EC: DEC: DMC is 1:1:1, and the lithium salt is LiPF6)。
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
Li of the present example4Ti5O12The preparation method comprises the following steps:
firstly, discharging the waste lithium titanate battery to 0V, then disassembling, taking out a negative plate, taking the negative plate as a cathode of an electrolytic cell, taking a graphite plate as an anode, and carrying out an electrolytic reaction of water in a sodium carbonate alkaline electrolyte with the pH value of 8 so as to separate a current collector from a film containing active powder. Placing the film obtained by separation, lithium source compound lithium hydroxide and deionized water in a hydrothermal reaction kettle, and reacting the film and the lithium hydroxide at the mass ratio of 100:2 at 180 ℃ for 10 hours to obtain a reaction precursor; and finally roasting the precursor for 3 hours in the air atmosphere at the temperature of 600 ℃ to obtain the final lithium titanate powder material, wherein the average particle diameter of the powder is less than 1000nm, and the intensity ratio of a main hetero-phase peak to a main lithium titanate peak in an X-ray diffraction peak of the prepared lithium titanate powder material is less than 2%.
Fig. 1 and 2 show SEM and XRD patterns of the lithium titanate material prepared in this example, respectively. Fig. 3 shows a graph of the charge-discharge performance of the half-cell of the lithium titanate material in this example. The charge-discharge cycle voltage range is 2.5-1V, and the charge-discharge multiplying power is 0.2C.
Example 2
Li of the present example4Ti5O12The preparation method comprises the following steps:
firstly, discharging the waste lithium titanate battery to 0.5V, then disassembling, taking out the negative plate, taking the negative plate as the cathode of the electrolytic cell, taking the graphite plate as the anode, and carrying out the electrolytic reaction of water in the sodium carbonate alkaline electrolyte with the pH value of 12, so that the current collector is separated from the film containing the active powder. Placing the film obtained by separation, lithium source compound lithium carbonate and deionized water into a hydrothermal reaction kettle, and reacting the film and lithium hydroxide for 16 hours at 160 ℃ according to the mass ratio of the film to the lithium of 100:1 to obtain a reaction precursor; and finally, roasting the precursor for 6 hours at the temperature of 450 ℃ in the air atmosphere to obtain the final lithium titanate powder material. The average particle diameter of the powder is less than 500nm, and the intensity ratio of a main hetero-phase peak to a main lithium titanate peak in an X-ray diffraction peak of the prepared lithium titanate powder material is less than 2%.
Example 3
Li of the present example4Ti5O12The preparation method comprises the following steps:
firstly, discharging the waste lithium titanate battery to 0.1V, then disassembling, taking out the negative plate, taking the negative plate as the cathode of the electrolytic cell, taking the graphite plate as the anode, and carrying out water electrolysis reaction in ammonia water alkaline electrolyte with the pH value of 12 so as to separate the current collector from the film containing active powder. Placing the separated film, lithium source compound lithium hydroxide and deionized water in a hydrothermal reaction kettle, and reacting the film and the lithium hydroxide for 8 hours at 220 ℃ according to the mass ratio of the film to the lithium of 100:5 to obtain a reaction precursor; and finally, roasting the precursor for 5 hours at the temperature of 500 ℃ in the air atmosphere to obtain the final lithium titanate powder material. The average particle diameter of the powder is less than 500nm, and the intensity ratio of a main hetero-phase peak to a main lithium titanate peak in an X-ray diffraction peak of the prepared lithium titanate powder material is less than 2%.
Example 4
Li of the present example4Ti5O12The preparation method comprises the following steps:
the method comprises the steps of firstly discharging the waste lithium titanate battery to 0V, then disassembling, taking out a negative plate, taking the negative plate as a cathode of an electrolytic cell, taking a graphite plate as an anode, and carrying out water electrolysis reaction in an ammonia water alkaline electrolyte with the pH value of 10, so that a current collector is separated from an active powder-containing film. Placing the film obtained by separation, lithium source compound lithium hydroxide and deionized water in a hydrothermal reaction kettle, and reacting the film and the lithium hydroxide for 10 hours at 180 ℃ according to the mass ratio of the film to the lithium of 100:1 to obtain a reaction precursor; and finally, roasting the precursor for 6 hours at the temperature of 600 ℃ in the air atmosphere to obtain the final lithium titanate powder material. The average particle diameter of the powder is less than 500nm, and the intensity ratio of a main hetero-phase peak to a main lithium titanate peak in an X-ray diffraction peak of the prepared lithium titanate powder material is less than 2%.
Example 5
Li of the present example4Ti5O12The preparation method comprises the following steps:
firstly, discharging the waste lithium titanate battery to 0, then disassembling the waste lithium titanate battery, taking out a negative plate, taking the negative plate as a cathode of an electrolytic cell, taking a graphite plate as an anode, and carrying out an electrolytic reaction of water in a sodium carbonate alkaline electrolyte with the pH value of 8 so as to separate a current collector from a film containing active powder. Placing the film obtained by separation, lithium source compound lithium hydroxide and deionized water in a hydrothermal reaction kettle, and reacting the film and the lithium hydroxide for 12 hours at 180 ℃ according to the mass ratio of the film to the lithium of 100:1 to obtain a reaction precursor; and finally, roasting the precursor in an air atmosphere at the temperature of 600 ℃ for 3 hours to obtain the final lithium titanate powder material. The average particle diameter of the powder is less than 800nm, and the intensity ratio of a main hetero-phase peak to a main lithium titanate peak in an X-ray diffraction peak of the prepared lithium titanate powder material is less than 2%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.
Claims (7)
1. A preparation method of a lithium titanate negative electrode material is characterized by comprising the following steps:
1) taking a negative plate of a waste lithium titanate battery as a cathode, and carrying out water electrolysis reaction in an alkaline aqueous solution to separate a current collector in the negative plate from a film containing active powder;
2) placing the film containing the active powder obtained in the step 1), a lithium source compound and deionized water in a hydrothermal reaction kettle, and reacting at 160-220 ℃ for 8-16 hours to obtain a reaction precursor;
3) roasting the reaction precursor obtained in the step 2) for 3-8 hours in an air atmosphere at the temperature of 500-700 ℃ to obtain a powdery lithium titanate negative electrode material.
2. The method for preparing a lithium titanate negative electrode material according to claim 1, wherein in step 1):
taking a graphite plate or a lead plate as an anode;
carrying out an electrolytic reaction of water in an alkaline electrolyte with a pH of 8-12.
3. The method for preparing a lithium titanate negative electrode material according to claim 1, wherein in step 2): the active powder-containing film and the lithium source compound are mixed according to the mass ratio of the active powder-containing film to lithium being 100 (1-5).
4. The method for preparing a lithium titanate negative electrode material according to claim 1, wherein in step 3): and roasting the reaction precursor for 3-6 hours in an air atmosphere at the temperature of 450-600 ℃ to obtain the powdery lithium titanate negative electrode material.
5. The method for preparing a lithium titanate negative electrode material according to any one of claims 1 to 4, characterized in that: in the step 1), the alkaline aqueous solution is selected from any one of sodium carbonate, sodium oxalate, sodium hydroxide or ammonia water.
6. The method for preparing a lithium titanate negative electrode material according to any one of claims 1 to 4, characterized in that: in the step 2), the lithium source compound is selected from any one of lithium sulfate, lithium oxalate, lithium phosphate, lithium dihydrogen phosphate, lithium chloride, lithium nitrate or lithium hydroxide.
7. The method for preparing a lithium titanate negative electrode material according to any one of claims 1 to 4, wherein in step 3):
the average particle diameter of the obtained lithium titanate negative electrode material is within the range of 200-1000 nm;
the intensity ratio of a main hetero-phase peak to a main lithium titanate peak in an X-ray diffraction peak of the lithium titanate negative electrode material is less than 2%.
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