CN112374536A - Rapid preparation of spinel type Li at low temperature4Ti5O12Method for preparing lithium titanate material - Google Patents
Rapid preparation of spinel type Li at low temperature4Ti5O12Method for preparing lithium titanate material Download PDFInfo
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 82
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 77
- 239000000463 material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 16
- 239000011029 spinel Substances 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 55
- 239000002243 precursor Substances 0.000 claims abstract description 47
- 238000005245 sintering Methods 0.000 claims abstract description 46
- 239000000843 powder Substances 0.000 claims abstract description 44
- 229910009866 Ti5O12 Inorganic materials 0.000 claims abstract description 32
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 claims abstract description 26
- 238000010304 firing Methods 0.000 claims abstract description 26
- 235000015895 biscuits Nutrition 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000009694 cold isostatic pressing Methods 0.000 claims abstract description 8
- 238000003980 solgel method Methods 0.000 claims abstract description 8
- 238000000748 compression moulding Methods 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- 238000010298 pulverizing process Methods 0.000 claims abstract description 3
- 239000010936 titanium Substances 0.000 claims description 48
- 229910052719 titanium Inorganic materials 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 44
- 150000001875 compounds Chemical class 0.000 claims description 37
- 238000000227 grinding Methods 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 12
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000007873 sieving Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000499 gel Substances 0.000 claims description 6
- 239000011240 wet gel Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002738 chelating agent Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 239000005456 alcohol based solvent Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 13
- 238000002485 combustion reaction Methods 0.000 description 12
- 239000007772 electrode material Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000005303 weighing Methods 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
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
-
- 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
-
- 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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- 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
- C01P2006/40—Electric 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
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- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
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Abstract
The invention provides a method for quickly preparing spinel Li at low temperature4Ti5O12A method for preparing a lithium titanate material, belonging to the technical field of lithium titanate preparation. The method comprises the following steps: 1) preparation of Li by solid oxide mixing method, hydrothermal method or sol-gel method4Ti5O12Flash-firing the precursor powder of (1); 2) putting the flash-burned precursor powder prepared in the step 1) into a mold, carrying out compression molding, demoulding, and carrying out cold isostatic pressing treatment to obtain a final flash-burned precursor biscuit; 3) applying direct current to two ends of the flash-burning precursor biscuit, and simultaneously heating the flash-burning precursor biscuit in a protective atmosphere until flash burning is finished; when flash occurs, the flash is started, the current density is controlled, and the flash is controlled to be continuously in a constant current stateStopping heating after flash firing is finished for a period of time, and cooling to room temperature to obtain Li4Ti5O12Sintering the resultant, and pulverizing the sintered product to obtain spinel-type Li4Ti5O12A lithium titanate powder product. The invention combines the preparation and flash burning technology of the precursor powder, reduces the temperature and time required by preparation, and saves the preparation energy consumption.
Description
Technical Field
The invention belongs to the technical field of lithium titanate preparation, and particularly relates to a method for quickly preparing spinel type Li at low temperature4Ti5O12A method of preparing lithium titanate material.
Background
Spinel type Li4Ti5O12Lithium titanate material is widely used as lithium battery material because of its good cycle performance, outstanding safety performance, very small volume change and low cost. Spinel type lithium titanate (Li)4Ti5O12) The traditional preparation methods mainly comprise a high-temperature solid-phase reaction method, a hydrothermal method and a sol-gel method.
In the traditional high-temperature solid-phase reaction preparation method, the synthesis process temperature is high, the sintering time is long, the energy consumption is high, the production efficiency is low, the particle size distribution of the product is difficult to control, and the uniformity, consistency and reproducibility are poor; the hydrothermal synthesis method generally needs 18-72 hours for hydrothermal reaction, and the obtained precursor powder needs to be further calcined at 800-850 ℃ for several hours to obtain the lithium titanate material; the material synthesized by the sol-gel method has obvious advantages, such as small product granularity, narrow distribution, good uniformity, large specific surface area and the like, but still needs synthesis temperature of about 800 ℃ and reaction time of several hours, and the preparation efficiency is lower.
In the above three methods, the high-temperature calcination process is required, which causes different losses to the lithium content of the material, and is very easy to generate non-stoichiometric compounds, thereby resulting in poor performance of the material.
Disclosure of Invention
The invention aims at spinel type Li4Ti5O12The problems of low preparation efficiency, lithium loss and the like in the prior preparation technology are solved, and the preparation of spinel type Li at low temperature is provided4Ti5O12A method of preparing lithium titanate material.
The purpose of the invention is realized by the following technical scheme:
rapid preparation of spinel type Li at low temperature4Ti5O12A method of lithium titanate material, comprising the steps of:
1) preparation of Li by solid oxide mixing method, hydrothermal method or sol-gel method4Ti5O12Flash-firing the precursor powder of (1);
2) putting the flash-burned precursor powder prepared in the step 1) into a mold, carrying out compression molding, demoulding, and carrying out cold isostatic pressing treatment to obtain a final flash-burned precursor biscuit;
3) applying direct current to two ends of the flash-burning precursor biscuit, and simultaneously heating the flash-burning precursor biscuit in a protective atmosphere until flash burning is finished; starting flash-burning when flash-burning occurs, controlling current density and flash-burning in a constant current state for a period of time, stopping heating after flash-burning is finished, and cooling the obtained flash-burning sample to room temperature to obtain Li4Ti5O12Sintering the resultant, and pulverizing the sintered product to obtain spinel-type Li4Ti5O12A lithium titanate powder product.
Further, the mould pressing pressure for mould pressing is 100-300MPa, and the pressure maintaining time is 1-20 min; the cold isostatic pressing pressure is 200-300 MPa, and the holding time is 1-2 minutes.
Further, the voltage of the direct current is 10-150V/cm; the heating rate of the heating is 1-20 ℃/min; the current density is 0-700 mA/mm2(ii) a The flash time is 0-600 s.
Further, preparation of Li by solid oxide mixing method4Ti5O12The specific process of flash-firing the precursor powder comprises the following steps: and (2) placing the lithium source compound, the titanium source compound, the grinding balls and the grinding medium in a ball milling tank for mixing, packaging the ball milling tank, placing the ball milling tank on a ball mill for ball milling to obtain a mixed solution, removing the solvent from the mixed solution, drying, grinding and sieving to obtain flash-burned precursor powder. The lithium source compound is one or more of lithium hydroxide, lithium carbonate and lithium nitrate, the titanium source compound is titanium dioxide, and the molar ratio of lithium in the lithium source compound to titanium in the titanium source compound is 0.75-0.85; the grinding balls are made of zirconium dioxide, the diameter of the grinding balls is 3-15mm, and the mass of the grinding balls is2-10 times of the mass of the compound powder; the grinding medium is one or more of water, an alcohol solvent and a ketone solvent, and the mass of the grinding medium is 1-5 times of that of the compound powder; the ball milling speed is 50-300r/min, and the time is 2-24 h; the drying temperature is 50-300 ℃, and the drying time is 6-24 h.
Further, preparation of Li by hydrothermal method4Ti5O12The specific process of flash-firing the precursor powder comprises the following steps: mixing the titanium source solution and the lithium source solution under the stirring condition to obtain a mixed solution, and then carrying out hydrothermal reaction on the mixed solution for 5-48 hours at the temperature of 120-250 ℃; and cooling the hydrothermal reaction product to room temperature, drying, grinding and sieving to obtain flash-burned precursor powder. The titanium source solution is obtained by dissolving a titanium source compound in a titanium source solvent, and the lithium source solution is obtained by dissolving a lithium source compound in a lithium source solvent; the molar concentration of a lithium source compound in the lithium source solution is 0.08-4 mol/L, the molar concentration of a titanium source compound in the titanium source solution is 0.1-5 mol/L, and the molar ratio of lithium atoms in the lithium source solution to titanium atoms in the titanium source solution is 0.80-0.85.
Further, Li is prepared by a sol-gel method4Ti5O12The specific process of flash-firing the precursor powder comprises the following steps: dissolving a lithium source compound and a chelating agent in a lithium source solvent and deionized water, and mixing to prepare a lithium source solution; dissolving a titanium source compound in a titanium source solvent to prepare a titanium source solution; strongly stirring the titanium source solution, slowly dropwise adding the lithium source solution into the titanium source solution, controlling the reaction temperature to be maintained at room temperature, continuously stirring to obtain transparent sol, and then aging to obtain milky wet gel; and (3) drying the wet gel in an oven to obtain dry gel, and then grinding and sieving the dry gel to obtain flash-burned precursor powder. Wherein the lithium source solvent and the titanium source solvent are one or more of methanol, ethanol, glycol, propanol, isopropanol, butanol, isobutanol and other alcohol solvents; the lithium source compound is one or more of lithium ethoxide, lithium acetate and lithium nitrate; the titanium source compound is one or two of butyl titanate and isopropyl titanate; the chelating agent is citric acid, oxalic acid, and propionic acidOne or more of olefine acid and tartaric acid. Furthermore, the molar concentration of the lithium source compound in the lithium source solution is 0.1-4 mol/L; the molar concentration of a titanium source compound in the titanium source solution is 0.1-5 mol/L; the molar ratio of lithium atoms in the lithium source solution to titanium atoms in the titanium source solution is 0.80-0.85, and the molar ratio of the chelate in the lithium source solution to the titanium source compound in the titanium source solution is 1-4: 1, the molar ratio of deionized water in the lithium source solution to a titanium source compound in the titanium source solution is 4-10: 1; the aging time is 12-48 h, and the drying is constant temperature drying at 80-160 ℃ for 12-48 h.
Spinel type Li4Ti5O12The lithium titanate material is prepared by the method.
The flash firing in step 3) of the preparation method of the present invention can be carried out by the flash firing system as shown in fig. 1, but other systems or apparatuses may be used as long as the effect of applying a direct current across the final flash firing precursor while raising the temperature during sintering can be achieved. The flash system shown in fig. 1 includes: the sintering device, the power supply, the data recording unit, the control unit and the junction box; the power supply is preferably a direct current power supply with a digital control function, the data recording unit is preferably a digital multimeter, the control unit is preferably a computer, the computer can control the sintering device and the power supply, the sintering device is preferably a tube furnace or a box-type resistance furnace, a sintering chamber is arranged in the sintering device, and the electrodes and the platinum wires or the platinum sheets are located in the sintering chamber.
The electrode penetrates through the sintering device through a platinum wire to be connected with an external lead, a ceramic insulating sleeve is arranged outside the platinum wire to be insulated with the shell of the sintering device, the lead is connected with a power supply through a junction box, and the data recording unit is connected with the electrode through the junction box; the power supply is connected with the control unit to realize the control of parameters such as voltage, current and the like of the power supply; the data recording unit is connected with the control unit, and records the measured voltage and current signals in the control unit, and the control unit simultaneously controls the sintering device. The sintering device, the power supply, the data recording unit, the control unit and each part and function of the junction box and the connection mode can be realized by adopting conventional products in the prior art and combining with the conventional known technology in the field.
In the sintering chamber, the sample is contacted with an electrode, and the electrode is connected with a platinum wire and led out of the sintering chamber to be connected with a lead. According to the shape of the sample, the connection mode of the electrode and the sample can be four, as shown in fig. 2: (a) the sheet electrodes clamp the sample from the left end and the right end and are suspended in the sintering chamber; (b) the flaky electrode contacts the sample from top to bottom, and high-temperature clamps can be arranged on the top and bottom of the electrode to ensure the contact between the sample and the electrode; (c) stick-shaped electrodes penetrate through small holes at two ends of the dog bone-shaped sample and are suspended in the sintering chamber; (d) electrodes were wound around both ends of the stick sample. The electrode materials used are metal platinum electrodes and graphite electrodes.
The operation method of the flash system comprises the following steps: and connecting two ends of the final flash-firing precursor with electrodes, firstly setting a temperature-raising program of a sintering device, then starting the sintering device to raise the temperature, and simultaneously starting a power supply to apply direct current to two ends of the blank. Continuously raising the temperature (till the flash combustion is finished), starting the flash combustion when the flash combustion occurs, controlling the flash combustion time to be continuous for a period of time in a constant current state, stopping heating after the flash combustion is finished, and cooling the obtained flash combustion sample to the room temperature to obtain Li4Ti5O12And (3) sintering the body. And the current and voltage changes are observed in real time in the whole sintering process and are recorded in real time by the data recording unit.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a method for quickly preparing spinel Li at low temperature4Ti5O12The method of the lithium titanate material combines the preparation and flash burning technology of the precursor powder, the temperature required by flash burning synthesis is 200-500 ℃ lower than that of the traditional synthesis technology, the time required by flash burning is not more than 10 minutes, the total energy consumption is far lower than that of the traditional sintering method, and the method is a preparation method which obviously reduces the energy consumption. The product prepared by the method has uniform granularity, excellent cycle performance, rate capability and higher specific capacity.
Drawings
FIG. 1 is a schematic diagram of a flash system;
FIG. 2 shows the connection between the sample and the electrode in the sintering chamber;
FIG. 3 shows Li prepared in example4Ti5O12XRD pattern of lithium titanate material.
FIG. 4 shows Li prepared in example4Ti5O12The charge-discharge cycle performance curve of the battery prepared by the lithium titanate material.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
In the embodiment, the spinel Li is prepared by combining a solid oxide mixing method and a flash burning process4Ti5O12The lithium titanate material is prepared by the following specific steps:
weighing 6.44g of lithium carbonate powder, 17.40g of titanium dioxide powder and 50mL of ethanol, mixing in a 250mL zirconia ball milling tank, adding 120g of zirconia grinding balls with the diameter of 3mm, and reinforcing a cover; placing the packaged ball milling tank on a ball mill for ball milling, setting the rotating speed at 100r/min and setting the ball milling time at 12 h; and (3) drying the obtained mixed solution in an oven after removing the solvent, setting the temperature of the oven at 60 ℃, fully grinding and sieving the dried product to obtain flash-burned precursor powder.
Filling the flash-burned precursor powder into a cuboid hard alloy mold, and carrying out compression molding, wherein the molding pressure is 200MPa, and the pressure maintaining time is 2 min; keeping the film at 280MPa for 2 minutes after demoulding, and carrying out cold isostatic pressing treatment to obtain a cross section area of 4 multiplied by 4mm2And a long strip-shaped flash-fired precursor biscuit with the length of 20 mm.
Sintering was carried out using a flash firing system as shown in fig. 1: and putting the flash-burning precursor biscuit into a sintering device of a flash-burning system, clamping two ends of the biscuit by using a graphite electrode material, and introducing argon gas into the furnace for protection. D, electrifying direct current, and controlling the voltage to be 40V/cm; meanwhile, a sintering device is arranged to heat up at the speed of 5 ℃/minRaising the temperature at a high speed until the flash burning is finished; when the temperature rises to 440 ℃, the flash combustion begins to occur, and the current is controlled to be reduced to 40mA/mm2Controlling the duration of the flash time to be 120s in a constant current state; after the flash burning is finished, disconnecting the power supply of the sintering device, stopping heating, and cooling the obtained flash burning sample to room temperature along with the furnace temperature to obtain Li4Ti5O12And (3) sintering the body. Mixing Li4Ti5O12The sintered body was pulverized, ground and sieved through a 200-mesh sieve to obtain Li4Ti5O12And (3) powder products.
Li prepared in this example4Ti5O12The XRD results of the powder product are shown in fig. 3. The material was measured to have a current density of 1.6mA/cm at room temperature2The first discharge specific capacity was 158mAh/g, and the discharge specific capacity retention after 50 cycles was 95.5%, as shown in FIG. 4.
Example 2
In the embodiment, the spinel Li is prepared by combining a hydrothermal method and a flash firing process4Ti5O12The lithium titanate material is prepared by the following specific steps:
dissolving 10.0g of butyl titanate in 60.0mL of ethanol to obtain a titanium source solution, and simultaneously dissolving 1.62g of lithium nitrate in 60.0mL of water to obtain a lithium source solution; fully stirring the titanium source solution and the lithium source solution to obtain a mixed solution; placing the mixed solution in a hydrothermal kettle, placing the hydrothermal kettle containing the mixed solution in an oven for hydrothermal reaction, wherein the filling degree in the hydrothermal kettle is 60%, the reaction temperature of the hydrothermal reaction is 180 ℃, and the reaction time of the hydrothermal reaction at the reaction temperature is 24 hours; and cooling the hydrothermal reaction product to room temperature, drying, grinding and sieving to obtain flash-burned precursor powder.
Filling the flash-burned precursor powder into a bone-shaped hard alloy die, and carrying out compression molding under the molding pressure of 100MPa for 1 min; keeping the film at 200MPa for 2 minutes after demoulding, carrying out cold isostatic pressing treatment, and then perforating to obtain a cross-sectional area of 2 x 3mm2And a bone-shaped flash-burned precursor biscuit with an effective length of 20 mm.
Sintering was carried out using a flash firing system as shown in fig. 1: flash-firing the precursorPutting the biscuit into a sintering device of a flash combustion system, and enabling a platinum wire electrode material to penetrate through small holes at two ends of the biscuit; d, electrifying direct current, and controlling the voltage to be 150V/cm; meanwhile, a sintering device is arranged to heat up at the heating rate of 5 ℃/min until the flash firing is finished; when the temperature rises to 587 ℃, the flash combustion begins to occur, and the current is controlled to be reduced to 20mA/mm2Controlling the duration of the flash time to be 120s in a constant current state; after the flash burning is finished, disconnecting the power supply of the sintering device, stopping heating, and cooling the obtained flash burning sample to room temperature along with the furnace temperature to obtain Li4Ti5O12A sintered body; mixing Li4Ti5O12The sintered body was pulverized, ground and sieved through a 200-mesh sieve to obtain Li4Ti5O12And (3) powder products.
Li prepared in this example4Ti5O12The XRD results of the powder product are shown in fig. 3. The material was measured to have a current density of 1.6mA/cm at room temperature2The first specific discharge capacity was 166mAh/g, and the specific discharge capacity retention after 50 cycles was 98.7%, as shown in FIG. 4.
Example 3
In the embodiment, spinel Li is prepared by combining a sol-gel method and a flash firing process4Ti5O12The specific preparation process of the lithium titanate material is as follows:
dissolving 2.64g of lithium acetate and 38.4g of citric acid in 75.0mL of ethanol and 5.0mL of deionized water, and mixing to prepare a lithium source solution; dissolving 17.0g of butyl titanate in 100mL of ethanol to prepare a titanium source solution; strongly stirring the titanium source solution, slowly dropwise adding the lithium source solution into the titanium source solution, controlling the reaction temperature to be maintained at room temperature, continuously stirring to obtain transparent sol, and then aging for 24 hours to obtain milky wet gel; and (3) placing the wet gel in an oven, drying at constant temperature of 120 ℃ for 18h to obtain dry gel, and then grinding and sieving the dry gel to obtain flash-burned precursor powder.
Filling the flash-burned precursor powder into a bone-shaped hard alloy mold, and carrying out compression molding, wherein the molding pressure is 150MPa, and the pressure maintaining time is 1 min; keeping the film at 200MPa for 2 minutes after demoulding, carrying out cold isostatic pressing treatment, and then perforating to obtain a cross-sectional area of 2 x 3mm2And a bone-shaped flash-burned precursor biscuit with an effective length of 20 mm.
Sintering was carried out using a flash firing system as shown in fig. 1: putting the bone-shaped flash-burning precursor biscuit into a sintering device of a flash-burning system, and enabling a platinum wire electrode material to penetrate through small holes at two ends of the biscuit; d, electrifying direct current, and controlling the voltage to be 125V/cm; meanwhile, a sintering device is arranged to heat up at the heating rate of 5 ℃/min until the flash firing is finished; when the temperature rises to 664 ℃, the flash combustion begins to occur, and the current is controlled to be reduced to 20mA/mm2Controlling the duration of the flash time to be 150s in a constant current state; after the flash burning is finished, disconnecting the power supply of the sintering device, stopping heating, and cooling the obtained flash burning sample to room temperature along with the furnace temperature to obtain Li4Ti5O12A sintered body; mixing Li4Ti5O12The sintered body was pulverized, ground and sieved through a 200-mesh sieve to obtain Li4Ti5O12And (3) powder products.
Li prepared in this example4Ti5O12The XRD results of the powder product are shown in fig. 3. The material was measured to have a current density of 1.6mA/cm at room temperature2The first discharge specific capacity was 162mAh/g, and the discharge specific capacity retention after 50 cycles was 98.9%, as shown in FIG. 4.
Comparative example 1
A flash-fired precursor powder was prepared in exactly the same manner as in example 2.
Sintering was carried out using a flash firing system as shown in fig. 1: putting the bone-shaped flash-burning precursor biscuit into a sintering device of a flash-burning system, and enabling a platinum wire electrode material to penetrate through small holes at two ends of the biscuit; d, electrifying direct current, and controlling the voltage to be 150V/cm; meanwhile, a sintering device is arranged to heat up at the heating rate of 5 ℃/min until the flash firing is finished; when the temperature rises to 589 ℃, flash combustion begins to occur, and the current is controlled to be reduced to 20mA/mm2Controlling the flash time to last for 600s in a constant current state; after the flash burning is finished, disconnecting the power supply of the sintering device, stopping heating, and cooling the obtained flash burning sample to room temperature along with the furnace temperature to obtain Li4Ti5O12A sintered body; mixing Li4Ti5O12The sintered body was pulverized, ground and sieved through a 200-mesh sieve to obtain Li4Ti5O12And (3) powder products.
The XRD results of the material obtained by the method are shown in figure 3, and compared with example 1, the material has obvious impurities and does not meet the basic requirements of battery performance tests on purity.
Comparative example 2
A flash-fired precursor powder was prepared in exactly the same manner as in example 1.
Sintering was carried out using a flash firing system as shown in fig. 1: putting the bone-shaped flash-burning precursor biscuit into a sintering device of a flash-burning system, and enabling a platinum wire electrode material to penetrate through small holes at two ends of the biscuit; d, electrifying direct current, and controlling the voltage to be 150V/cm; meanwhile, a sintering device is arranged to heat up at the heating rate of 5 ℃/min until the flash firing is finished; when the temperature rises to 565 ℃, the flash combustion begins to occur, and the current is controlled to be reduced to 0.5mA/mm2Controlling the flash time to last for 10s in a constant current state; after the flash burning is finished, disconnecting the power supply of the sintering device, stopping heating, and cooling the obtained flash burning sample to room temperature along with the furnace temperature to obtain Li4Ti5O12A sintered body; mixing Li4Ti5O12The sintered body was pulverized, ground and sieved through a 200-mesh sieve to obtain Li4Ti5O12And (3) powder products.
The XRD result of the material obtained by the method is shown in figure 3, and the material is basically free from the product and does not meet the basic requirement of the battery performance test on the purity.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. Rapid preparation of spinel type Li at low temperature4Ti5O12A method of producing a lithium titanate material, comprising the steps of:
1) preparation of Li by solid oxide mixing method, hydrothermal method or sol-gel method4Ti5O12Flash-firing the precursor powder of (1);
2) putting the flash-burned precursor powder prepared in the step 1) into a mold, carrying out compression molding, demoulding, and carrying out cold isostatic pressing treatment to obtain a final flash-burned precursor biscuit;
3) applying direct current to two ends of the flash-burning precursor biscuit, and simultaneously heating the flash-burning precursor biscuit in a protective atmosphere until flash burning is finished; starting flash-burning when flash-burning occurs, controlling current density and flash-burning in a constant current state for a period of time, stopping heating after flash-burning is finished, and cooling the obtained flash-burning sample to room temperature to obtain Li4Ti5O12Sintering the resultant, and pulverizing the sintered product to obtain spinel-type Li4Ti5O12A lithium titanate powder product.
2. The method of claim 1 for rapidly preparing spinel-type Li at low temperature4Ti5O12The method for preparing the lithium titanate material is characterized in that the mould pressing pressure for mould pressing forming is 100-300Mpa, and the pressure maintaining time is 1-20 min; the cold isostatic pressing pressure is 200-300 MPa, and the holding time is 1-2 minutes.
3. The method of claim 1 for rapidly preparing spinel-type Li at low temperature4Ti5O12The method for preparing the lithium titanate material is characterized in that the voltage of the direct current is 10-150V/cm; the heating rate of the heating is 1-20 ℃/min; the current density is 0-700 mA/mm2(ii) a The flash time is 0-600 s.
4. The method of claim 1 for rapidly preparing spinel-type Li at low temperature4Ti5O12The method for preparing the lithium titanate material is characterized in that the Li is prepared by utilizing a solid oxide mixing method4Ti5O12The specific process of flash-firing the precursor powder comprises the following steps: placing a lithium source compound, a titanium source compound, grinding balls and a grinding medium in a ball milling tank for mixing, packaging the ball milling tank, placing the ball milling tank on a ball mill for ball milling to obtain a mixed solution, removing the solvent from the mixed solution, drying, grinding and sieving to obtain flash-fired precursor powderAnd (3) grinding.
5. The method of claim 4 for rapidly preparing spinel-type Li at low temperature4Ti5O12The method for preparing the lithium titanate material is characterized in that the lithium source compound is one or more of lithium hydroxide, lithium carbonate and lithium nitrate, the titanium source compound is titanium dioxide, and the molar ratio of lithium in the lithium source compound to titanium in the titanium source compound is 0.75-0.85; the grinding balls are made of zirconium dioxide, the diameter of the grinding balls is 3-15mm, and the mass of the grinding balls is 2-10 times of that of the compound powder; the grinding medium is one or more of water, an alcohol solvent and a ketone solvent, and the mass of the grinding medium is 1-5 times of that of the compound powder; the ball milling speed is 50-300r/min, and the time is 2-24 h; the drying temperature is 50-300 ℃, and the drying time is 6-24 h.
6. The method of claim 1 for rapidly preparing spinel-type Li at low temperature4Ti5O12The method for preparing the lithium titanate material is characterized in that Li is prepared by a hydrothermal method4Ti5O12The specific process of flash-firing the precursor powder comprises the following steps: mixing the titanium source solution and the lithium source solution under the stirring condition to obtain a mixed solution, and then carrying out hydrothermal reaction on the mixed solution for 5-48 hours at the temperature of 120-250 ℃; and cooling the hydrothermal reaction product to room temperature, drying, grinding and sieving to obtain flash-burned precursor powder.
7. The method of claim 6 for rapidly preparing spinel-type Li at low temperature4Ti5O12The method for preparing the lithium titanate material is characterized in that the titanium source solution is obtained by dissolving a titanium source compound in a titanium source solvent, and the lithium source solution is obtained by dissolving a lithium source compound in a lithium source solvent; the molar concentration of a lithium source compound in the lithium source solution is 0.08-4 mol/L, the molar concentration of a titanium source compound in the titanium source solution is 0.1-5 mol/L, and the molar ratio of lithium atoms in the lithium source solution to titanium atoms in the titanium source solution is 0.80-0.85.
8. The method of claim 1 for rapidly preparing spinel-type Li at low temperature4Ti5O12The method for preparing the lithium titanate material is characterized in that the Li is prepared by a sol-gel method4Ti5O12The specific process of flash-firing the precursor powder comprises the following steps: dissolving a lithium source compound and a chelating agent in a lithium source solvent and deionized water, and mixing to prepare a lithium source solution; dissolving a titanium source compound in a titanium source solvent to prepare a titanium source solution; strongly stirring the titanium source solution, slowly dropwise adding the lithium source solution into the titanium source solution, controlling the reaction temperature to be maintained at room temperature, continuously stirring to obtain transparent sol, and then aging to obtain milky wet gel; and (3) drying the wet gel in an oven to obtain dry gel, and then grinding and sieving the dry gel to obtain flash-burned precursor powder.
9. The method of claim 8 for rapidly preparing spinel-type Li at low temperature4Ti5O12The method for preparing the lithium titanate material is characterized in that the lithium source solvent and the titanium source solvent are one or more of methanol, ethanol, glycol, propanol, isopropanol, butanol, isobutanol and other alcohol solvents; the lithium source compound is one or more of lithium ethoxide, lithium acetate and lithium nitrate; the titanium source compound is one or two of butyl titanate and isopropyl titanate; the chelating agent is one or more of citric acid, oxalic acid, acrylic acid and tartaric acid.
10. Spinel type Li4Ti5O12A lithium titanate material characterized by being produced by the method according to any one of claims 1 to 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114907100A (en) * | 2022-05-19 | 2022-08-16 | 中国科学院长春应用化学研究所 | Instantaneous synthesis process of Ba-matrix sub-conductor electrolyte |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100027191A1 (en) * | 2006-04-19 | 2010-02-04 | Centre National De La Recherche Scientifique (Cnrs) | Ceramics Based on Lanthanum-Doped Barium Titanate, Method of Preparation and Uses |
| CN102303902A (en) * | 2011-08-05 | 2012-01-04 | 青岛乾运高科新材料有限公司 | Preparation method of lithium secondary battery negative electrode material nano spinel type lithium titanate |
| CN103400977A (en) * | 2013-08-19 | 2013-11-20 | 攀枝花学院 | Sol-gel method for preparing lithium titanate |
| CN108335768A (en) * | 2018-02-01 | 2018-07-27 | 中国工程物理研究院材料研究所 | A kind of preparation method of the fuel pellet based on nanometer titanium dioxide uranium or its compound |
| CN109192945A (en) * | 2018-08-21 | 2019-01-11 | 苏州山人纳米科技有限公司 | The flash burning preparation method of ternary anode material of lithium battery |
| CN109942303A (en) * | 2019-04-22 | 2019-06-28 | 浙江晨华科技有限公司 | A kind of flash burning molding method for preparing of ceramic crystal |
-
2020
- 2020-10-19 CN CN202011118082.1A patent/CN112374536A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100027191A1 (en) * | 2006-04-19 | 2010-02-04 | Centre National De La Recherche Scientifique (Cnrs) | Ceramics Based on Lanthanum-Doped Barium Titanate, Method of Preparation and Uses |
| CN102303902A (en) * | 2011-08-05 | 2012-01-04 | 青岛乾运高科新材料有限公司 | Preparation method of lithium secondary battery negative electrode material nano spinel type lithium titanate |
| CN103400977A (en) * | 2013-08-19 | 2013-11-20 | 攀枝花学院 | Sol-gel method for preparing lithium titanate |
| CN108335768A (en) * | 2018-02-01 | 2018-07-27 | 中国工程物理研究院材料研究所 | A kind of preparation method of the fuel pellet based on nanometer titanium dioxide uranium or its compound |
| CN109192945A (en) * | 2018-08-21 | 2019-01-11 | 苏州山人纳米科技有限公司 | The flash burning preparation method of ternary anode material of lithium battery |
| CN109942303A (en) * | 2019-04-22 | 2019-06-28 | 浙江晨华科技有限公司 | A kind of flash burning molding method for preparing of ceramic crystal |
Non-Patent Citations (2)
| Title |
|---|
| PETER JAKES ET AL.: "Mixed Ionic–Electronic Conducting Li4Ti5O12 as Anode Material for Lithium Ion Batteries with Enhanced Rate Capability – Impact of Oxygen Non-Stoichiometry and Aliovalent Mg2+-Doping Studied by Electron Paramagnetic Resonance", 《Z. PHYS. CHEM.》 * |
| SHIPEIRAN ET AL.: "An ultrafast synthesis method of LiNi1/3Co1/3Mn1/3O2 cathodes by flash/field-assisted sintering", 《J AM CERAM SOC.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114907100A (en) * | 2022-05-19 | 2022-08-16 | 中国科学院长春应用化学研究所 | Instantaneous synthesis process of Ba-matrix sub-conductor electrolyte |
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