CN111137916B - Preparation method of self-activated lithium titanate material - Google Patents
Preparation method of self-activated lithium titanate material Download PDFInfo
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- CN111137916B CN111137916B CN201911388163.0A CN201911388163A CN111137916B CN 111137916 B CN111137916 B CN 111137916B CN 201911388163 A CN201911388163 A CN 201911388163A CN 111137916 B CN111137916 B CN 111137916B
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- 239000000463 material Substances 0.000 title claims abstract description 26
- -1 activated lithium titanate Chemical class 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 64
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 63
- KELHQGOVULCJSG-UHFFFAOYSA-N n,n-dimethyl-1-(5-methylfuran-2-yl)ethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=C(C)O1 KELHQGOVULCJSG-UHFFFAOYSA-N 0.000 claims abstract description 57
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000000843 powder Substances 0.000 claims abstract description 29
- 238000001816 cooling Methods 0.000 claims abstract description 24
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 21
- 235000019441 ethanol Nutrition 0.000 claims abstract description 20
- 238000005507 spraying Methods 0.000 claims abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 15
- 239000000725 suspension Substances 0.000 claims abstract description 15
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 14
- 238000001125 extrusion Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002791 soaking Methods 0.000 claims abstract description 7
- 238000002604 ultrasonography Methods 0.000 claims description 33
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 2
- 206010021143 Hypoxia Diseases 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- 239000004408 titanium dioxide Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 208000021760 high fever Diseases 0.000 description 2
- 241000272194 Ciconiiformes Species 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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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
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
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- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a preparation method of an auto-active lithium titanate material, which comprises the following steps: step 1, adding lithium acetate into absolute ethyl alcohol, and uniformly stirring for 1-3h to obtain a lithium alcohol solution; step 2, adding titanium monoxide powder into the lithium alcohol solution, and carrying out low-temperature ultrasonic treatment for 2-4h to obtain a mixed suspension; step 3, uniformly spraying the mixed suspension into a sealed reaction kettle, standing at a constant temperature for 1-2 hours, and decompressing and cooling to obtain coated titanium monoxide particles; step 4, adding the coated titanium monoxide particles into a mold, and reacting for 2-4 hours at constant temperature and constant pressure to obtain a lithium titanate primary plate; and 5, soaking the lithium titanate primary plate in tetrabutyl titanate, performing low-temperature ultrasonic treatment for 3-5h, performing extrusion reaction for 2-4h in a humid environment, and sintering to obtain the self-activated lithium titanate material. The invention solves the problem of poor conductivity of the lithium titanate, and the titanium monoxide is used as the core, and the oxygen deficiency of the titanium monoxide is utilized to endow the lithium titanate with oxygen deficiency, so that the electron-hole structure of the lithium titanate is realized, and the overall conductivity and activity are greatly improved.
Description
Technical Field
The invention belongs to lithium battery materials, and particularly relates to a preparation method of an auto-active lithium titanate material.
Background
Lithium titanate "zero strain materials" are being increasingly used in lithium ion batteries due to their superior cycle performance, good rate capability and reliable safety. Lithium titanate has a three-dimensional lithium ion diffusion channel unique to a spinel structure, Li+Diffusion coefficient of 2 x 10-8cm2The diffusion in graphite is more than 10 times that in the graphite, so that the graphite has obvious quick-charging advantage and good high-low temperature performance; in addition, the safety is good, the service life is long, and the environment is protected, so that the electric vehicle has wide application space in the fields of electric motor coaches, energy storage, high-power equipment and the like. Especially in the field of energy storage, along with the continuous deepening of the power system reform in China and the rise of energy Internet, the increase of peak-load and frequency modulation requirements in the 'three north' area and the highlighting of the problems of wind abandonment and light abandonment, the application value of the energy storage in the fields of renewable energy consumption, distributed power generation, micro-grid and the like is more and more emphasized. Different from a power battery, the energy storage battery pays more attention to the performances of long service life, low cost and high safety of the battery, so that the advantages of the lithium titanate energy storage battery are very obvious. However, lithium titanate has its own defects, such as poor conductivity and severe discharge polarization at high current, and thus has poor performance at high rate.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a self-activated lithium titanate material, which solves the problem of poor conductivity of lithium titanate, and titanium monoxide is used as an inner core, and oxygen deficiency of the titanium monoxide is utilized to endow the lithium titanate with oxygen deficiency, so that an electron-hole structure of the lithium titanate is realized, and the overall conductivity and activity are greatly improved.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a preparation method of a self-activated lithium titanate material comprises the following steps:
step 1, adding lithium acetate into absolute ethyl alcohol, and uniformly stirring for 1-3h to obtain a lithium alcohol solution;
step 2, adding titanium monoxide powder into the lithium alcohol solution, and carrying out low-temperature ultrasonic treatment for 2-4h to obtain a mixed suspension;
step 3, uniformly spraying the mixed suspension into a sealed reaction kettle, standing at a constant temperature for 1-2 hours, and decompressing and cooling to obtain coated titanium monoxide particles;
step 4, adding the coated titanium monoxide particles into a mold, and reacting for 2-4 hours at constant temperature and constant pressure to obtain a lithium titanate primary plate;
and 5, soaking the lithium titanate primary plate in tetrabutyl titanate, performing low-temperature ultrasonic treatment for 3-5h, performing extrusion reaction for 2-4h in a humid environment, and sintering to obtain the self-activated lithium titanate material.
The concentration of the lithium acetate in the absolute ethyl alcohol in the step 1 is 20-50g/L, and the stirring speed is 1000-2000 r/min.
The concentration of the titanium monoxide powder in the lithium alcohol solution in the step 2 is 10-20g/L, and the titanium monoxide powder adopts micron-sized powder with the particle size of 100-800 mu m.
The low-temperature ultrasound in the step 2 adopts low-temperature gap ultrasound, the temperature is 1-6 ℃, the ultrasound frequency is 60-90kHz, the single ultrasound time is 10-15s, and the interval time is 30-60 s.
The amount of spraying in the step 3 is 10-15g/m3The temperature is 80-90 ℃, the sealed reaction kettle is in nitrogen atmosphere, the temperature of constant temperature standing is 90-100 ℃, and the pressure of standing is 3-5 MPa.
The pressure relief cooling in the step 3 adopts the mode of firstly slowly relieving pressure and then rapidly cooling, the pressure relief speed is 0.1-0.3MPa/min, and the cooling speed is 20-30 ℃/min.
The pressure of the constant-temperature and constant-pressure reaction in the step 4 is 3-6MPa, and the temperature is 100-120 ℃.
The temperature of the low-temperature ultrasound in the step 5 is 5-10 ℃, and the ultrasound frequency is 40-80 kHz; the humidity under the humid environment is 50 percent, the temperature of the extrusion reaction is 100-120 ℃, the pressure is 3-7MPa, and the sintering temperature is 400-500 ℃.
From the above description, it can be seen that the present invention has the following advantages:
1. the invention solves the problem of poor conductivity of the lithium titanate, and the titanium monoxide is used as the core, and the oxygen deficiency of the titanium monoxide is utilized to endow the lithium titanate with oxygen deficiency, so that the electron-hole structure of the lithium titanate is realized, and the overall conductivity and activity are greatly improved.
2. According to the invention, titanium monoxide is converted into titanium dioxide under an oxidation condition, and lithium acetate can be wrapped by the permeability of tetrabutyl titanate, so that lithium titanate with an internal and external stable structure is realized.
Detailed Description
The present invention is described in detail with reference to examples, but the present invention is not limited to the claims.
A preparation method of a self-activated lithium titanate material comprises the following steps:
step 1, adding lithium acetate into absolute ethyl alcohol, and uniformly stirring for 1-3h to obtain a lithium alcohol solution;
step 2, adding titanium monoxide powder into the lithium alcohol solution, and performing low-temperature ultrasonic treatment for 2-4 hours to obtain a mixed suspension;
step 3, uniformly spraying the mixed suspension into a sealed reaction kettle, standing at a constant temperature for 1-2 hours, and decompressing and cooling to obtain coated titanium monoxide particles;
step 4, adding the coated titanium monoxide particles into a mold, and reacting for 2-4 hours at constant temperature and constant pressure to obtain a lithium titanate primary plate;
and 5, soaking the lithium titanate primary plate in tetrabutyl titanate, performing low-temperature ultrasonic treatment for 3-5h, performing extrusion reaction for 2-4h in a humid environment, and sintering to obtain the self-activated lithium titanate material.
The concentration of the lithium acetate in the absolute ethyl alcohol in the step 1 is 20-50g/L, and the stirring speed is 1000-2000 r/min.
The concentration of the titanium monoxide powder in the lithium alcohol solution in the step 2 is 10-20g/L, and the titanium monoxide powder adopts micron-sized powder with the particle size of 100-800 mu m.
The low-temperature ultrasound in the step 2 adopts low-temperature gap ultrasound, the temperature is 1-6 ℃, the ultrasonic frequency is 60-90kHz, the single-time ultrasound time is 10-15s, the interval time is 30-60s, and the low-temperature ultrasound can permeate lithium acetate into the gap on the surface of the titanium monoxide by utilizing the high-frequency vibration of the ultrasound and form a stable lithium acetate film on the surface of the titanium monoxide; supersound itself belongs to the resonance that high frequency vibration brought the intermolecular, and high fever can be brought in long-time vibration to cause the transition of intermolecular, for solving this problem, adopt the supersound under the low temperature environment can utilize the influence of solution temperature to titanium monoxide under the low temperature condition, high frequency clearance supersound can utilize high frequency supersound to solve the effectual reunion problem of solving titanium monoxide of connecting unstable titanium monoxide powder simultaneously, and intermittent type supersound can prevent that the supersound from lasting the heat supply, causes local high fever phenomenon to produce.
The amount of spraying in the step 3 is 10-15g/m3The temperature is 80-90 ℃, the sealed reaction kettle is in nitrogen atmosphere, the temperature of constant temperature standing is 90-100 ℃, and the standing pressure is 3-5 MPa; spraying the mixed suspension in a sealed reaction kettle to form a good spraying dispersion effect, uniformly dispersing the coated titanium monoxide powder, and separating the anhydrous ethanol from the lithium acetate coated titanium monoxide powder at the temperature; in the process of standing at constant temperature, the coated titanium monoxide slowly settles to the bottom of the reaction kettle, and the absolute ethyl alcohol and the nitrogen form mixed gas; the nitrogen atmosphere ensures that no oxygen is present in the entire atmosphere, prevents the penetration of oxygen, and prevents the oxygen from reacting with the titanium monoxide, causing deterioration of the titanium monoxide powder inside.
The pressure relief cooling in the step 3 adopts the mode of firstly slowly relieving pressure and then rapidly cooling, the pressure relief speed is 0.1-0.3MPa/min, and the cooling speed is 20-30 ℃/min. In the pressure relief process, the absolute ethyl alcohol is still in a steam state, in the slow pressure relief process, a large amount of absolute ethyl alcohol is discharged in a pressure relief mode, the absolute ethyl alcohol content is extremely low after cooling, lithium acetate cannot be dissolved, and the lithium acetate can form a damp system to form a surface wet film.
The pressure of the constant-temperature and constant-pressure reaction in the step 4 is 3-6MPa, and the temperature is 100-120 ℃; converting absolute ethyl alcohol into a gas state under a constant temperature condition, uniformly dispersing lithium acetate onto the surface of titanium monoxide, forming tight combination under a constant pressure condition, oxidizing oxygen in the air and titanium monoxide molecules on the surface layer of titanium monoxide particles to convert the oxygen into titanium dioxide, and forming a primary combination film layer of the lithium acetate and the titanium dioxide on the surface of the penguin.
The temperature of the low-temperature ultrasound in the step 5 is 5-10 ℃, and the ultrasound frequency is 40-80 kHz; the tetrabutyl titanate can be permeated into gaps of the lithium acetate in a low-temperature ultrasonic mode; the humidity in a humid environment is 50%, the temperature of the extrusion reaction is 100-120 ℃, the pressure is 3-7MPa, in the humid environment, tetrabutyl titanate is hydrolyzed to form titanium dioxide, and at the moment, the inside and the outside of lithium acetate can form the titanium dioxide; the sintering temperature is 400-500 ℃, and based on the formation of titanium dioxide on the surface of titanium monoxide, a good sealing effect can be achieved, a protection effect is achieved in the sintering process, and lithium acetate is converted into lithium oxide in the sintering process and is converted into a lithium titanate structure together with the titanium dioxide.
Example 1
A preparation method of an auto-active lithium titanate material comprises the following steps:
step 1, adding lithium acetate into absolute ethyl alcohol, and stirring uniformly for 1h to obtain a lithium alcohol solution;
step 2, adding titanium monoxide powder into the lithium alcohol solution, and carrying out low-temperature ultrasonic treatment for 2 hours to obtain a mixed suspension;
step 3, uniformly spraying the mixed suspension into a sealed reaction kettle, standing at a constant temperature for 1h, and decompressing and cooling to obtain coated titanium monoxide particles;
step 4, adding the coated titanium monoxide particles into a mold, and reacting for 2 hours at constant temperature and constant pressure to obtain a lithium titanate primary plate;
and 5, soaking the lithium titanate primary plate in tetrabutyl titanate, performing low-temperature ultrasonic treatment for 3 hours, performing extrusion reaction for 2 hours in a humid environment, and sintering to obtain the self-activated lithium titanate material.
The concentration of the lithium acetate in the absolute ethyl alcohol in the step 1 is 20g/L, and the stirring speed is 1000 r/min.
The concentration of the titanium monoxide powder in the lithium alcohol solution in the step 2 is 10g/L, and the titanium monoxide powder is micron-sized powder with the particle size of 100 mu m.
The low-temperature ultrasonic in the step 2 adopts low-temperature gap ultrasonic, the temperature is 1 ℃, the ultrasonic frequency is 60kHz, the single ultrasonic time is 10s, and the interval time is 30 s.
The amount of spraying in the step 3 is 10g/m3The temperature is 80 ℃, the sealed reaction kettle is in nitrogen atmosphere, the temperature of constant temperature standing is 90 ℃, and the pressure of standing is 3 MPa.
And 3, the pressure relief cooling in the step 3 is carried out by adopting a mode of firstly slowly relieving pressure and then rapidly cooling, wherein the pressure relief speed is 0.1MPa/min, and the cooling speed is 20 ℃/min.
The pressure of the constant-temperature and constant-pressure reaction in the step 4 is 3MPa, and the temperature is 100 ℃.
The temperature of the low-temperature ultrasound in the step 5 is 5 ℃, and the ultrasound frequency is 40 kHz; the humidity in a humid environment is 50%, the temperature of the extrusion reaction is 100 ℃, the pressure is 3MPa, and the sintering temperature is 400 ℃.
With a commercially available lithium titanate material as a comparative example, under the same detection conditions, the conductivity of the lithium titanate material with titanium monoxide as the core prepared in the example is improved by 5% compared with the comparative example, and after 200 times of repeated use, the conductivity loss of the lithium titanate in the example is only 2%, which shows good stability.
Example 2
A preparation method of an auto-active lithium titanate material comprises the following steps:
step 1, adding lithium acetate into absolute ethyl alcohol, and uniformly stirring for 3 hours to obtain a lithium alcohol solution;
step 2, adding titanium monoxide powder into the lithium alcohol solution, and carrying out low-temperature ultrasonic treatment for 4 hours to obtain a mixed suspension;
step 3, uniformly spraying the mixed suspension into a sealed reaction kettle, standing at a constant temperature for 2 hours, and decompressing and cooling to obtain coated titanium monoxide particles;
step 4, adding the coated titanium monoxide particles into a mold, and reacting for 4 hours at constant temperature and constant pressure to obtain a lithium titanate primary plate;
and 5, soaking the lithium titanate primary plate in tetrabutyl titanate, performing low-temperature ultrasonic treatment for 5 hours, performing extrusion reaction for 4 hours in a humid environment, and sintering to obtain the self-activated lithium titanate material.
The concentration of the lithium acetate in the absolute ethyl alcohol in the step 1 is 50g/L, and the stirring speed is 2000 r/min.
The concentration of the titanium monoxide powder in the lithium alcohol solution in the step 2 is 20g/L, and the titanium monoxide powder is micron-sized powder with the particle size of 800 microns.
The low-temperature ultrasound in the step 2 adopts low-temperature gap ultrasound, the temperature is 6 ℃, the ultrasound frequency is 90kHz, the single ultrasound time is 15s, and the interval time is 60 s.
The amount of spraying in the step 3 is 15g/m3The temperature is 90 ℃, the sealed reaction kettle is in nitrogen atmosphere, the temperature of constant temperature standing is 100 ℃, and the pressure of standing is 5 MPa.
And 3, the pressure relief cooling in the step 3 is carried out by adopting a mode of firstly slowly relieving pressure and then rapidly cooling, wherein the pressure relief speed is 0.3MPa/min, and the cooling speed is 30 ℃/min.
The pressure of the constant-temperature and constant-pressure reaction in the step 4 is 6MPa, and the temperature is 120 ℃.
The temperature of the low-temperature ultrasound in the step 5 is 10 ℃, and the ultrasound frequency is 80 kHz; the humidity under the humid environment is 50%, the temperature of the extrusion reaction is 120 ℃, the pressure is 3-7MPa, and the sintering temperature is 500 ℃.
With a commercially available lithium titanate material as a comparative example, under the same detection conditions, the conductivity of the lithium titanate material with titanium monoxide as the core prepared in the example is improved by 8% compared with the comparative example, and after 200 times of repeated use, the conductivity loss of the lithium titanate in the example is only 3%, which shows good stability.
Example 3
A preparation method of an auto-active lithium titanate material comprises the following steps:
step 1, adding lithium acetate into absolute ethyl alcohol, and stirring uniformly for 2 hours to obtain a lithium alcohol solution;
step 2, adding titanium monoxide powder into the lithium alcohol solution, and carrying out low-temperature ultrasonic treatment for 3 hours to obtain a mixed suspension;
step 3, uniformly spraying the mixed suspension into a sealed reaction kettle, standing at a constant temperature for 2 hours, and decompressing and cooling to obtain coated titanium monoxide particles;
step 4, adding the coated titanium monoxide particles into a mold, and reacting for 3 hours at constant temperature and constant pressure to obtain a lithium titanate primary plate;
and 5, soaking the lithium titanate primary plate in tetrabutyl titanate, performing low-temperature ultrasonic treatment for 4 hours, performing extrusion reaction for 3 hours in a humid environment, and sintering to obtain the self-activated lithium titanate material.
The concentration of the lithium acetate in the absolute ethyl alcohol in the step 1 is 40g/L, and the stirring speed is 1500 r/min.
The concentration of the titanium monoxide powder in the lithium alcohol solution in the step 2 is 15g/L, and the titanium monoxide powder is micron-sized powder with the particle size of 600 mu m.
The low-temperature ultrasound in the step 2 adopts low-temperature gap ultrasound, the temperature is 4 ℃, the ultrasound frequency is 70kHz, the single ultrasound time is 13s, and the interval time is 50 s.
The amount of spraying in the step 3 is 13g/m3The temperature is 85 ℃, the sealed reaction kettle is in nitrogen atmosphere, the temperature of constant temperature standing is 95 ℃, and the pressure of standing is 4 MPa.
The pressure relief cooling in the step 3 is processed by adopting a mode of firstly slowly relieving pressure and then rapidly reducing temperature, wherein the pressure relief speed is 0.2MPa/min, and the temperature reduction speed is 25 ℃/min.
The pressure of the constant-temperature and constant-pressure reaction in the step 4 is 5MPa, and the temperature is 110 ℃.
The temperature of the low-temperature ultrasound in the step 5 is 8 ℃, and the ultrasound frequency is 60 kHz; the humidity under the humid environment is 50%, the temperature of the extrusion reaction is 110 ℃, the pressure is 3-7MPa, and the sintering temperature is 450 ℃.
With a commercially available lithium titanate material as a comparative example, under the same detection conditions, the conductivity of the lithium titanate material with titanium monoxide as the core prepared in the example is improved by 7% compared with the comparative example, and after 200 times of repeated use, the conductivity loss of the lithium titanate in the example is only 1%, thus showing good stability.
It should be understood that the detailed description of the invention is merely illustrative of the invention and is not intended to limit the invention to the specific embodiments described. It will be appreciated by those skilled in the art that the present invention may be modified or substituted equally as well to achieve the same technical result; as long as the use requirements are met, the method is within the protection scope of the invention.
Claims (1)
1. A preparation method of a self-activated lithium titanate material comprises the following steps:
step 1, adding lithium acetate into absolute ethyl alcohol, and uniformly stirring for 1-3h to obtain a lithium alcohol solution;
step 2, adding titanium monoxide powder into the lithium alcohol solution, and carrying out low-temperature ultrasonic treatment for 2-4h to obtain a mixed suspension;
step 3, uniformly spraying the mixed suspension into a sealed reaction kettle, standing at a constant temperature for 1-2 hours, and decompressing and cooling to obtain coated titanium monoxide particles;
step 4, adding the coated titanium monoxide particles into a mold, and reacting for 2-4 hours at constant temperature and constant pressure to obtain a lithium titanate primary plate;
step 5, soaking the lithium titanate primary plate into tetrabutyl titanate, performing low-temperature ultrasonic treatment for 3-5h, performing extrusion reaction for 2-4h in a humid environment, and sintering to obtain a self-activated lithium titanate material;
the concentration of the lithium acetate in the absolute ethyl alcohol in the step 1 is 20-50g/L, and the stirring speed is 1000-2000 r/min;
the concentration of the titanium monoxide powder in the lithium alcohol solution in the step 2 is 10-20g/L, and the titanium monoxide powder is micron-sized powder with the particle size of 100-800 mu m; the low-temperature ultrasound adopts low-temperature gap ultrasound, the temperature is 1-6 ℃, the ultrasound frequency is 60-90kHz, the single ultrasound time is 10-15s, and the interval time is 30-60 s;
the amount of spraying in the step 3 is 10-15g/m3Spraying at 80-90 deg.C, sealing the reaction kettle in nitrogen atmosphere, standing at 90-100 deg.C and 3-5 MPa; the pressure relief cooling is carried out by adopting a mode of firstly slowly relieving pressure and then rapidly cooling, the pressure relief speed is 0.1-0.3MPa/min, and the cooling speed is 20-30 ℃/min;
the pressure of the constant-temperature and constant-pressure reaction in the step 4 is 3-6MPa, and the temperature is 100-120 ℃;
the temperature of the low-temperature ultrasound in the step 5 is 5-10 ℃, and the ultrasound frequency is 40-80 kHz; the humidity under the humid environment is 50 percent, the temperature of the extrusion reaction is 100-120 ℃, the pressure is 3-7MPa, and the sintering temperature is 400-500 ℃.
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