CN110745851B - Spherical alpha-alumina fire retardant and preparation method thereof - Google Patents
Spherical alpha-alumina fire retardant and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
- C01F7/308—Thermal decomposition of nitrates
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- C—CHEMISTRY; METALLURGY
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
- C01F7/302—Hydrolysis or oxidation of gaseous aluminium compounds in the gaseous phase
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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- 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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- 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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- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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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
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- 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
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Abstract
The invention relates to a spherical alpha-alumina flame retardant and a preparation method thereof, wherein a dispersant is prepared from deionized water, absolute ethyl alcohol, citric acid and tris (hydroxymethyl) aminomethane, alkali and aluminate are added into the dispersant to form a mixed solution, a superfine short fiber product is obtained by reaction, and the spherical alpha-alumina is obtained by spraying and sintering. The spherical alpha-alumina has the characteristics of uniform particle size, regular spherical shape, no moisture and high purity phase, has higher electronic insulativity, electrolyte corrosion resistance and thermal stability, has enough electrochemical and chemical stability as a flame retardant, and has good homogenization effect.
Description
Technical Field
The invention relates to the technical field of preparation of alpha-alumina, in particular to a high-purity spherical alpha-alumina flame retardant with uniform particle size and a preparation method thereof.
Background
Since human beings are aware of energy problems and environmental problems, new clean energy is receiving much attention. The chargeable and dischargeable battery is developed to the present, the lithium sodium ion battery gradually becomes a mainstream product in the market, and according to website market statistics such as a lithium power grid, a big lithium ion battery, and a financial institution, the lithium sodium ion battery is mainly and widely applied to daily electronic equipment, new energy automobiles and large power equipment. Among them, new energy vehicles have been listed as key development projects by the nation. Under the condition of wide application, the problems of the lithium-sodium ion battery also come along, especially the safety accidents of the lithium battery equipment are frequent and comprehensive, and the safety accidents are mainly found under the conditions that the battery is collided, punctured or at high temperature.
The Shandong Industrial ceramics research institute in 1981 published in the journal article of ceramics shows that the inorganic diaphragm of the alkaline battery has good high temperature resistance and oxidation resistance, and has high capability of blocking silver diffusion migration and resisting zinc dendrite growth and spread. The publication by Daigo Takemura et al (10.1016/j. Popowsur.2005.03.159) in 2005 showed that the ceramic powder based separator was able to improve the thermal stability of the separator. Comprehensive reports show that the improvement of a lithium sodium ion battery diaphragm which mainly forms one of the core parts of the lithium sodium ion battery can improve the safety performance of the lithium battery and stabilize the application of the lithium battery, and the ceramic coating diaphragm is one of the main means for improving the performance of the diaphragm. In 2019, the latest progress of the lithium battery diaphragm in the content of the medium-star material increase and reserve plans is planned to collect 20 hundred million funds and construct a super-coating plant project.
Most studies (CN 201410542516.9, CN201811072618.3, cn201711395405. X) use alumina powder or boehmite powder for ceramic coating, which are generally referred to as flame retardants. Because the aluminum oxide has physicochemical properties such as corrosion resistance, high-temperature stability and the like, particularly the alpha-aluminum oxide has the characteristics of structural stability, no water and the like, the ceramic coating of the lithium battery diaphragm can solve the problems of high temperature resistance, electrolyte corrosion resistance and electronic insulativity which are not possessed by a common diaphragm, and can improve the partial safety performance of the lithium battery. According to experiments, the safety performance of the lithium battery under the collision or puncture condition can be improved by using the superfine high-purity spherical alpha-alumina as the lithium battery diaphragm flame retardant compared with the common alpha-alumina.
However, most of the aluminum oxide powders prepared by the current methods, such as a high-temperature solid phase method (CN 107032765A), a sol-gel method (CN 108863435A, CN 106430266A), a combustion method (CN 107620026A), a hydrothermal method (preparation and characterization of nano Al2O3 modified polyimide film synthesized by the hydrothermal method, CN105417562A, CN 104477926A), and an alkoxide method (CN 102491392A), are mostly irregular in morphology, or contain certain magnetic element impurities, or have characteristics of uneven particle size, or high cost, and cannot simultaneously improve the relationship between the particle size, morphology, purity and cost of the aluminum oxide.
Disclosure of Invention
The invention aims to solve the technical problem of providing a spherical alpha-alumina flame retardant with uniform particle size and a preparation method thereof.
According to an aspect of the present invention, there is provided a method for preparing a spherical α -alumina flame retardant, comprising:
preparing a dispersing agent from deionized water, absolute ethyl alcohol, citric acid and tris (hydroxymethyl) aminomethane, adding alkali and aluminate into the dispersing agent to form a mixed solution, and stirring the mixed solution until the mixed solution is in a microemulsion state, wherein the pH value is 7-7.5; the dispersing agent comprises the following components in proportion: 35ml of deionized water, 2ml of absolute ethyl alcohol, 10ml of citric acid aqueous solution (the concentration is 0.1 mol/ml) and 10ml of tris (hydroxymethyl) aminomethane aqueous solution (the concentration is 0.1 mol/ml);
step two, adding deionized water into the mixed solution for dilution, and stirring the diluted solution;
step three, spraying and drying the stirred diluted solution in spray drying equipment filled with nitrogen to obtain powder;
step four, washing the powder with deionized water, filtering, and drying;
and (V) sintering the dried powder at high temperature of 1200-1300 ℃ in a muffle furnace to obtain the product.
Further, in the step (one), the stirring speed of the mixed solution is 1000r/min.
Further, in the step (one), the alkali is ammonium bicarbonate, the aluminate is one of aluminum nitrate or aluminum chloride, and the molar ratio of the alkali to the aluminate is 1:4.
further, in the step (II), the stirring speed of the diluted solution is 600r/min.
Further, in the step (three), the inlet temperature of the spray drying was 150 ℃ and the outlet temperature was 80 ℃.
Further, in the step (IV), the cleaning is carried out by ultrasonic cleaning for 2 hours at the ultrasonic frequency of 100 Hz.
Further, in the step (V), the sintering route is to heat up to 1200 ℃ at 10K/min, then keep the temperature at 1200 ℃ for 2 hours, and then cool down to 500 ℃ at 10K/min.
Further, in the step (V), the sintering route is to heat up to 1300 ℃ at 10K/min and then cool down to room temperature at 20K/min.
According to another aspect of the present invention, there is provided a spherical alpha-alumina flame retardant obtained by the above method.
In addition, the invention also claims the application of the spherical alpha-alumina flame retardant in the lithium ion battery diaphragm.
According to the invention, aluminate is used as an aluminum source, and the prepared sample can keep the shape and particle size before sintering at high temperature through the prepared dispersing agent, the regulation and control of spraying parameters and ultrasonic cleaning. Compared with other ceramic samples with uneven or larger particle size and irregular appearance, the alpha-alumina of the invention has the characteristics of uniform particle size, regular spherical appearance, no moisture and high purity phase, and has higher electronic insulation, electrolyte corrosion resistance and thermal stability.
The characteristics of the invention ensure that the alpha-alumina as the flame retardant has sufficient electrochemical and chemical stability and good homogenization effect, and compared with the flame retardant prepared by other methods, the safety performance of the diaphragm under the physical environment changes such as high temperature, collision, puncture and the like can be better improved.
Drawings
FIG. 1 is an SEM image of the powder of a sample obtained by spray drying in example 1;
FIG. 2 is a graph of the powder phase of the sample obtained by spray drying +1200 ℃ sintering of example 2 compared to a standard card;
FIG. 3 is an infrared spectrum of a sample powder obtained by spray drying +1200 ℃ sintering of example 2;
FIG. 4 is an SEM image of the powder of a sample obtained by spray drying +1200 ℃ sintering of example 2;
FIG. 5 is an SEM image of the powder of a sample obtained by spray drying +1300 ℃ sintering of example 3.
Detailed Description
An exemplary embodiment of the present invention provides a method for preparing a spherical alpha-alumina flame retardant. The preparation method comprises the following steps:
step one, preparing a dispersing agent by deionized water, absolute ethyl alcohol, citric acid and tris (hydroxymethyl) aminomethane, adding alkali and aluminate into the dispersing agent to form a mixed solution, and stirring the mixed solution until the mixed solution is in a microemulsion state, wherein the pH value is 7-7.5. The preparation proportion of each component in the dispersant is as follows: 35ml of deionized water, 2ml of absolute ethyl alcohol, 10ml of an aqueous citric acid solution (concentration: 0.1 mol/ml), and 10ml of an aqueous tris (hydroxymethyl) aminomethane solution (concentration: 0.1 mol/ml). Citric acid and Tris are mainly used as buffering agents and dispersing agents. The alkali is ammonium bicarbonate. Is easy to decompose. The control is good when the spray drying is carried out. The aluminate is one of aluminum nitrate or aluminum chloride, and the molar ratio of the alkali to the aluminate is 1:4. in specific implementation, the alkali and the aluminate are respectively added into deionized water to prepare a solution, and then slowly dropped into the prepared and stirring dispersing agent. The pH of the dispersant was varied from 3.5 to (7-7.5) during the addition. The stirring speed of the mixed solution is preferably 1000r/min.
And (II) adding deionized water into the mixed solution for dilution, and stirring the diluted solution. The stirring speed of the diluted solution is preferably 600r/min.
And (III) performing spray drying on the stirred diluted solution in spray drying equipment filled with nitrogen to obtain powder. The inlet temperature for spray drying was 150 ℃ and the outlet temperature was 80 ℃. The spray drying operation was carried out at a constant temperature of 26 ℃ at room temperature under aeration and drying.
And step four, washing the powder with deionized water, filtering, and drying. Ultrasonic cleaning is adopted, the ultrasonic frequency is 100 Hz, and the ultrasonic cleaning is carried out for 2 hours.
And (V) sintering the dried powder at high temperature of 1200-1300 ℃ in a muffle furnace to obtain the product. The sintering route is heating to 1200 ℃ at 10K/min, then keeping the temperature at 1200 ℃ for 2 hours, and then cooling to 500 ℃ at 10K/min. Or heating to 1300 ℃ at the speed of 10K/min, and then cooling to room temperature at the speed of 20K/min to obtain the spherical a-phase alumina flame retardant.
The method takes aluminate and alkali as raw materials, controls the grain diameter, the dispersibility and the solid content of a reaction product by adding a dispersant to obtain a superfine short fiber-shaped product, and obtains the spherical alpha-alumina by spraying and sintering. The alpha-alumina has a spherical shape, a uniform particle size and a high-purity alpha phase, and the alpha-alumina has no moisture.
In the method, the reaction activity and the molecular tension between reaction products are increased by adding the dispersing agent, and the particle size, the dispersibility in the solution and the solid content of the reaction products are controlled to obtain the superfine short fiber-shaped product. The appearance and the particle size of a product obtained by spray drying are controlled by combining the outlet temperature and the inlet temperature of a spraying device, the inlet speed and the nitrogen circulation, and finally the phase purity of the product is controlled by a sintering method.
The preparation method can prepare the high-purity spherical alpha alumina with uniform particle size by using the spray drying equipment and the muffle furnace equipment, and has the advantages of low cost, less electric energy consumption, safety, simple preparation process, no corrosion to used equipment and the like.
The technical solution claimed by the present invention is further illustrated by the following examples. However, the examples are intended to illustrate embodiments of the invention without departing from the scope of the subject matter of the invention, and the scope of the invention is not limited by the examples. Unless otherwise specifically indicated, the materials and reagents used in the present invention are available from commercial products in the art.
Example 1
1mol of aluminum nitrate nonahydrate is prepared into solution in 450ml of deionized water, and the solution is stirred at the rotating speed of 600 r/min; the resulting solution was spray dried in a nitrogen sparge spray apparatus to obtain a powder, which was dried at an inlet temperature of 150 ℃ and an outlet temperature of 80 ℃. The obtained powder was washed and dried. From FIG. 1, it can be seen that the sample powder obtained by spray drying using aluminum nitrate as an aluminum source is spherical or nearly spherical. However, this preparation method is liable to cause corrosion of the apparatus.
Example 2
1) Respectively adding 1mol of aluminum nitrate nonahydrate and 4mol of ammonium bicarbonate into 100ml of deionized water to prepare solutions, simultaneously dripping the solutions into a dispersant solution prepared by 350ml of deionized water, 20ml of ethanol, 10ml of citric acid aqueous solution (the concentration is 0.1 mol/ml) and 10ml of Tris aqueous solution (the concentration is 0.1 mol/ml), stirring the dispersant solution by using a centrifugal stirrer at the rotating speed of 1000r/min, and controlling the pH value of the solution after the reaction is completely carried out to be 7-7.5;
2) Taking 50ml of the mixed solution in the step 1), adding 100ml of deionized water for dilution, and stirring the diluted solution at the rotating speed of 600 r/min;
3) Carrying out spray drying on the solution obtained in the step 2) in a spraying device filled with nitrogen, and granulating to obtain powder; drying was carried out at an inlet temperature of 150 ℃ and an outlet temperature of 80 ℃.
4) Washing the powder obtained in the step 3) by using deionized water, filtering by using filter paper, and drying at 60 ℃; the cleaning is carried out for 2 hours by ultrasonic wave at the ultrasonic frequency of 100 Hz.
5) Uniformly dispersing the powder obtained in the step 4) in a crucible, wherein the sintering route is to sinter the powder to 1200 ℃ at 10K/min, and then, preserving the heat at 1200 ℃ for 2 hours, and cooling the powder to 500 ℃ at 10K/min. Spherical a-phase alumina powder was obtained as shown in FIG. 4.
The spherical alpha-phase alumina flame retardant prepared in this example is characterized in the graph shown in FIGS. 1-3.
As can be seen from FIG. 2, the XRD phase of the alumina flame retardant prepared in this example is a complete alpha phase. Has the physicochemical property of alpha-phase alumina.
As can be seen from fig. 3, the α -phase alumina flame retardant prepared in this example does not contain hydroxyl groups, i.e., the sample contains no moisture.
As can be seen from FIG. 4, the sample prepared in this example was spherical in shape and had a particle size of at most 2.76um.
Example 3
1) Preparing 1mol of aluminum chloride and 4mol of ammonium bicarbonate into solutions by respectively using 100ml of pure water, simultaneously dripping the solutions into a dispersant solution prepared by using 350ml of deionized water, 20ml of ethanol, 10ml of citric acid aqueous solution (the concentration is 0.1 mol/ml) and 10ml of Tlris aqueous solution (the concentration is 0.1 mol/ml), stirring the dispersant solution by using a centrifugal stirrer at the rotating speed of 1000r/min, and controlling the pH value of the solution after the reaction is completely carried out to be 7-7.5;
2) Taking out 50ml of the mixed solution in the step 1), adding 100ml of deionized water for dilution, and stirring the diluted solution at the rotating speed of 600 r/min;
3) Carrying out spray drying on the solution obtained in the step 2) in a spraying device filled with nitrogen, and granulating to obtain powder; drying was carried out at an inlet temperature of 150 ℃ and an outlet temperature of 80 ℃.
4) Washing the powder obtained in the step 3) by using deionized water, filtering by using filter paper, and drying at 60 ℃; the cleaning is carried out for 4 hours under the ultrasonic frequency of 100 Hz.
5) Uniformly dispersing the powder obtained in the step 4) in a crucible, wherein the sintering route is to sinter the powder to 1300 ℃ at 10K/min, and then cooling to room temperature at 20K/min to obtain the alpha-phase alumina.
Claims (4)
1. A preparation method of a spherical alpha-alumina flame retardant is characterized by comprising the following steps:
preparing a dispersing agent from deionized water, absolute ethyl alcohol, citric acid and tris (hydroxymethyl) aminomethane, adding alkali and aluminate into the dispersing agent to form a mixed solution, and stirring the mixed solution until the mixed solution is in a microemulsion state, wherein the pH value is 7-7.5; the preparation proportion of each component in the dispersant is as follows: 35ml of deionized water, 2ml of absolute ethyl alcohol, 10ml of citric acid aqueous solution with the concentration of 0.1mol/ml and 10ml of tris (hydroxymethyl) aminomethane aqueous solution with the concentration of 0.1 mol/ml;
step two, adding deionized water into the mixed solution for dilution, and stirring the diluted solution;
step three, performing spray drying on the stirred diluted solution in spray drying equipment filled with nitrogen to obtain powder; the inlet temperature of spray drying is 150 ℃, and the outlet temperature is 80 ℃;
step four, washing the powder with deionized water, filtering, and drying; the cleaning is carried out for 2 hours at the ultrasonic frequency of 100 Hz;
and (V) sintering the dried powder in a muffle furnace at high temperature, wherein the sintering route is to heat up to 1200 ℃ at 10K/min, then preserving the heat at 1200 ℃ for 2 hours, and cooling to 500 ℃ at 10K/min to obtain a product without hydroxyl.
2. The method of claim 1, wherein: in the step (one), the stirring speed of the mixed solution is 1000r/min.
3. The method of claim 1, wherein: in the step (one), the alkali is ammonium bicarbonate, the aluminate is one of aluminum nitrate or aluminum chloride, and the molar ratio of the alkali to the aluminate is 1:4.
4. the method of claim 1, wherein: in the second step, the stirring speed of the diluted solution is 600r/min.
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Effective date of registration: 20230413 Address after: 408300 Chengxi group, Dianjiang Industrial Park, Chongqing Patentee after: CHONGQING RESEARCH BETTER SCIENCE & TECHNOLOGY Co.,Ltd. Address before: 300384 No. 391 Binshui West Road, Xiqing District, Tianjin Patentee before: TIANJIN University OF TECHNOLOGY |