CN107867711B - Production process of mesoporous and microporous graded alumina, production process of mesoporous alumina and application of mesoporous alumina - Google Patents
Production process of mesoporous and microporous graded alumina, production process of mesoporous alumina and application of mesoporous alumina 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
- C01F7/44—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water
- C01F7/441—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by calcination
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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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- 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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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/12—Surface area
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- C01P2006/14—Pore volume
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- C01P2006/16—Pore diameter
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/80—Compositional purity
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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
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a process for producing mesoporous and microporous graded alumina, which takes water-soluble pigment carbon black as a hard template agent, forms pigment carbon black/aluminum hydroxide composite gel by aluminum hydroxide and the water-soluble pigment carbon black, and forms mesoporous and microporous graded gamma-alumina after crystallization, dehydration and calcination to remove the hard template agent. The invention also discloses a production process of the mesoporous alpha-alumina and application of the mesoporous alpha-alumina in a lithium ion battery PET ceramic diaphragm.
Description
Technical Field
The invention relates to a production process of mesoporous and microporous graded gamma-alumina, a production process of mesoporous alpha-alumina and application of mesoporous alpha-alumina in a PET (polyethylene terephthalate) ceramic diaphragm of a lithium ion battery.
Background
The preparation method of the mesoporous alumina comprises a hydrothermal synthesis method, a sol-gel method, a soft template method, an ionic liquid method, a reverse microemulsion method and the like. The methods for preparing mesoporous alumina are mostly limited to basic research of material synthesis, and the industrial production of the mesoporous alumina is difficult due to factors such as high price of raw materials (such as organic templates, organic metal salts, organic solvents and the like) and complex process. There is a report in the literature that mesoporous alumina is prepared by using a hard template method, and a double mesoporous structure is prepared by using a single mesoporous carbon template through an organic-organic self-assembly mode. By designing the mesoporous structure of the synthetic carbon material, alumina is selectively loaded into the mesoporous structure by utilizing the ordered mesoporous structure and the surface function, and an alumina coating is formed on the inner surface of macropores with different thicknesses until the macropores are saturated, so that the mesoporous alumina with various void structures and adjustable mesoporous aperture within a certain range can be obtained. The hard template method has certain advantages compared with the alumina prepared by the soft template method. However, the reaction conditions are also high, the process control is difficult, particularly, alumina is difficult to polymerize well in the pore channels of the hard template, and meanwhile, the cost for synthesizing the hard template is also high, so that the industrialization is difficult to realize. In a word, the research on the field of mesoporous molecular sieves at home and abroad is limited to the basic research of material synthesis, the process is complex, the cost is high, and the difficulty in the industrial scale of the mesoporous alumina is caused.
Disclosure of Invention
The invention aims to provide a production process of mesoporous and microporous graded gamma-alumina.
The second purpose of the invention is to provide a production process of mesoporous alpha-alumina.
The third purpose of the invention is to provide the application of the mesoporous alpha-alumina in the PET ceramic diaphragm of the lithium ion battery.
In order to achieve the first object, the invention provides the following technical scheme:
a process for preparing the mesoporous and microporous graded alumina includes such steps as preparing the pigment carbon black/aluminium hydroxide composite gel from water-soluble carbon black as hard template, crystallizing, dewatering, calcining to remove hard template, and preparing the mesoporous and microporous graded gamma-alumina.
The process uses water-soluble pigment carbon black as a hard template agent, and utilizes the large specific surface area and the porous structure of the water-soluble pigment carbon black, the hydrophilic performance of hydrophilic groups on the surface of the water-soluble pigment carbon black and water to form carbon black hydrogel, then selectively loads aluminum hydroxide on the inner and outer surfaces of the mesopores and micropores of the carbon black hydrogel to form a layer of aluminum hydroxide coating, and then obtains the mesoporous and micropore graded gamma-alumina with adjustable pore diameter and various void structures through aging, crystallization and removal of the hard template agent.
Further, the process comprises the following steps:
1) mixing water-soluble pigment carbon black with water, and stirring to obtain pigment carbon black hydrogel;
2) adding aluminum hydroxide into the pigment carbon black hydrogel, and stirring to form pigment carbon black/aluminum hydroxide composite gel;
3) and (3) standing and aging the composite gel, removing the upper layer liquid, drying the water, crystallizing, dehydrating, calcining to remove the water-soluble pigment carbon black, and cooling to obtain the mesoporous and microporous graded gamma-alumina.
Further, the water-soluble pigment carbon black is a nano-scale pigment carbon black. Can be purchased commercially.
Further, the particle diameter of the water-soluble pigment carbon black is 8-40nm, and the specific surface area is 100-450m2(ii) in terms of/g. According to the particle size, specific surface area and pore size of the water-soluble pigment carbon black molecules, the aluminum oxide with certain pore size, specific surface area and pore volume can be designed and produced.
Further, in the process, the weight ratio of the water-soluble pigment carbon black, water and aluminum hydroxide is 30 parts: 130 parts of: 180 parts.
Further, the water content of the aluminum hydroxide was 36%.
Further, in step 1), stirring is carried out at room temperature, and the stirring speed is 1100-.
Further, in step 2), stirring is carried out at room temperature, and the stirring speed is 1100-.
Further, in the step 3), the composite gel is kept stand and aged for 12 hours, then the upper layer liquid is removed, the moisture is dried at the temperature of 80-90 ℃, the composite gel is crystallized and dehydrated for 2 hours at the temperature of 350 ℃, and the water-soluble pigment carbon black is removed by calcination at the temperature of 600 ℃.
In order to achieve the second object, the invention provides the following technical scheme:
the mesoporous alumina producing process includes further calcining the gamma-alumina obtained through the said production process to obtain mesoporous alpha-alumina.
Further, the calcination temperature is not lower than 1100 ℃.
The specific limitations of the preparation steps of mesoporous and microporous graded gamma-alumina are as described above and will not be described herein again.
In order to achieve the third object, the invention provides the following technical solutions:
application of mesoporous alpha-alumina obtained by utilizing production process in preparation of PET-alpha-Al2O3A ceramic diaphragm.
Further, the PET-alpha-Al2O3The ceramic diaphragm is obtained by uniformly mixing mesoporous alpha-alumina, PVDF and NMP, coating the mixture on a PET diaphragm and drying the mixture.
Furthermore, the weight ratio of the mesoporous alpha-alumina to the PVDF to the NMP is 3.03 parts to 0.28 part to 12.4 parts, which is a preferable formula.
Further, the coating film thickness was 300-600 μm.
Further, the coating film was dried at 90 ℃ after coating on a PET separator.
Further, the dry coating film thickness is 100-200 μm, and the coating film mass per unit area is 5-10mg/cm2。
The invention has the following advantages:
the production process of the invention is a hard template agent gel method, which absorbs the advantages of the hard template method and the sol-gel method, the hard template agent is water-soluble pigment carbon black, the aluminum source is inorganic aluminum hydroxide, the aluminum hydroxide in gel state is dispersed on the inner and outer surfaces of the pore channel of the pigment carbon black hydrogel hard template agent under the condition of high-speed stirring dispersion, the gamma-alumina with the medium and micro pore diameter hierarchical structure is obtained by aging, dehydration and removal of the hard template agent, and then the mesoporous alpha-alumina is obtained by further calcining at high temperature. The method has the advantages of simple process, easily obtained raw materials, low price and environmental protection, and can realize industrial production by adopting the streamline operation of the electric heating tunnel kiln.
The mesoporous alpha-alumina obtained by the invention can be used for preparing PET-alpha-Al for lithium ion batteries2O3A ceramic diaphragm.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Examples
Production of mesoporous alumina with high specific surface area
1300 liters of deionized water was pumped into a 3000 liter agitation reaction tank, and then 300kg of water-soluble pigment carbon black (particle diameter 20-40nm, specific surface area 207 m)2G, average pore diameter of 15.7nm and specific pore volume of 0.82cm3And/g) pumping the mixture into a reaction tank, stirring and dispersing the mixture at a high speed of 1100-2000 rpm for 1.5-2.0 hours, sampling the mixture from the reaction tank, and checking whether a sample forms pigment carbon black hydrogel.
After the pigment carbon black hydrogel is formed, 1800kg of aluminum hydroxide raw material with the water content of 36 percent is put into a reaction tank under low-speed stirring, and is sheared and stirred at high speed for 2 hours, and then a sample is sampled from the stirring reaction tank, and whether the pigment carbon black/aluminum hydroxide composite gel is formed in the sample is checked.
The resulting pigment carbon black/aluminum hydroxide composite gel was left to stand in a reaction tank for 12 hours, and the upper layer liquid was separated by a liquid pump and stored as a raw material for the next production batch.
Injecting pigment carbon black/aluminum hydroxide composite gel into a quartz sagger of an electric heating tunnel kiln in batches one by one, setting the temperature in the electric heating tunnel kiln to be about 90 ℃, drying for 2 hours, sending the quartz sagger filled with the composite gel into a low-temperature electric heating tunnel kiln by a transfer belt, crystallizing and dehydrating for 2 hours in a 300 ℃ tunnel kiln, sending the quartz sagger filled with a precursor after primary dehydration into a 600 ℃ tunnel kiln by the transfer belt, calcining for 6 hours to remove a template agent, and cooling to obtain mesoporous and microporous gamma-Al with nano and micron-sized particle diameters and graded apertures2O3White powder (particle size)<10 μm, specific surface area 150m2G, average pore diameter of 10.5nm and specific pore volume of 0.39cm3In terms of/g) and a yield of about 700 kg. The obtained meso-microporous gamma-Al2O3Calcining for 2 hours in a tunnel kiln at 1100 ℃, and cooling to obtain the mesoporous alpha-Al with nano and micron particle size2O3(particle diameter)<10 μm, specific surface area 50m2G, average pore diameter of 20nm and specific pore volume of 0.25cm3/g)。
The obtained gamma-Al with medium and micro pore grading2O3The performance indexes of (A) are as follows:
appearance: a white powder;
particle size: <10 μm;
purity: 99.99 percent;
compacting density: 0.5-0.7g/cm3；
Specific surface area: 100-300m2/g；
Specific pore volume: 0.25-0.48cm3/g；
Average pore diameter: 5-10 nm.
The obtained mesoporous alpha-Al2O3The performance indexes of (A) are as follows:
appearance: a white powder;
particle size: <10 μm;
purity: 99.99 percent;
compacting density: 0.56-0.75g/cm3；
Specific surface area: 50-100m2/g；
Specific pore volume: 0.25-0.50cm3/g；
Average pore diameter: 10-20 nm.
Second, lithium ion battery PET-alpha-Al2O3Preparation and performance of ceramic diaphragm
1.PET-α-Al2O3Ceramic diaphragm preparation process
2.745g of polyvinylidene fluoride (PVDF) as a binder were accurately weighed, dissolved in 120mL of N-methylpyrrolidone (NMP) solvent, and 30.302g of mesoporous alpha-Al was weighed2O3Adding into PVDF emulsion, stirring and mixing uniformly, coating the N-methyl pyrrolidone emulsion of alumina on a PET diaphragm uniformly by using a coater, wherein the coating thickness is about 300-600 mu m, and drying the coating at the temperature of 90 ℃ to obtain the PET-alpha-Al of the lithium ion battery2O3A ceramic diaphragm. The dry coating film thickness is 100-200 mu m, and the coating film mass per unit area is 5-10mg/cm2. The composite PET ceramic diaphragm can be widely applied to various types of lithiumThe ion battery has excellent performance.
2.PET-α-Al2O3Properties of ceramic diaphragm
PET-α-Al2O3The ceramic diaphragm has strong affinity to electrolyte solution and small ion permeation resistance. Through detection, compared with a pure PET diaphragm, the mass transfer impedance of ions in the electrolyte of the lithium ion battery is only increased by 1-2 ohms; the ceramic diaphragm can be repeatedly folded, and the aluminum oxide coating does not crack or fall powder; compared with a pure PET diaphragm, the puncture resistance of the ceramic diaphragm is improved by 3 times; the fusing temperature of the ceramic diaphragm is 151 ℃; the ceramic diaphragm is applied to a ternary material lithium ion battery, and the performance of the diaphragm still keeps stable after 1800 times of charging and discharging.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (9)
1. A production process of mesoporous and microporous graded alumina is characterized in that water-soluble pigment carbon black is used as a hard template agent, aluminum hydroxide and the water-soluble pigment carbon black form pigment carbon black/aluminum hydroxide composite gel, and then the mesoporous and microporous graded gamma-alumina is formed after crystallization, dehydration and calcination are carried out to remove the hard template agent; the method specifically comprises the following steps:
1) mixing water-soluble pigment carbon black with water, and stirring to obtain pigment carbon black hydrogel;
2) adding aluminum hydroxide into the pigment carbon black hydrogel, and stirring to form pigment carbon black/aluminum hydroxide composite gel;
3) and (3) standing and aging the composite gel, removing the upper layer liquid, drying the water, crystallizing, dehydrating, calcining to remove the water-soluble pigment carbon black, and cooling to obtain the mesoporous and microporous graded gamma-alumina.
2. The process for producing mesoporous and microporous graded alumina according to claim 1, wherein the water-soluble pigment carbon black is nanoscale pigment carbon black; the particle diameter of the water-soluble pigment carbon black is 8-40nm, and the specific surface area is 100-450m2/g。
3. The process for producing mesoporous and microporous graded alumina as claimed in claim 1, wherein the weight ratio of the water-soluble pigment carbon black, the water and the aluminum hydroxide is 30: 130: 180.
4. The process for preparing meso-or microporous graded alumina as claimed in claim 1, wherein the composite gel in step 3) is left to stand and age for 12 hours, then the supernatant liquid is removed, the moisture is dried at 80-90 ℃, the composite gel is crystallized and dehydrated for 2 hours at 350 ℃, and the water-soluble pigment carbon black is removed by calcination at 600 ℃.
5. A process for producing mesoporous alumina, characterized in that mesoporous and microporous graded gamma-alumina obtained by the production process according to any one of claims 1 to 4 is further calcined to obtain mesoporous alpha-alumina.
6. The process for producing mesoporous alumina as claimed in claim 5, wherein the calcination temperature is not lower than 1100 ℃.
7. Use of mesoporous alumina obtained by the process according to claim 5 or 6, for the preparation of PET- α -Al2O3A ceramic diaphragm.
8. Use according to claim 7, wherein the PET- α -Al is present2O3The ceramic diaphragm is obtained by uniformly mixing mesoporous alpha-alumina, PVDF and NMP, coating the mixture on a PET diaphragm and drying the mixture.
9. The use according to claim 8, wherein the weight ratio of the mesoporous α -alumina to the PVDF to the NMP is 3.03 parts: 0.28 part: 12.4 parts; the coating thickness is 300-600 μm; coating on a PET diaphragm, and drying the coating at 90 ℃; the dry coating film thickness is 100-200 mu m, and the coating film mass per unit area is 5-10mg/cm2。
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| CN109244315A (en) * | 2018-08-24 | 2019-01-18 | 中国电力科学研究院有限公司 | A kind of anodic aluminium oxide membrane preparation process based on mesoporous material |
| CN111019409A (en) * | 2019-12-20 | 2020-04-17 | 江苏厚生新能源科技有限公司 | High-wetting long-cycle alumina ceramic slurry, preparation method thereof and lithium battery diaphragm |
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| CN1044337C (en) * | 1993-11-23 | 1999-07-28 | 中国石油化工总公司 | Preparing method for aluminium oxide carrier with double-hole |
| CN102795648A (en) * | 2011-05-27 | 2012-11-28 | 中国科学院过程工程研究所 | Mesoporous hexaaluminate prepared by carbon template method and having large specific surface area and preparation method of hexaaluminate |
| CN103199209A (en) * | 2013-04-01 | 2013-07-10 | 中国海诚工程科技股份有限公司 | Non-woven ceramic membrane with excellent closed-pore performance for lithium ion battery and technology |
| CN106111214A (en) * | 2015-05-07 | 2016-11-16 | Ifp 新能源公司 | There is the spherical alumina granule of mechanical strength that count diameter in the macropore of 0.05 to 30 μm, that have improvement |
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| CN1044337C (en) * | 1993-11-23 | 1999-07-28 | 中国石油化工总公司 | Preparing method for aluminium oxide carrier with double-hole |
| CN102795648A (en) * | 2011-05-27 | 2012-11-28 | 中国科学院过程工程研究所 | Mesoporous hexaaluminate prepared by carbon template method and having large specific surface area and preparation method of hexaaluminate |
| CN103199209A (en) * | 2013-04-01 | 2013-07-10 | 中国海诚工程科技股份有限公司 | Non-woven ceramic membrane with excellent closed-pore performance for lithium ion battery and technology |
| CN106111214A (en) * | 2015-05-07 | 2016-11-16 | Ifp 新能源公司 | There is the spherical alumina granule of mechanical strength that count diameter in the macropore of 0.05 to 30 μm, that have improvement |
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| Jerzy Walendziewski等.Preparation of large pore alumina supports for hydrodesulfurization catalysts.《Applied Catalysis A》.1993,第163-174页. * |
| Preparation of large pore alumina supports for hydrodesulfurization catalysts;Jerzy Walendziewski等;《Applied Catalysis A》;19931231;第163-174页 * |
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