CN109935757B - Preparation method of composite lithium ion battery diaphragm - Google Patents
Preparation method of composite lithium ion battery diaphragm Download PDFInfo
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Abstract
The invention relates to the field of lithium ion batteries, in particular to a preparation method of a composite lithium ion battery diaphragm, which comprises the following preparation steps: 1) dissolving cotton fiber and sodium alginate in a sodium hydroxide/urea mixed solution, adding a glutaraldehyde solution, and coating to prepare a hydrogel film; 2) extracting and drying by using supercritical carbon dioxide to obtain a gel film; 3) coating isobornyl methacrylate on the silica particles; 4) coating the silicon dioxide emulsion on the surface of the aerogel film; according to the invention, sodium alginate and cotton fiber are modified by glutaraldehyde to obtain the aerogel with high liquid absorption rate, strong lyophilic property and high strength, and the isobornyl methacrylate coated silica emulsion coating is carried out on the surface of the aerogel, so that when the temperature of the battery suddenly rises, a compact isobornyl methacrylate film layer can be formed on the surface of the aerogel to block holes on the surface of the aerogel, so that the lithium ion battery stops working, and the safety of the lithium ion battery is improved.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a preparation method of a composite lithium ion battery diaphragm.
Background
The lithium ion battery is a rechargeable and dischargeable type secondary battery, and is composed of a positive electrode, a negative electrode, a separator, and an electrolyte, where the separator is also called a "third electrode" of the lithium ion battery, and is an important component of the lithium ion battery. The lithium ion battery has the main functions of insulating short circuit caused by physical contact of the positive pole and the negative pole, and serving as an ion conductor, so that ions can freely shuttle between the positive pole and the negative pole through the diaphragm smoothly, and the process of inserting and extracting lithium ions between the positive pole and the negative pole is realized. Therefore, the quality of the separator material plays a decisive role in the basic electrical properties of the lithium-ion battery, the separator not only needs to have good insulation properties, but also has proper pore size and porosity, however, the polyolefin separator which is successfully commercialized at present is not high in mechanical properties, low in heat-resistant temperature, and easy to be heated and softened when the environmental temperature is too high or the battery current is too large in the use process of the battery, so that the short circuit of the lithium-ion battery is easily caused to cause explosion.
For example, an invention patent "a method for improving the surface activity of a separator of a polyethylene lithium battery" disclosed in chinese patent literature, which is publication No. CN104821382B, a method for improving the surface activity of a separator of a polyethylene lithium battery, comprises: dissolving the modified polyolefin material in white oil to obtain a white oil mixture containing the modified polyolefin material; feeding polyethylene powder and a white oil mixture containing modified polyolefin into a double-screw extruder, and obtaining an oil-containing cast sheet through metering, filtering, an extrusion die head and a cooling device; the oil-containing cast sheet is subjected to biaxial tension to obtain an oil-containing diaphragm; the oil-containing diaphragm enters an extraction tank, and white oil in the oil-containing diaphragm is extracted by using an extracting agent; drying the extracted diaphragm by hot air or hot rollers to obtain a dry diaphragm; the polyethylene is adopted as the material for preparing the diaphragm, and because the polyethylene has low use temperature, when the heat release of the lithium ion battery is large, the polyethylene diaphragm can be softened and loses the barrier effect, so that the battery is easy to short circuit and explode.
Disclosure of Invention
The invention provides a composite lithium ion battery diaphragm comprising an intermediate layer, an upper surface layer and a lower surface layer, which aims to overcome the problems, improve the mechanical strength of the diaphragm and endow the diaphragm with thermal break resistance.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the composite lithium ion battery diaphragm comprises the following preparation steps;
(1) dissolving cotton fiber and sodium alginate in mixed aqueous solution of 5-10wt% sodium hydroxide and 10-15wt% urea, and stirring at 20-30 deg.C for 5-10min to obtain mixed solution;
(2) adding 20-30wt% glutaraldehyde water solution into the mixed solution at 20-30 deg.C, coating, and reacting at 50-70 deg.C for 5-8 hr to obtain cotton fiber/sodium alginate hydrogel membrane;
(3) immersing the cotton fiber/sodium alginate hydrogel film into deionized water and acetone in sequence for washing, then placing the film into a high-pressure reaction kettle, introducing carbon dioxide until the pressure is 8.5-10Mpa, extracting at 30-50 ℃ for 10-15h, then slowly reducing the pressure in the kettle to atmospheric pressure, and then cooling to room temperature to obtain the cotton fiber/sodium alginate hydrogel film;
(4) dispersing the silicon dioxide particles in absolute ethyl alcohol, performing ultrasonic dispersion for 30-50min, then adding methacryloxypropyl trimethoxy silane, reacting for 12-18h, performing suction filtration, and drying at the temperature of 100-120 ℃ to obtain silane modified silicon dioxide particles;
(5) dispersing silane modified silica particles in deionized water, adding isobornyl methacrylate, then adding sodium dodecyl benzene sulfonate, sodium bicarbonate and ammonium persulfate, and heating to 60-80 ℃ to obtain silica emulsion coated with isobornyl methacrylate;
(6) and (3) coating the cotton fiber/sodium alginate aerogel film with the silicon dioxide emulsion coated with the isobornyl methacrylate on two sides, and drying at 50-70 ℃ for 4-8h to obtain the finished product of the composite lithium ion battery diaphragm.
The sodium alginate/cotton fiber aerogel is successfully prepared by dissolving sodium alginate and cotton fiber, performing sol-gel and glutaraldehyde crosslinking modification, and drying by supercritical carbon dioxide. In the dissolving of sodium alginate and cotton fiber, sodium hydroxide and urea solution weaken hydrogen bond in cotton fiber, destroy the crystalline structure of cotton fiber, open the free chain segment of cotton fiber, and carbonyl, amino and other polar groups in the solution form hydrogen bond with cotton fiber molecule to dissolve it, then, because sodium alginate and cotton fiber are rich in hydroxyl and carboxyl, after glutaraldehyde solution is added, sodium alginate and cotton fiber are cross-linked, condensed and agglomerated continuously under the action of glutaraldehyde to form cotton fiber/sodium alginate hydrogel membrane with network structure, then, deionized water and acetone are used to soak and remove residual molecules in gel, the dispersion medium in gel is replaced, carbon dioxide extraction is carried out on the dispersion medium, deionized water and acetone in hydrogel are replaced gradually to obtain cotton fiber/sodium alginate aerogel membrane, during carbon dioxide extraction, in order to enable carbon dioxide to reach a supercritical state and enable the carbon dioxide to have good fluidity and extraction performance, the flushing pressure of the carbon dioxide in a high-pressure reaction kettle must be higher than 8.5Mpa, the environmental temperature must be higher than 30 ℃, and the cotton fiber/sodium alginate aerogel film has high porosity and air permeability and is endowed with high strength after being modified by glutaraldehyde crosslinking.
And then, coating the upper and lower surfaces of the cotton fiber/sodium alginate aerogel film by using the silica emulsion coated with the isobornyl methacrylate, and forming a silica particle layer coated with the isobornyl methacrylate on the surface of the cotton fiber/sodium alginate aerogel film to prepare the composite lithium ion battery diaphragm. Because the glass transition temperature of the isobornyl methacrylate is about 110 ℃, when the temperature of the battery rises and exceeds the glass transition temperature of the isobornyl methacrylate, the isobornyl methacrylate coated on the silicon dioxide particles can be gradually softened and bonded, so that a layer of compact film is formed on the surface of the cotton fiber/sodium alginate aerogel film, holes in the surface of the aerogel film are blocked, lithium ions can not penetrate through a diaphragm for transmission, the lithium ion battery stops working, accidents such as explosion and the like caused by overhigh temperature of the battery are prevented, in addition, the thermal stability of the cotton fiber/sodium alginate aerogel film is also increased by adding the silicon dioxide particles, and the shrinkage of the cotton fiber/sodium alginate aerogel film when the cotton fiber/sodium alginate aerogel film is heated is effectively prevented.
Preferably, the mass ratio of the cotton fiber to the sodium alginate in the step (1) is 3-5: 1.
Preferably, the addition amount of the glutaraldehyde in the step (2) is 0.5-1.5% of the mass sum of the cotton fiber and the sodium alginate.
Preferably, the silica particles in step (4) have a particle size of 50 to 200 nm.
Preferably, the volume ratio of the absolute ethyl alcohol to the methacryloxypropyltrimethoxysilane in the step (4) is 100: 0.5-2.
Preferably, the preparation in the step (5) comprises the following components in parts by mass: 1-1.5 parts of silane modified silica particles, 100-150 parts of isobornyl methacrylate, 0.1-0.3 part of sodium dodecyl benzene sulfonate, 0.05-0.1 part of sodium bicarbonate and 1-1.5 parts of ammonium persulfate.
Preferably, the thickness of the cotton fiber/sodium alginate aerogel film in the step (3) is 15-25 μm.
Preferably, the coating thickness of the silica particles in the step (5) is 50 to 120 nm.
The particle size of silica particles and the coating thickness of silica particles are not too high or too low, if the particle size and the thickness are too low, the poly isobornyl methacrylate on the silica particles is not easy to form a compact film after being softened, so that the holes on the surface of the aerogel film can not be blocked, and the particle size and the thickness are too high, when the poly isobornyl methacrylate coated silica emulsion is coated on the surface of the aerogel film, the holes on the surface of the aerogel film can be blocked, so that the porosity of the aerogel film is influenced.
Preferably, the coating thickness of the polyisobornyl methacrylate-coated silica emulsion in the step (6) is 2 to 5 μm.
Therefore, the invention has the following beneficial effects: according to the invention, sodium alginate and cotton fiber are modified by glutaraldehyde to obtain the cotton fiber/sodium alginate aerogel with high liquid absorption rate, strong lyophilic property and high strength, and the isobornyl methacrylate coated silica emulsion coating is carried out on the surface of the aerogel, so that when the temperature of the battery suddenly rises, a compact isobornyl methacrylate film layer can be formed on the surface of the aerogel, the holes on the surface of the aerogel are blocked, the lithium ion battery stops working, and the safety of the lithium ion battery is improved.
Detailed Description
The present invention will be described more clearly and completely with reference to the following specific embodiments, which are obviously only a part of the embodiments of the present invention, but not all of them. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, belong to the scope of the present invention.
Example 1: the preparation method of the composite lithium ion battery diaphragm comprises the following preparation steps;
(1) dissolving 8g of cotton fiber and 1.6g of sodium alginate in 100ml of mixed aqueous solution of 10wt% of sodium hydroxide and 10wt% of urea, and stirring for 7min at 25 ℃ to obtain mixed solution;
(2) at the temperature of 20 ℃, adding 0.2g of 25 wt% glutaraldehyde aqueous solution into the mixed solution, coating, and reacting for 7 hours at the temperature of 60 ℃ to obtain a cotton fiber/sodium alginate hydrogel membrane;
(3) immersing the cotton fiber/sodium alginate hydrogel film into deionized water and acetone in sequence for washing, then placing the film into a high-pressure reaction kettle, introducing carbon dioxide to the pressure of 8.5Mpa, extracting at 50 ℃ for 10h, then slowly reducing the pressure in the kettle to atmospheric pressure, and then cooling to room temperature to obtain the cotton fiber/sodium alginate hydrogel film with the thickness of 15 mu m;
(4) dissolving 0.25g of silicon dioxide particles with the particle size of 100nm in 100ml of absolute ethyl alcohol, performing ultrasonic dispersion for 40min, then adding 1g of methacryloxypropyltrimethoxysilane, reacting for 16h, performing suction filtration, and drying at 110 ℃ to obtain silane modified silicon dioxide particles;
(5) dispersing silane modified silicon dioxide particles in 100ml of deionized water, adding 25g of isobornyl methacrylate, then adding 0.025g of sodium dodecyl benzene sulfonate, 0.0125g of sodium bicarbonate and 0.25g of ammonium persulfate, and heating to 60 ℃ to obtain isobornyl methacrylate coated silicon dioxide emulsion with the coating thickness of 100 nm;
(6) and (3) coating the cotton fiber/sodium alginate aerogel film with the silica emulsion coated with the isobornyl methacrylate on two sides, wherein the coating thickness is 2 microns, and drying for 6 hours at the temperature of 60 ℃ to obtain the finished product of the composite lithium ion battery diaphragm.
Example 2: the preparation method of the composite lithium ion battery diaphragm comprises the following preparation steps;
(1) dissolving 10g of cotton fiber and 3.4g of sodium alginate in 120ml of mixed aqueous solution of 5wt% of sodium hydroxide and 15wt% of urea, and stirring for 5min at 30 ℃ to obtain mixed solution;
(2) adding 0.67g of 30wt% glutaraldehyde aqueous solution into the mixed solution at 30 ℃, coating, and reacting for 8 hours at 50 ℃ to obtain a cotton fiber/sodium alginate hydrogel membrane;
(3) immersing the cotton fiber/sodium alginate hydrogel film into deionized water and acetone in sequence for washing, then placing the film into a high-pressure reaction kettle, introducing carbon dioxide to the pressure of 10Mpa, extracting at 30 ℃ for 15h, then slowly reducing the pressure in the kettle to atmospheric pressure, and then cooling to room temperature to obtain the cotton fiber/sodium alginate aerogel film with the thickness of 25 mu m;
(4) dissolving 0.25g of silicon dioxide particles with the particle size of 200nm in 100ml of absolute ethyl alcohol, performing ultrasonic dispersion for 50min, then adding 2g of methacryloxypropyl trimethoxy silane, reacting for 18h, performing suction filtration, and drying at 100 ℃ to obtain silane modified silicon dioxide particles;
(5) dispersing silane modified silica particles in 100ml of deionized water, adding 37.5g of isobornyl methacrylate, then adding 0.075g of sodium dodecyl benzene sulfonate, 0.025g of sodium bicarbonate and 0.075g of ammonium persulfate, and heating to 80 ℃ to obtain a silica emulsion coated with isobornyl methacrylate, wherein the coating thickness is 50 nm;
(6) and (3) coating the cotton fiber/sodium alginate aerogel film with the silica emulsion coated with the isobornyl methacrylate on two sides, wherein the coating thickness is 5 microns, and drying for 4 hours at 70 ℃ to obtain the finished product of the composite lithium ion battery diaphragm.
Example 3: the preparation method of the composite lithium ion battery diaphragm comprises the following preparation steps;
(1) dissolving 10g of cotton fiber and 5g of sodium alginate in 100ml of mixed aqueous solution of 8 wt% of sodium hydroxide and 12 wt% of urea, and stirring for 10min at 20 ℃ to obtain mixed solution;
(2) at 25 ℃, adding 0.75g of 20 wt% glutaraldehyde aqueous solution into the mixed solution, coating, and reacting for 5 hours at 70 ℃ to obtain a cotton fiber/sodium alginate hydrogel membrane;
(3) immersing the cotton fiber/sodium alginate hydrogel film into deionized water and acetone in sequence for washing, then placing the film into a high-pressure reaction kettle, introducing carbon dioxide to the pressure of 9Mpa, extracting at 40 ℃ for 13h, then slowly reducing the pressure in the kettle to atmospheric pressure, and then cooling to room temperature to obtain the cotton fiber/sodium alginate aerogel film with the thickness of 20 mu m;
(4) dissolving 0.25g of silicon dioxide particles with the particle size of 50nm in 100ml of absolute ethyl alcohol, performing ultrasonic dispersion for 30min, then adding 0.5g of methacryloxypropyl trimethoxy silane, reacting for 12h, performing suction filtration, and drying at 120 ℃ to obtain silane modified silicon dioxide particles;
(5) dispersing silane modified silicon dioxide particles in 100ml of deionized water, adding 30g of isobornyl methacrylate, then adding 0.05g of sodium dodecyl benzene sulfonate, 0.018g of sodium bicarbonate and 0.049g of ammonium persulfate, and heating to 70 ℃ to obtain a silicon dioxide emulsion coated with the isobornyl methacrylate, wherein the coating thickness is 120 nm;
(6) and (3) coating the cotton fiber/sodium alginate aerogel film with the silica emulsion coated with the isobornyl methacrylate on two sides, wherein the coating thickness is 3 microns, and drying for 8 hours at 50 ℃ to obtain the finished product of the composite lithium ion battery diaphragm.
Comparative example 1: the difference from example 1 is that no glutaraldehyde crosslinking modification was performed.
The compression strength of example 1 and comparative example 1 was tested and the results are given in the table below.
| Compressive strength (MPa) | |
| Example 1 | 5.89 |
| Comparative example 1 | 3.57 |
Self-crosslinking reaction can occur between the sodium alginate and the cotton fiber molecular chains, and the addition of glutaraldehyde can promote the further progress of the crosslinking reaction between the molecular chains, so that a more complex spatial network structure is formed, and higher compressive strength is given to the cotton fiber/sodium alginate aerogel film.
Comparative example 2 is different from example 1 in that the particle size of the silica particles used is about 300nm and the coating thickness of the silica particles is about 200 nm.
Comparative example 3 is different from example 1 in that the particle size of the silica particles used is about 30nm and the coating thickness of the silica particles is about 20 nm.
The porosity at different temperatures was measured for example 1 and comparative examples 2 and 3, and the results are shown in the following table.
The porosity is higher at 40 ℃ and lower at 150 ℃ in example 1, which shows that when the temperature is higher than the softening point of the isobornyl methacrylate, the film formed by softening the isobornyl methacrylate can better cover the holes of the cotton fiber/sodium alginate aerogel film, compared with example 1, the particle size of the silica particles in comparative example 2 is smaller, the coating thickness of the silica particles is thinner, the porosity at 40 ℃ and 150 ℃ is higher and has small difference, and when the temperature is higher than the softening point of the isobornyl methacrylate, the film formed by softening the isobornyl methacrylate cannot better cover the holes of the cotton fiber/sodium alginate aerogel film, so that the blocking effect cannot be better achieved; the silica particles of comparative example 3, which have a larger particle size and a smaller porosity at 40 c than the silica particles having a larger coating thickness, and the porosity of which also sharply decreases at 150 c, indicate that when the silica particles are larger and the silica particles have a larger coating thickness, the pores of the cotton fiber/sodium alginate aerogel film are covered at a temperature less than the softening point of polyisobornyl methacrylate.
Claims (9)
1. The preparation method of the composite lithium ion battery diaphragm is characterized by comprising the following preparation steps;
(1) dissolving cotton fiber and sodium alginate in mixed aqueous solution of 5-10wt% sodium hydroxide and 10-15wt% urea, and stirring at 20-30 deg.C for 5-10min to obtain mixed solution;
(2) adding 20-30wt% glutaraldehyde water solution into the mixed solution at 20-30 deg.C, coating, and reacting at 50-70 deg.C for 5-8 hr to obtain cotton fiber/sodium alginate hydrogel membrane;
(3) immersing the cotton fiber/sodium alginate hydrogel film into deionized water and acetone in sequence for washing, then placing the film into a high-pressure reaction kettle, introducing carbon dioxide until the pressure is 8.5-10Mpa, extracting at 30-50 ℃ for 10-15h, then slowly reducing the pressure in the kettle to atmospheric pressure, and then cooling to room temperature to obtain the cotton fiber/sodium alginate hydrogel film;
(4) dispersing the silicon dioxide particles in absolute ethyl alcohol, performing ultrasonic dispersion for 30-50min, then adding methacryloxypropyl trimethoxy silane, reacting for 12-18h, performing suction filtration, and drying at the temperature of 100-120 ℃ to obtain silane modified silicon dioxide particles;
(5) dispersing silane modified silica particles in deionized water, adding isobornyl methacrylate, then adding sodium dodecyl benzene sulfonate, sodium bicarbonate and ammonium persulfate, and heating to 60-80 ℃ to obtain silica emulsion coated with isobornyl methacrylate;
(6) and (3) coating the cotton fiber/sodium alginate aerogel film with the silicon dioxide emulsion coated with the isobornyl methacrylate on two sides, and drying at 50-70 ℃ for 4-8h to obtain the finished product of the composite lithium ion battery diaphragm.
2. The preparation method of the composite lithium ion battery separator according to claim 1, wherein the mass ratio of the cotton fiber to the sodium alginate in the step (1) is 3-5: 1.
3. The preparation method of the composite lithium ion battery separator according to claim 1, wherein the addition amount of the glutaraldehyde in the step (2) is 0.5% -1.5% of the sum of the mass of the cotton fiber and the mass of the sodium alginate.
4. The preparation method of the composite lithium ion battery separator according to claim 1, wherein the particle size of the silica particles in the step (4) is 50-200 nm.
5. The preparation method of the composite lithium ion battery separator according to claim 1, wherein the volume ratio of the absolute ethyl alcohol to the methacryloxypropyltrimethoxysilane in the step (4) is 100: 0.5-2.
6. The preparation method of the composite lithium ion battery separator according to claim 1, wherein the preparation in the step (5) comprises the following components in parts by mass: 1-1.5 parts of silane modified silica particles, 100-150 parts of isobornyl methacrylate, 0.1-0.3 part of sodium dodecyl benzene sulfonate, 0.05-0.1 part of sodium bicarbonate and 1-1.5 parts of ammonium persulfate.
7. The preparation method of the composite lithium ion battery separator according to claim 1, wherein the coating thickness of the silica particles in the step (5) is 50-120 nm.
8. The preparation method of the composite lithium ion battery separator according to any one of claims 1 to 7, wherein the thickness of the cotton fiber/sodium alginate aerogel film in the step (3) is 15 to 25 μm.
9. The preparation method of the composite lithium ion battery separator according to claim 8, wherein the coating thickness of the poly (isobornyl methacrylate) -coated silica emulsion in the step (6) is 2-5 μm.
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