CN105098118A - Battery diaphragm employing polypropylene-compounded natural cellulose membrane as base material and preparation method of battery diaphragm - Google Patents
Battery diaphragm employing polypropylene-compounded natural cellulose membrane as base material and preparation method of battery diaphragm Download PDFInfo
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- CN105098118A CN105098118A CN201510406355.5A CN201510406355A CN105098118A CN 105098118 A CN105098118 A CN 105098118A CN 201510406355 A CN201510406355 A CN 201510406355A CN 105098118 A CN105098118 A CN 105098118A
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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
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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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
- H01M50/411—Organic material
- H01M50/429—Natural polymers
- H01M50/4295—Natural cotton, cellulose or wood
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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
- H01M50/44—Fibrous material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to the technical field of preparation of lithium ion battery diaphragms, and discloses a battery diaphragm employing a polypropylene-compounded natural cellulose membrane as a base material and a preparation method of the battery diaphragm. The diaphragm comprises a diaphragm base material and a coating, wherein the diaphragm base material is prepared from the following materials in parts by weight: 50-60 parts of natural cellulose pulp, 10-15 parts of keratin, 5-10 parts of ethylene glycol diglycidyl ether, 5-10 parts of a brown algae extract, 10-15 parts of polypropylene and 4-6 parts of vinyl acrylate; and the coating is formed by coating the surface of the diaphragm base material with coating slurry, and is prepared from the following materials in parts by weight: 1-5 parts of a nano inorganic filler, 3-5 parts of a binder, 20-30 parts of vinyl acrylate, 1-5 parts of mussel shell powder, 1-5 parts of halloysite nanotubes and 57-67 parts of an organic solvent. The diaphragm disclosed by the invention has relatively good high-temperature resistance, dimensional stability, tensile strength and anti-spine strength, and simultaneously has relatively high moisture absorption and liquid retention capacities and relatively good wettability on electrolyte.
Description
Technical field
The present invention relates to lithium ion battery separator preparing technical field, particularly relate to a kind of to be compounded with battery diaphragm that polyacrylic natural cellulose membrane is base material and preparation method thereof.
Background technology
Barrier film is very important part in lithium ion battery, and the Main Function of barrier film is that the both positive and negative polarity of battery is separated, and prevents both positive and negative polarity from contacting and short circuit.Barrier film certainly as non-conducting material, and has certain micropore and porosity, and electrolyte ion can be made to pass through.The performance of barrier film determines the interfacial structure, internal resistance etc. of battery, directly affects the capacity of battery, cycle performance, security performance etc.In prior art, lithium ion battery great majority select polyolefin porous membrane as its diaphragm material.
But, be that the barrier film of material is in thermal stability, to not ideal enough in the wetting property of electrolyte, moisture absorption liquid-keeping property with polyolefin.The wetting property of electrolyte and the deficiency of moisture absorption liquid-keeping property are limited to the high rate performance of lithium ion battery; And when internal temperature of lithium ion battery sharply rises, the easy melted by heating of polyalkene diaphragm, diaphragm size easily shrinks and directly causes battery short circuit.In order to address this problem, common solution can be coated with one deck ceramic size on the surface of barrier film, and ceramic size has higher heat-resisting quantity, substantially increases the dimensional stability of barrier film.But on the other hand, being arranged on of ceramic size plugs the micropore on barrier film originally to a certain extent, and reduce wettability and the gas permeability of barrier film to a certain extent, ceramic size generally adheres on barrier film basement membrane by adhesive in addition, cohesive force is strong not, easily comes off after long-time.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of to be compounded with battery diaphragm that polyacrylic natural cellulose membrane is base material and preparation method thereof.Barrier film of the present invention can be high temperature resistant, and hot strength is high, while can keeping dimensionally stable, also has stronger moisture absorption liquid-keeping property and to the good wettability of electrolyte after being heated; In addition barrier film of the present invention also has good anti-spine intensity.
Concrete technical scheme of the present invention is: a kind of to be compounded with the battery diaphragm that polyacrylic natural cellulose membrane is base material, comprise barrier film base material and the coating being located at described barrier film substrate surface, the material that described barrier film base material is 100 parts by following total weight parts is prepared from: the native cellulose slurry of 50-60 weight portion, the keratin of 10-15 weight portion, the ethylene glycol diglycidylether of 5-10 weight portion, the brown alga extract of 5-10 weight portion, the polypropylene of 10-15 weight portion, the vinyl acrylate of 4-6 weight portion; Described coating is coated barrier film substrate surface by coating paste and is formed, the material that described coating paste is 100 parts by following weight portion is prepared from: the nanometer inorganic filler of 1-5 weight portion, the binding agent of 3-5 weight portion, the vinyl acrylate of 20-30 weight portion, the mussel shell powder of 1-5 weight portion, the halloysite nanotubes of 1-5 weight portion, the organic solvent of 57-67 weight portion; Described nanometer inorganic filler be selected from nano aluminium oxide, nano-titanium oxide or nano zircite one or more.
Containing a large amount of native celluloses and a small amount of pectin in native cellulose slurry, native cellulose and pectin all have good moisture absorption, thermal stability, by itself and polypropylene composite materials, after carrying out film forming with paper technology, polypropylene moisture absorption can be made up, the defect that thermal stability is poor, but also there is certain defect in cellulose, be exactly that its wet strength is poor, the present invention is by using ethylene glycol diglycidylether, keratin and native cellulose are occurred crosslinked, native cellulose and keratin are cross-linked thick, its wet strength can be increased dramatically, in addition keratin and brown alga extract also have good moisture absorption simultaneously, the imbibition moisture-retaining capacity of barrier film can be improved further.Nanometer inorganic filler in coating paste can promote heat-resisting quantity and the mechanical strength of coating, mussel shell powder and halloysite nanotubes all have pore passage structure, the moisture absorption of coating can be improved, mechanical strength, additionally can also strengthen the fire resistance of coating simultaneously, vinyl acrylate in barrier film base material and coating paste is can self-initiation ultraviolet-curing material, when coating paste is coated on after on barrier film base material, the vinyl acrylate in the vinyl acrylate in coating paste and barrier film base material can be made after carrying out UV-irradiation rapidly curing cross-linked to occur, add the bonding of common bond, compared with single bonding agent, the adhesive fastness of coating is stronger, nanometer inorganic filler in coating, mussel shell powder and halloysite nanotubes difficult drop-off, and it is also more obvious to the lifting of barrier film substrate sizes stability.
As preferably, the preparation method of described native cellulose slurry is as follows:
(1) cotton of short staple of 100 weight portions and the bamboo slag of 100 weight portions is taken respectively, and described cotton of short staple to be added together with bamboo slag to 600 weight portion concentration be in the sodium hydroxide solution of 15wt%, boiling is vacuumized to the sodium hydroxide solution containing short velveteen and bamboo slag, boiling temperature is 220 DEG C, and digestion time is 4h.
(2) the short velveteen after boiling and bamboo slag are taken out and washed, short velveteen being joined together with bamboo slag 2000 weight portion concentration is in the ethanolic solution of 40wt%, then Microwave Treatment is carried out to ethanolic solution, wherein microwave frequency is 2450MHZ, microwave power is 800W, temperature is 150 DEG C, and the time is 45min; After Microwave Treatment, ethanolic solution is filtered, get solid-state filtrate.
Native cellulose is insoluble in water and organic solvent, carries out Microwave Treatment to the short velveteen after boiling and bamboo slag, and gets solid-state filtrate after filtering, and can remove lignin in short velveteen and bamboo slag, pectin class impurity, promotes the purity of native cellulose.
(3) adopt beater to pull an oar to it by after solid-state filtrate washing, after successively chlorination, alkalization, bleaching, removal of impurities, concentration being carried out to gains after making beating, obtain natural cellulose fiber slurry.
As preferably, the solid content of described natural cellulose fiber slurry is 75-85wt%.
As preferably, described keratic preparation method is as follows:
(1) get the degreasing drake feather of 500 weight portions, added in water to horizontal high voltage boiling of going forward side by side, wherein, temperature is 160 DEG C, and pressure is 1.8-2.0Mpa, and digestion time is 1h.Boiling carried out to degreasing drake feather, degreasing drake feather part can be made to be hydrolyzed, soften, be more conducive to follow-up lixiviate.
(2) water of 5000 weight portions is separately taken, Xiang Shuizhong successively adds neopelex, vulcanized sodium and urea, and be mixed with leaching liquor, in described leaching liquor, the concentration of neopelex is 0.1mol/L, the concentration of vulcanized sodium is the concentration 6mol/L of 1mol/L, urea.
(3) added in above-mentioned leaching liquor by the degreasing drake feather after above-mentioned boiling and carry out keratin extraction, wherein the temperature of leaching liquor is 90-95 DEG C, and extraction time is 12 hours;
(4) after keratin extracts, leaching liquor is filtered, filtered fluid is loaded in bag filter and seals, described bag filter is positioned in deionized water and dialyses, wherein, the volumetric usage of deionized water is 100 times of filtered fluid, and dialysis time is 24 hours, and every 8 hours change a deionized water, the specification of bag filter is the molecular cut off of 25000.Keratin carries out dialysing and can obtain the keratin of specified molecular weight scope, and this keratin like protein is conducive to the mechanical strength in promoting native cellulose.
(5), after dialysis, use Rotary Evaporators to carry out concentration to liquid in bag filter, after concentrate is the 10-15% of original volume, after vacuumize and pulverization process are carried out to concentrate, obtain keratin.
As preferably, the preparation method of described brown alga extract is as follows:
(1) take the brown alga of 100 weight portions, described brown alga is minced into brown alga particle, described brown alga particle is added in the boiling water of 2000 weight portions and carries out boiling 30 minutes;
(2) the brown alga particle after boiling is leached from water, and to be added to 50 weight portion concentration be in the sodium pyrophosphate solution of 5wt%, stir and obtain thick liquid after 45 minutes.
(3) be that the thick liquid of above-mentioned gained is neutralized to neutrality by the sodium hydroxide solution of 5wt% by concentration, finally vacuumize carried out to thick liquid, pulverize after obtained brown alga extract.
The brown alga extract adopting said method to obtain has the active ingredient of high level, good hygroscopicity, with better dispersed after polypropylene composite materials.
As preferably, described mussel shell powder and halloysite nanotubes are all through modification, and concrete grammar is as follows:
(1) take halloysite nanotubes or the mussel shell powder of 100 weight portions, being impregnated in 1000 weight portion concentration is that in the hydrochloric acid solution of 10wt%, acid treatment was taken out after 3 hours.
(2) be positioned in water-bath the halloysite nanotubes after acid treatment or mussel shell powder and carry out ultrasonic wave process, bath temperature is 40 DEG C, and the time is 30 minutes.
(3) halloysite nanotubes after ultrasonic wave process or mussel shell powder are carried out drying under vacuum, temperature is 50 DEG C, and the time is 3 hours; Then calcine halloysite nanotubes or mussel shell powder, calcining heat is 600-650 DEG C, and the time is 5 hours.
(4) halloysite nanotubes after calcining or mussel shell powder and silane coupler priority are distributed in toluene and carry out ultrasonic wave process 30 minutes, wherein the quality amount ratio of halloysite nanotubes or mussel shell powder and silane coupler, toluene is 50:(1-5): (450-550); Then toluene stirred and be heated to 70 DEG C, after 6 hours, taking out halloysite nanotubes or mussel shell powder, finally after washing, obtaining halloysite nanotubes or the mussel shell powder of modification.
Halloysite nanotubes or mussel shell powder are through said method modification, and eliminate the inner crystallization water, have better adsorption capacity, simultaneously through the modification of silane coupler, hydrophobic performance obtains enhancing, more easily adsorbs electrolyte organic solvent.
As preferably, the particle diameter of described mussel shell powder and halloysite nanotubes is 150-250 nanometer.
Above-mentioned with the preparation method being compounded with the battery diaphragm that polyacrylic natural cellulose membrane is base material, carry out as follows:
(1) each raw material of barrier film base material is taken respectively by proportioning, described keratin and ethylene glycol diglycidylether are successively added in native cellulose slurry, 1-2 hour is left standstill after stirring, and then described brown alga extract to be added in native cellulose slurry and to stir, obtain the first mixed slurry;
(2) polypropylene and vinyl acrylate are together added in above-mentioned the first obtained mixed slurry, stir in homogenizer after slurry is uniformly dispersed, take out and obtain the second mixed slurry;
(3) described second mixed slurry added water dilute, obtain dilution mixture slurry, the volume that wherein adds water be the 1000-5000 of the second mixed slurry volume doubly;
(4) after the dilution mixture slurry of above-mentioned gained successively being carried out online dehydration forming, squeezing, hot-roll forming according to paper technology, obtained barrier film base material;
(5) each raw material of coating paste is taken respectively by proportioning, by nanometer inorganic filler, binding agent, vinyl acrylate, mussel shell powder, halloysite nanotubes to add in organic solvent and after grinding evenly, obtained coating paste;
(6) above-mentioned obtained coating paste is heated to 50-60 DEG C, then the surface of above-mentioned obtained barrier film base material is coated, leave standstill after 15-20 minute, UV-irradiation 4-6 minute is carried out to the surface after the coating of barrier film base material, obtained to be compounded with the battery diaphragm that polyacrylic natural cellulose membrane is base material after finally drying.
As preferably, in hot rolling molding process, the temperature of hot-roll forming is 110-130 DEG C, and linear pressure is 120-140 kilogram every centimetre.
As preferably, the coating weight of described coating paste on barrier film base material is 4-6 gram every square metre.
Be compared with the prior art, the invention has the beneficial effects as follows: barrier film of the present invention has good heat-resisting quantity, hot strength, dimensional stability and anti-spine intensity, have good wettability to electrolyte simultaneously, the caking property of coating and barrier film base material is better, coating difficult drop-off.
Embodiment
Below in conjunction with embodiment, the invention will be further described.Raw materials used in the present invention, equipment, unless otherwise noted, is conventional raw material, the equipment of this area; Method therefor in the present invention, unless otherwise noted, is the conventional method of this area.
Embodiment 1
To be compounded with the battery diaphragm that polyacrylic natural cellulose membrane is base material, comprise barrier film base material and the coating being located at described barrier film substrate surface.Be wherein 38-42 micron every mould base material thickness, single coating thickness is 1.5-2.5 micron.
Described barrier film base material is prepared from by following material: the native cellulose slurry of 55 weight portions, the keratin of 12.5 weight portions, the ethylene glycol diglycidylether of 7.5 weight portions, the brown alga extract of 7.5 weight portions, the polypropylene of 12.5 weight portions, the vinyl acrylate of 5 weight portions.
Described coating is coated barrier film substrate surface by coating paste and is formed, described coating paste is prepared from by following material: the nano aluminium oxide of 1 weight portion, the nano-titanium oxide of 1 weight portion, the nano zircite of 1 weight portion, the Kynoar of 4 weight portions, the vinyl acrylate of 25 weight portions, the mussel shell powder of 3 weight portions, the halloysite nanotubes of 3 weight portions, the carbon tetrachloride of 62 weight portions.
To be compounded with the preparation method of the battery diaphragm that polyacrylic natural cellulose membrane is base material, carry out as follows:
(1) each raw material of barrier film base material is taken respectively by proportioning, described keratin and ethylene glycol diglycidylether are successively added in native cellulose slurry, 1.5 hours are left standstill after stirring, and then described brown alga extract to be added in native cellulose slurry and to stir, obtain the first mixed slurry.
(2) polypropylene and vinyl acrylate are together added in above-mentioned the first obtained mixed slurry, stir in homogenizer after slurry is uniformly dispersed, take out and obtain the second mixed slurry.
(3) add water to described second mixed slurry and dilute, obtain dilution mixture slurry, the volume that wherein adds water is 3000 times of the second mixed slurry volume.
(4) after the dilution mixture slurry of above-mentioned gained successively being carried out online dehydration forming, squeezing, hot-roll forming according to paper technology, obtained barrier film base material.Wherein the temperature of hot-roll forming is 120 DEG C, and linear pressure is 130 kilograms every centimetre.
(5) take each raw material of coating paste respectively by proportioning, by nanometer inorganic filler, binding agent, vinyl acrylate, mussel shell powder, halloysite nanotubes to add in organic solvent and after grinding evenly, obtained coating paste.
(6) above-mentioned obtained coating paste is heated to 55 DEG C, then coats the surface of above-mentioned obtained barrier film base material, the coating weight of coating paste is 5 grams every square metre.Leave standstill after 18 minutes, UV-irradiation is carried out 5 minutes to the surface after the coating of barrier film base material, obtained battery diaphragm after finally drying.
The preparation method of above-mentioned native cellulose slurry is as follows:
(1) cotton of short staple of 100 weight portions and the bamboo slag of 100 weight portions is taken respectively, and described cotton of short staple to be added together with bamboo slag to 600 weight portion concentration be in the sodium hydroxide solution of 15wt%, boiling is vacuumized to the sodium hydroxide solution containing short velveteen and bamboo slag, boiling temperature is 220 DEG C, and digestion time is 4h.
(2) the short velveteen after boiling and bamboo slag are taken out and washed, short velveteen being joined together with bamboo slag 2000 weight portion concentration is in the ethanolic solution of 40wt%, then Microwave Treatment is carried out to ethanolic solution, wherein microwave frequency is 2450MHZ, microwave power is 800W, temperature is 150 DEG C, and the time is 45min; After Microwave Treatment, ethanolic solution is filtered, get solid-state filtrate.
(3) adopt beater to pull an oar to it by after solid-state filtrate washing, after successively chlorination, alkalization, bleaching, removal of impurities, concentration being carried out to gains after making beating, obtain the natural cellulose fiber slurry that solid content is 80wt%.
Above-mentioned keratic preparation method is as follows:
(1) get the degreasing drake feather of 500 weight portions, added in water to horizontal high voltage boiling of going forward side by side, wherein, temperature is 160 DEG C, and pressure is 1.8-2.0Mpa, and digestion time is 1h.
(2) water of 5000 weight portions is separately taken, Xiang Shuizhong successively adds neopelex, vulcanized sodium and urea, and be mixed with leaching liquor, in described leaching liquor, the concentration of neopelex is 0.1mol/L, the concentration of vulcanized sodium is the concentration 6mol/L of 1mol/L, urea.
(3) added in above-mentioned leaching liquor by the degreasing drake feather after above-mentioned boiling and carry out keratin extraction, wherein the temperature of leaching liquor is 93 DEG C, and extraction time is 12 hours.
(4) after keratin extracts, leaching liquor is filtered, filtered fluid is loaded in bag filter and seals, described bag filter is positioned in deionized water and dialyses, wherein, the volumetric usage of deionized water is 100 times of filtered fluid, and dialysis time is 24 hours, and every 8 hours change a deionized water, the specification of bag filter is the molecular cut off of 25000.
(5), after dialysis, use Rotary Evaporators to carry out concentration to liquid in bag filter, when concentrate is after 13% of original volume, after vacuumize and pulverization process are carried out to concentrate, obtain keratin.
The preparation method of above-mentioned brown alga extract is as follows:
(1) take the brown alga of 100 weight portions, described brown alga is minced into brown alga particle, described brown alga particle is added in the boiling water of 2000 weight portions and carries out boiling 30 minutes.
(2) the brown alga particle after boiling is leached from water, and to be added to 50 weight portion concentration be in the sodium pyrophosphate solution of 5wt%, stir and obtain thick liquid after 45 minutes.
(3) be that the thick liquid of above-mentioned gained is neutralized to neutrality by the sodium hydroxide solution of 5wt% by concentration, finally vacuumize carried out to thick liquid, pulverize after obtained brown alga extract.
Above-mentioned mussel shell powder and halloysite nanotubes are all through modification, and concrete grammar is as follows:
(1) take halloysite nanotubes or the mussel shell powder of 100 weight portions, the particle diameter of described mussel shell powder and halloysite nanotubes is 150-250 nanometer.Mussel shell powder and halloysite nanotubes being impregnated in 1000 weight portion concentration is that in the hydrochloric acid solution of 10wt%, acid treatment was taken out after 3 hours.
(2) be positioned in water-bath the halloysite nanotubes after acid treatment or mussel shell powder and carry out ultrasonic wave process, bath temperature is 40 DEG C, and the time is 30 minutes.
(3) halloysite nanotubes after ultrasonic wave process or mussel shell powder are carried out drying under vacuum, temperature is 50 DEG C, and the time is 3 hours; Then calcine halloysite nanotubes or mussel shell powder, calcining heat is 625 DEG C, and the time is 5 hours.
(4) halloysite nanotubes after calcining or mussel shell powder and silane coupler priority are distributed in toluene and carry out ultrasonic wave process 30 minutes, wherein the quality amount ratio of halloysite nanotubes or mussel shell powder and silane coupler, toluene is 50:3:500; Then toluene stirred and be heated to 70 DEG C, after 6 hours, taking out halloysite nanotubes or mussel shell powder, finally after washing, obtaining halloysite nanotubes or the mussel shell powder of modification.
Embodiment 2
To be compounded with the battery diaphragm that polyacrylic natural cellulose membrane is base material, comprise barrier film base material and the coating being located at described barrier film substrate surface.Be wherein 30-35 micron every mould base material thickness, single coating thickness is 1-2 micron.
Described barrier film base material is prepared from by following material: the native cellulose slurry of 54 weight portions, the keratin of 10 weight portions, the ethylene glycol diglycidylether of 5 weight portions, the brown alga extract of 10 weight portions, the polypropylene of 15 weight portions, the vinyl acrylate of 6 weight portions.
Described coating is coated barrier film substrate surface by coating paste and is formed, described coating paste is prepared from by following material: the nano aluminium oxide of 1 weight portion, the Kynoar of 3 weight portions, the vinyl acrylate of 30 weight portions, the mussel shell powder of 4 weight portions, the halloysite nanotubes of 5 weight portions, the carbon tetrachloride of 57 weight portions.
To be compounded with the preparation method of the battery diaphragm that polyacrylic natural cellulose membrane is base material, carry out as follows:
(1) each raw material of barrier film base material is taken respectively by proportioning, described keratin and ethylene glycol diglycidylether are successively added in native cellulose slurry, 1 hour is left standstill after stirring, and then described brown alga extract to be added in native cellulose slurry and to stir, obtain the first mixed slurry.
(2) polypropylene and vinyl acrylate are together added in above-mentioned the first obtained mixed slurry, stir in homogenizer after slurry is uniformly dispersed, take out and obtain the second mixed slurry.
(3) add water to described second mixed slurry and dilute, obtain dilution mixture slurry, the volume that wherein adds water is 1000 times of the second mixed slurry volume.
(4) after the dilution mixture slurry of above-mentioned gained successively being carried out online dehydration forming, squeezing, hot-roll forming according to paper technology, obtained barrier film base material.Wherein the temperature of hot-roll forming is 110 DEG C, and linear pressure is 120 kilograms every centimetre.
(5) take each raw material of coating paste respectively by proportioning, by nanometer inorganic filler, binding agent, vinyl acrylate, mussel shell powder, halloysite nanotubes to add in organic solvent and after grinding evenly, obtained coating paste.
(6) above-mentioned obtained coating paste is heated to 50 DEG C, then coats the surface of above-mentioned obtained barrier film base material, the coating weight of coating paste is 4 grams every square metre.Leave standstill after 15 minutes, UV-irradiation is carried out 4 minutes to the surface after the coating of barrier film base material, obtained battery diaphragm after finally drying.
The preparation method of above-mentioned native cellulose slurry is as follows:
(1) cotton of short staple of 100 weight portions and the bamboo slag of 100 weight portions is taken respectively, and described cotton of short staple to be added together with bamboo slag to 600 weight portion concentration be in the sodium hydroxide solution of 15wt%, boiling is vacuumized to the sodium hydroxide solution containing short velveteen and bamboo slag, boiling temperature is 220 DEG C, and digestion time is 4h.
(2) the short velveteen after boiling and bamboo slag are taken out and washed, short velveteen being joined together with bamboo slag 2000 weight portion concentration is in the ethanolic solution of 40wt%, then Microwave Treatment is carried out to ethanolic solution, wherein microwave frequency is 2450MHZ, microwave power is 800W, temperature is 150 DEG C, and the time is 45min; After Microwave Treatment, ethanolic solution is filtered, get solid-state filtrate.
(3) adopt beater to pull an oar to it by after solid-state filtrate washing, after successively chlorination, alkalization, bleaching, removal of impurities, concentration being carried out to gains after making beating, obtain the natural cellulose fiber slurry that solid content is 75-85wt%.
Above-mentioned keratic preparation method is as follows:
(1) get the degreasing drake feather of 500 weight portions, added in water to horizontal high voltage boiling of going forward side by side, wherein, temperature is 160 DEG C, and pressure is 1.8-2.0Mpa, and digestion time is 1h.
(2) water of 5000 weight portions is separately taken, Xiang Shuizhong successively adds neopelex, vulcanized sodium and urea, and be mixed with leaching liquor, in described leaching liquor, the concentration of neopelex is 0.1mol/L, the concentration of vulcanized sodium is the concentration 6mol/L of 1mol/L, urea.
(3) added in above-mentioned leaching liquor by the degreasing drake feather after above-mentioned boiling and carry out keratin extraction, wherein the temperature of leaching liquor is 90 DEG C, and extraction time is 12 hours.
(4) after keratin extracts, leaching liquor is filtered, filtered fluid is loaded in bag filter and seals, described bag filter is positioned in deionized water and dialyses, wherein, the volumetric usage of deionized water is 100 times of filtered fluid, and dialysis time is 24 hours, and every 8 hours change a deionized water, the specification of bag filter is the molecular cut off of 25000.
(5), after dialysis, use Rotary Evaporators to carry out concentration to liquid in bag filter, when concentrate is after 10% of original volume, after vacuumize and pulverization process are carried out to concentrate, obtain keratin.
The preparation method of above-mentioned brown alga extract is as follows:
(1) take the brown alga of 100 weight portions, described brown alga is minced into brown alga particle, described brown alga particle is added in the boiling water of 2000 weight portions and carries out boiling 30 minutes.
(2) the brown alga particle after boiling is leached from water, and to be added to 50 weight portion concentration be in the sodium pyrophosphate solution of 5wt%, stir and obtain thick liquid after 45 minutes.
(3) be that the thick liquid of above-mentioned gained is neutralized to neutrality by the sodium hydroxide solution of 5wt% by concentration, finally vacuumize carried out to thick liquid, pulverize after obtained brown alga extract.
Above-mentioned mussel shell powder and halloysite nanotubes are all through modification, and concrete grammar is as follows:
(1) take halloysite nanotubes or the mussel shell powder of 100 weight portions, the particle diameter of described mussel shell powder and halloysite nanotubes is 150-250 nanometer.Mussel shell powder and halloysite nanotubes being impregnated in 1000 weight portion concentration is that in the hydrochloric acid solution of 10wt%, acid treatment was taken out after 3 hours.
(2) be positioned in water-bath the halloysite nanotubes after acid treatment or mussel shell powder and carry out ultrasonic wave process, bath temperature is 40 DEG C, and the time is 30 minutes.
(3) halloysite nanotubes after ultrasonic wave process or mussel shell powder are carried out drying under vacuum, temperature is 50 DEG C, and the time is 3 hours; Then calcine halloysite nanotubes or mussel shell powder, calcining heat is 600 DEG C, and the time is 5 hours.
(4) halloysite nanotubes after calcining or mussel shell powder and silane coupler priority are distributed in toluene and carry out ultrasonic wave process 30 minutes, wherein the quality amount ratio of halloysite nanotubes or mussel shell powder and silane coupler, toluene is 50:1:450; Then toluene stirred and be heated to 70 DEG C, after 6 hours, taking out halloysite nanotubes or mussel shell powder, finally after washing, obtaining halloysite nanotubes or the mussel shell powder of modification.
Embodiment 3
To be compounded with the battery diaphragm that polyacrylic natural cellulose membrane is base material, comprise barrier film base material and the coating being located at described barrier film substrate surface.Be wherein 45-50 micron every mould base material thickness, single coating thickness is 2-3 micron.
Described barrier film base material is prepared from by following material: the native cellulose slurry of 56 weight portions, the keratin of 15 weight portions, the ethylene glycol diglycidylether of 10 weight portions, the brown alga extract of 5 weight portions, the polypropylene of 10 weight portions, the vinyl acrylate of 4 weight portions.
Described coating is coated barrier film substrate surface by coating paste and is formed, described coating paste is prepared from by following material: the nano aluminium oxide of 2 weight portions, the nano-titanium oxide of 3 weight portions, the Kynoar of 5 weight portions, the vinyl acrylate of 20 weight portions, the mussel shell powder of 1 weight portion, the halloysite nanotubes of 2 weight portions, the carbon tetrachloride of 67 weight portions.
To be compounded with the preparation method of the battery diaphragm that polyacrylic natural cellulose membrane is base material, carry out as follows:
(1) each raw material of barrier film base material is taken respectively by proportioning, described keratin and ethylene glycol diglycidylether are successively added in native cellulose slurry, 2 hours are left standstill after stirring, and then described brown alga extract to be added in native cellulose slurry and to stir, obtain the first mixed slurry.
(2) polypropylene and vinyl acrylate are together added in above-mentioned the first obtained mixed slurry, stir in homogenizer after slurry is uniformly dispersed, take out and obtain the second mixed slurry.
(3) add water to described second mixed slurry and dilute, obtain dilution mixture slurry, the volume that wherein adds water is 5000 times of the second mixed slurry volume.
(4) after the dilution mixture slurry of above-mentioned gained successively being carried out online dehydration forming, squeezing, hot-roll forming according to paper technology, obtained barrier film base material.Wherein the temperature of hot-roll forming is 130 DEG C, and linear pressure is 140 kilograms every centimetre.
(5) take each raw material of coating paste respectively by proportioning, by nanometer inorganic filler, binding agent, vinyl acrylate, mussel shell powder, halloysite nanotubes to add in organic solvent and after grinding evenly, obtained coating paste.
(6) above-mentioned obtained coating paste is heated to 60 DEG C, then coats the surface of above-mentioned obtained barrier film base material, the coating weight of coating paste is 6 grams every square metre.Leave standstill after 20 minutes, UV-irradiation is carried out 6 minutes to the surface after the coating of barrier film base material, obtained battery diaphragm after finally drying.
The preparation method of above-mentioned native cellulose slurry is as follows:
(1) cotton of short staple of 100 weight portions and the bamboo slag of 100 weight portions is taken respectively, and described cotton of short staple to be added together with bamboo slag to 600 weight portion concentration be in the sodium hydroxide solution of 15wt%, boiling is vacuumized to the sodium hydroxide solution containing short velveteen and bamboo slag, boiling temperature is 220 DEG C, and digestion time is 4h.
(2) the short velveteen after boiling and bamboo slag are taken out and washed, short velveteen being joined together with bamboo slag 2000 weight portion concentration is in the ethanolic solution of 40wt%, then Microwave Treatment is carried out to ethanolic solution, wherein microwave frequency is 2450MHZ, microwave power is 800W, temperature is 150 DEG C, and the time is 45min; After Microwave Treatment, ethanolic solution is filtered, get solid-state filtrate.
(3) adopt beater to pull an oar to it by after solid-state filtrate washing, after successively chlorination, alkalization, bleaching, removal of impurities, concentration being carried out to gains after making beating, obtain the natural cellulose fiber slurry that solid content is 85wt%.
Above-mentioned keratic preparation method is as follows:
(1) get the degreasing drake feather of 500 weight portions, added in water to horizontal high voltage boiling of going forward side by side, wherein, temperature is 160 DEG C, and pressure is 1.8-2.0Mpa, and digestion time is 1h.
(2) water of 5000 weight portions is separately taken, Xiang Shuizhong successively adds neopelex, vulcanized sodium and urea, and be mixed with leaching liquor, in described leaching liquor, the concentration of neopelex is 0.1mol/L, the concentration of vulcanized sodium is the concentration 6mol/L of 1mol/L, urea.
(3) added in above-mentioned leaching liquor by the degreasing drake feather after above-mentioned boiling and carry out keratin extraction, wherein the temperature of leaching liquor is 95 DEG C, and extraction time is 12 hours.
(4) after keratin extracts, leaching liquor is filtered, filtered fluid is loaded in bag filter and seals, described bag filter is positioned in deionized water and dialyses, wherein, the volumetric usage of deionized water is 100 times of filtered fluid, and dialysis time is 24 hours, and every 8 hours change a deionized water, the specification of bag filter is the molecular cut off of 25000.
(5), after dialysis, use Rotary Evaporators to carry out concentration to liquid in bag filter, when concentrate is after 15% of original volume, after vacuumize and pulverization process are carried out to concentrate, obtain keratin.
The preparation method of above-mentioned brown alga extract is as follows:
(1) take the brown alga of 100 weight portions, described brown alga is minced into brown alga particle, described brown alga particle is added in the boiling water of 2000 weight portions and carries out boiling 30 minutes.
(2) the brown alga particle after boiling is leached from water, and to be added to 50 weight portion concentration be in the sodium pyrophosphate solution of 5wt%, stir and obtain thick liquid after 45 minutes.
(3) be that the thick liquid of above-mentioned gained is neutralized to neutrality by the sodium hydroxide solution of 5wt% by concentration, finally vacuumize carried out to thick liquid, pulverize after obtained brown alga extract.
Above-mentioned mussel shell powder and halloysite nanotubes are all through modification, and concrete grammar is as follows:
(1) take halloysite nanotubes or the mussel shell powder of 100 weight portions, the particle diameter of described mussel shell powder and halloysite nanotubes is 150-250 nanometer.Mussel shell powder and halloysite nanotubes being impregnated in 1000 weight portion concentration is that in the hydrochloric acid solution of 10wt%, acid treatment was taken out after 3 hours.
(2) be positioned in water-bath the halloysite nanotubes after acid treatment or mussel shell powder and carry out ultrasonic wave process, bath temperature is 40 DEG C, and the time is 30 minutes.
(3) halloysite nanotubes after ultrasonic wave process or mussel shell powder are carried out drying under vacuum, temperature is 50 DEG C, and the time is 3 hours; Then calcine halloysite nanotubes or mussel shell powder, calcining heat is 650 DEG C, and the time is 5 hours.
(4) halloysite nanotubes after calcining or mussel shell powder and silane coupler priority are distributed in toluene and carry out ultrasonic wave process 30 minutes, wherein the quality amount ratio of halloysite nanotubes or mussel shell powder and silane coupler, toluene is 50:5:550; Then toluene stirred and be heated to 70 DEG C, after 6 hours, taking out halloysite nanotubes or mussel shell powder, finally after washing, obtaining halloysite nanotubes or the mussel shell powder of modification.
The barrier film obtained to above embodiment carries out properties test, and result is as follows:
| Group | Porosity/% | Electrolyte absorptivity/% | Hot strength/MPa | Percent thermal shrinkage/% |
| Embodiment 1 | 58 | 460 | 49 | 0 |
| Embodiment 2 | 66 | 340 | 41 | 1 |
| Embodiment 3 | 53 | 410 | 53 | 0 |
Wherein the method for testing of porosity, electrolyte absorptivity, hot strength, percent thermal shrinkage is the general standard method of test of the industry.
The above; it is only preferred embodiment of the present invention; not the present invention is imposed any restrictions, every above embodiment is done according to the technology of the present invention essence any simple modification, change and equivalent transformation, all still belong to the protection range of technical solution of the present invention.
Claims (10)
1. one kind to be compounded with the battery diaphragm that polyacrylic natural cellulose membrane is base material, comprise barrier film base material and the coating being located at described barrier film substrate surface, it is characterized in that: the material that described barrier film base material is 100 parts by following total weight parts is prepared from: the native cellulose slurry of 50-60 weight portion, the keratin of 10-15 weight portion, the ethylene glycol diglycidylether of 5-10 weight portion, the brown alga extract of 5-10 weight portion, the polypropylene of 10-15 weight portion, the vinyl acrylate of 4-6 weight portion; Described coating is coated barrier film substrate surface by coating paste and is formed, the material that described coating paste is 100 parts by following weight portion is prepared from: the nanometer inorganic filler of 1-5 weight portion, the binding agent of 3-5 weight portion, the vinyl acrylate of 20-30 weight portion, the mussel shell powder of 1-5 weight portion, the halloysite nanotubes of 1-5 weight portion, the organic solvent of 57-67 weight portion; Described nanometer inorganic filler be selected from nano aluminium oxide, nano-titanium oxide or nano zircite one or more.
2. as claimed in claim 1 to be compounded with the battery diaphragm that polyacrylic natural cellulose membrane is base material, it is characterized in that, the preparation method of described native cellulose slurry is as follows:
(1) cotton of short staple of 100 weight portions and the bamboo slag of 100 weight portions is taken respectively, and described cotton of short staple to be added together with bamboo slag to 600 weight portion concentration be in the sodium hydroxide solution of 15wt%, boiling is vacuumized to the sodium hydroxide solution containing short velveteen and bamboo slag, boiling temperature is 220 DEG C, and digestion time is 4h;
(2) the short velveteen after boiling and bamboo slag are taken out and washed, short velveteen being joined together with bamboo slag 2000 weight portion concentration is in the ethanolic solution of 40wt%, then Microwave Treatment is carried out to ethanolic solution, wherein microwave frequency is 2450MHZ, microwave power is 800W, temperature is 150 DEG C, and the time is 45min; After Microwave Treatment, ethanolic solution is filtered, get solid-state filtrate;
(3) adopt beater to pull an oar to it by after solid-state filtrate washing, after successively chlorination, alkalization, bleaching, removal of impurities, concentration being carried out to gains after making beating, obtain natural cellulose fiber slurry.
3. as claimed in claim 2 to be compounded with the battery diaphragm that polyacrylic natural cellulose membrane is base material, it is characterized in that, the solid content of described natural cellulose fiber slurry is 75-85wt%.
4. as claimed in claim 1 to be compounded with the battery diaphragm that polyacrylic natural cellulose membrane is base material, it is characterized in that, described keratic preparation method is as follows:
(1) get the degreasing drake feather of 500 weight portions, added in water to horizontal high voltage boiling of going forward side by side, wherein, temperature is 160 DEG C, and pressure is 1.8-2.0Mpa, and digestion time is 1h;
(2) water of 5000 weight portions is separately taken, Xiang Shuizhong successively adds neopelex, vulcanized sodium and urea, and be mixed with leaching liquor, in described leaching liquor, the concentration of neopelex is 0.1mol/L, the concentration of vulcanized sodium is the concentration 6mol/L of 1mol/L, urea;
(3) added in above-mentioned leaching liquor by the degreasing drake feather after above-mentioned boiling and carry out keratin extraction, wherein the temperature of leaching liquor is 90-95 DEG C, and extraction time is 12 hours;
(4) after keratin extracts, leaching liquor is filtered, filtered fluid is loaded in bag filter and seals, described bag filter is positioned in deionized water and dialyses, wherein, the volumetric usage of deionized water is 100 times of filtered fluid, and dialysis time is 24 hours, and every 8 hours change a deionized water, the specification of bag filter is the molecular cut off of 25000;
(5), after dialysis, use Rotary Evaporators to carry out concentration to liquid in bag filter, after concentrate is the 10-15% of original volume, after vacuumize and pulverization process are carried out to concentrate, obtain keratin.
5. as claimed in claim 1 to be compounded with the battery diaphragm that polyacrylic natural cellulose membrane is base material, it is characterized in that, the preparation method of described brown alga extract is as follows:
(1) take the brown alga of 100 weight portions, described brown alga is minced into brown alga particle, described brown alga particle is added in the boiling water of 2000 weight portions and carries out boiling 30 minutes;
(2) the brown alga particle after boiling is leached from water, and to be added to 50 weight portion concentration be in the sodium pyrophosphate solution of 5wt%, stir and obtain thick liquid after 45 minutes;
(3) be that the thick liquid of above-mentioned gained is neutralized to neutrality by the sodium hydroxide solution of 5wt% by concentration, finally vacuumize carried out to thick liquid, pulverize after obtained brown alga extract.
6. as claimed in claim 1 to be compounded with the battery diaphragm that polyacrylic natural cellulose membrane is base material, it is characterized in that, described mussel shell powder and halloysite nanotubes are all through modification, and concrete grammar is as follows:
(1) take halloysite nanotubes or the mussel shell powder of 100 weight portions, being impregnated in 1000 weight portion concentration is that in the hydrochloric acid solution of 10wt%, acid treatment was taken out after 3 hours;
(2) be positioned in water-bath the halloysite nanotubes after acid treatment or mussel shell powder and carry out ultrasonic wave process, bath temperature is 40 DEG C, and the time is 30 minutes;
(3) halloysite nanotubes after ultrasonic wave process or mussel shell powder are carried out drying under vacuum, temperature is 50 DEG C, and the time is 3 hours; Then calcine halloysite nanotubes or mussel shell powder, calcining heat is 600-650 DEG C, and the time is 5 hours;
(4) halloysite nanotubes after calcining or mussel shell powder and silane coupler priority are distributed in toluene and carry out ultrasonic wave process 30 minutes, wherein the quality amount ratio of halloysite nanotubes or mussel shell powder and silane coupler, toluene is 50:(1-5): (450-550); Then toluene stirred and be heated to 70 DEG C, after 6 hours, taking out halloysite nanotubes or mussel shell powder, finally after washing, obtaining halloysite nanotubes or the mussel shell powder of modification.
7. as claimed in claim 6 to be compounded with the battery diaphragm that polyacrylic natural cellulose membrane is base material, it is characterized in that, the particle diameter of described mussel shell powder and halloysite nanotubes is 150-250 nanometer.
8. the preparation method to be compounded with the battery diaphragm that polyacrylic natural cellulose membrane is base material as described in one of claim 1-7, is characterized in that carrying out as follows:
(1) each raw material of barrier film base material is taken respectively by proportioning, described keratin and ethylene glycol diglycidylether are successively added in native cellulose slurry, 1-2 hour is left standstill after stirring, and then described brown alga extract to be added in native cellulose slurry and to stir, obtain the first mixed slurry;
(2) polypropylene and vinyl acrylate are together added in above-mentioned the first obtained mixed slurry, stir in homogenizer after slurry is uniformly dispersed, take out and obtain the second mixed slurry;
(3) described second mixed slurry added water dilute, obtain dilution mixture slurry, the volume that wherein adds water be the 1000-5000 of the second mixed slurry volume doubly;
(4) after the dilution mixture slurry of above-mentioned gained successively being carried out online dehydration forming, squeezing, hot-roll forming according to paper technology, obtained barrier film base material;
(5) each raw material of coating paste is taken respectively by proportioning, by nanometer inorganic filler, binding agent, vinyl acrylate, mussel shell powder, halloysite nanotubes to add in organic solvent and after grinding evenly, obtained coating paste;
(6) above-mentioned obtained coating paste is heated to 50-60 DEG C, then the surface of above-mentioned obtained barrier film base material is coated, leave standstill after 15-20 minute, UV-irradiation 4-6 minute is carried out to the surface after the coating of barrier film base material, obtained to be compounded with the battery diaphragm that polyacrylic natural cellulose membrane is base material after finally drying.
9. as claimed in claim 8 to be compounded with the preparation method of the battery diaphragm that polyacrylic natural cellulose membrane is base material, it is characterized in that, in hot rolling molding process, the temperature of hot-roll forming is 110-130 DEG C, and linear pressure is 120-140 kilogram every centimetre.
10. as claimed in claim 8 to be compounded with the preparation method of the battery diaphragm that polyacrylic natural cellulose membrane is base material, it is characterized in that, the coating weight of described coating paste on barrier film base material is 4-6 gram every square metre.
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