CN104022244A - Zinc-silver primary battery composite diaphragm with liquid-absorbing layer and functional layer, and preparation method thereof - Google Patents
Zinc-silver primary battery composite diaphragm with liquid-absorbing layer and functional layer, and preparation method thereof Download PDFInfo
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- CN104022244A CN104022244A CN201410213667.XA CN201410213667A CN104022244A CN 104022244 A CN104022244 A CN 104022244A CN 201410213667 A CN201410213667 A CN 201410213667A CN 104022244 A CN104022244 A CN 104022244A
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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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the field of preparation of zinc-silver battery diaphragms, and particularly relates to a zinc-silver primary battery composite diaphragm with a liquid-absorbing layer and a functional layer, and a preparation method thereof. The composite diaphragm is composed of a zinc and silver resistant porous fibrous membrane liquid-absorbing layer and a functional layer adhered thereon; the porous fibrous membrane guarantees zinc and silver resistance and liquid-absorbing property of the diaphragm; the functional layer endows the diaphragm with high silver resistance, a certain oxidation resistance and alkali corrosion resistance; and inorganic particles in the functional layer have the effects of regulating the aperture size of the diaphragm. The preparation method comprises the steps of mixing the inorganic particles, a binding agent and an additive to obtain a coating slurry; preparing a coating on the surface of a thin porous fibrous membrane; obtaining the functional layer through processes of drying and the like; then adhering the functional layer and the porous fibrous layer to obtain the primary zinc-silver battery diaphragm. The composite diaphragm combines the liquid-absorbing layer and the functional layer organically, replaces a main diaphragm and an assistant diaphragm in a conventional battery, increases battery assembly efficiency, has the advantages of simple membrane preparation process, low cost and excellent comprehensive performance, and can be produced in a large scale easily.
Description
Technical field
The present invention relates to zinc-silver oxide cell barrier film preparation field, particularly a kind of zinc-silver primary cell composite diaphragm with liquid-adsorption layer and functional layer and preparation method thereof.
Background technology
The history that is developed so far existing more than 50 year of zinc-silver oxide cell, because it has the unrivaled advantage of other kind batteries, be widely used on guided missile, rocket, torpedo, on the military equipment such as satellite, for the systems such as power, instrument, steering wheel, computer, control, remote measurement, safety provide electric power, aspect civilian, telephotography, news photography, walkie-talkie, portable communications machine etc. are also widely used, and button zinc-silver primary cell can be applicable to electronic watch, hearing aids and cardiac pacemaker etc.
Zinc-silver cell is made up of several of pole plate group, shell monomer, monomer lid, pole, vent plugs etc., and pole plate group comprises positive plate, negative plate and barrier film three parts, and the performance of whole battery is determined by above-mentioned three kinds of materials.Barrier film has isolation positive and negative electrode, and the effect of ion diffusion admittance is provided, and for a zinc-silver oxide cell, the performance of barrier film directly affects rate of activation and the hygrometric state life-span of battery.
Taking the materials such as cellulose, modified cellulose, the modified polyvinylalcohol resistance good as the barrier film of main body has silver performance, low resistance and higher-strength, be current zinc-silver once, the material of secondary battery membrane extensive use.But, for primary cell barrier film, the absorbency deficiency of above-mentioned material, assembling also needs to install additional auxiliary barrier film when battery helps main barrier film Electolyte-absorptive and completes the requirement of battery quick active, for battery assembling makes troubles, and because main barrier film is dense film, could transmit preferably ion after only having abundant Electolyte-absorptive swelling, cause the internal resistance of cell larger, affect the discharge performance of primary cell.In order to solve the problems referred to above of battery diaphragm, improve absorbency and the hygrometric state life-span of primary cell barrier film simultaneously, researcher has carried out a large amount of explorations.Some researchers do not use main barrier film, only assemble battery with crimped paper as barrier film, although absorbency can reach requirement, the hygrometric state life-span of battery is but difficult to ensure.An effective method and main barrier film and auxiliary barrier film are organically integrated into one, this barrier film is unsymmetric structure, comprise liquid-adsorption layer and functional layer, the imbibition effect of the original auxiliary barrier film of liquid-adsorption layer performance, the resistance silver of the original main barrier film of functional layer performance waits barrier film effect.Meanwhile, functional layer comprises inorganic particulate, both can stop silver migration, can limit again dendritic growth, meets the requirement of zinc-silver primary cell.
Summary of the invention
The object of the present invention is to provide a kind of zinc-silver primary cell composite diaphragm with liquid-adsorption layer and functional layer and preparation method thereof, this barrier film includes liquid-adsorption layer and functional layer, the advantages such as the battery diaphragm of preparing by the method has that electrolyte rate of liquid aspiration is fast, alkali corrosion resistance, oxidative resistance are strong, can significantly improve charge-discharge performance and the useful life of zinc-silver primary cell, meet the strict demand of high-performance zinc-silver primary cell to barrier film.
Technical scheme of the present invention is:
A kind of zinc-silver primary cell composite diaphragm with liquid-adsorption layer and functional layer, composite diaphragm is by the porous fibre of resistance to zinc-silver liquid-adsorption layer and be attached to its surperficial functional layer and form, functional layer comprises porous counterdie and inorganic coating, by the film slurry that contains inorganic particulate through coating process, dry after, on porous counterdie, form inorganic coating, obtain functional layer, by adhesion technique, liquid-adsorption layer and functional layer are combined;
Described porous fibre liquid-adsorption layer or porous counterdie are nonwoven fabrics or the paper-like materials that absorbency, oxidative resistance and resistance to zinc-silver are higher, the ceramic-like materials that described inorganic particulate is oxidative resistance, resistance to zinc-silver is high.
The described zinc-silver primary cell composite diaphragm with liquid-adsorption layer and functional layer, nonwoven fabrics is polyolefin nonwoven fabrics or the polyester non-woven fabric of cellulosic nonwoven fabric, cellulose acetate nonwoven fabrics, polyvinyl alcohol nonwoven fabrics, hydrophilic treated, and paper-like materials is the porous paper structural material with high liquid-absorbing: crimped paper, porous cotton paper or ceramic fiber paper.
The described zinc-silver primary cell composite diaphragm with liquid-adsorption layer and functional layer, the film slurry that contains inorganic particulate is made up of the raw material of following mass parts: 500～10000 mass parts solvents, 10～300 mass parts adhesives, 15～2400 mass parts inorganic particulates, 20～300 mass parts additives; Wherein,
Solvent is one or more arbitrary proportion mixtures of toluene, acetone, dimethyl formamide, 1-METHYLPYRROLIDONE, N-METHYLFORMAMIDE, carrene, chloroform;
Adhesive is one or more arbitrary proportion mixtures in polyvinyl alcohol, cellulose acetate, methyl hydroxyethylcellulose, ethylhydroxyethylcellulose, methylhydroxypropylcellulose, Kynoar-hexafluoropropylene copolymer, polymethyl methacrylate solution or SBR emulsion, the sticking high-molecular organic material of tool;
Inorganic particulate is one or more arbitrary proportion mixtures in micropore, mesopore or macropore class zeolite particles, alundum (Al2O3), silicon dioxide, zirconia, titanium oxide, magnesium oxide, inorganic particulate is Powdered, particle diameter is evenly distributed, and scope is 0.02 μ m～10.0 μ m;
Additive is one or more arbitrary proportion mixtures of water, methyl alcohol, ethanol, isopropyl alcohol, cyclohexane, oxolane.
The solid content of described film slurry is 5wt%～60wt%, wherein the mass ratio 10:1～1:8 of inorganic particulate, adhesive.
Described adhesion technique is the technique that materials at two layers is bonded into one, and comprising: hot-rolling pressure viscosity close or applying glue bonding.
The described porous fibre of resistance to zinc-silver liquid-adsorption layer thickness is 20 μ m～500 μ m, and porosity is 30%～95%, and average pore size is 0.1 μ m～1000 μ m.
Described porous counterdie thickness is 5 μ m～100 μ m, and porosity is 20%～90%, and average pore size is 0.02 μ m～50 μ m.
The preparation method of the described zinc-silver primary cell composite diaphragm with liquid-adsorption layer and functional layer, comprise inoganic particle modified, prepare film slurry, preparation functional layer, adhesive function layer and liquid-adsorption layer; Wherein,
Described is inoganic particle modified for carrying out surface treatment through silane coupler, and silane coupler is one or more arbitrary proportion mixtures of vinyl silanes, amino silane, methacryloxypropyl silane, 3-aminopropyl triethoxysilane, vinyltrimethoxy silane;
The described film slurry of preparing, mixes solvent, adhesive, inorganic particulate and additive, and the hybrid mode of slurry adopts one or more cooperations in mechanical agitation, ball grinding stirring and ultrasound treatment patterns;
Described preparation functional layer process using spray embrane method, scrape one or more in embrane method, the tape casting, rolling method and share, at porous counterdie surface-coated inorganic coating.
Described preparation functional layer also comprises hydrophilic treatment process, adopts the alkali lye of 5wt%～50wt% in 25 DEG C～90 DEG C processing capacity layer 0.5h～10h.
Advantage of the present invention and beneficial effect are:
1, the defect based on traditional zinc-silver primary cell barrier film, the present invention proposes following idea: by integral to main tradition barrier film and auxiliary barrier film organic combination, form new types of diaphragm by porous liquid sucting fiber layer and micropore functional layer, the absorbency that makes full use of stationery, fiber-like material keeps the high rate of liquid aspiration of barrier film.Meanwhile, utilize micropore functional layer to regulate and control the resistance silver of whole composite membrane, obtain all good composite diaphragms of absorbent, mechanical performance and electric property, the method can comprehensively improve rate of activation and wet the shelf-lifeing of zinc-silver oxide cell.
2, the zinc-silver primary cell barrier film that uses technique of the present invention to prepare has the features such as production technology is simple, with low cost, excellent combination property, can realize large-scale industrial production.
In a word, composite diaphragm of the present invention comprises porous liquid-adsorption layer and adheres to its surperficial functional layer.Liquid-adsorption layer ensures that composite diaphragm has the rate of liquid aspiration of original auxiliary barrier film, and functional layer is given oxidative resistance and the alkali corrosion resistance that composite diaphragm is strong.Meanwhile, the inorganic particulate in functional layer also has the effect of regulation and control composite diaphragm aperture size.Inorganic particulate is mixed with adhesive and additive etc. and obtain film slurry, be coated on porous counterdie surface, the techniques such as drying obtain functional layer, then by this functional layer and the bonding acquisition new types of diaphragm of liquid-adsorption layer with fiber or stationery structure.The present invention is by main tradition barrier film and auxiliary barrier film organic composite, make a kind of film combine the advantage of two kinds of barrier films, overcome the shortcoming of traditional zinc-silver primary cell barrier film, have that filming technology is simple, cost is low, the features such as barrier film combination property is superior, easily extensive large scale is produced.
Embodiment
The present invention has the zinc-silver primary cell composite diaphragm of liquid-adsorption layer and functional layer, composite diaphragm is by the porous fibre of resistance to zinc-silver liquid-adsorption layer and be attached to its surperficial functional layer and form, functional layer comprises porous counterdie and inorganic coating, by the film slurry that contains inorganic particulate through coating process, dry after, on porous counterdie, form inorganic coating, obtain functional layer, by adhesion technique, liquid-adsorption layer and functional layer are combined; Described porous fibre liquid-adsorption layer or porous counterdie are nonwoven fabrics or the paper-like materials that absorbency, oxidative resistance and resistance to zinc-silver are higher, the ceramic-like materials that described inorganic particulate is oxidative resistance, resistance to zinc-silver is high.
Described porous fibre liquid-adsorption layer or the material of porous counterdie comprise: the nonwoven fabrics such as polyolefin, polyester of cellulosic nonwoven fabric, cellulose acetate nonwoven fabrics, polyvinyl alcohol nonwoven fabrics, hydrophilic treated, and crimped paper, porous cotton paper, ceramic fiber paper etc. have the porous paper structural material of high liquid-absorbing.
The described film slurry that contains inorganic particulate is made up of the raw material of following mass parts: 500～10000 mass parts solvents, 10～300 mass parts adhesives, 15～2400 mass parts inorganic particulates, 20～300 mass parts additives.The solvent of described film slurry is one or more arbitrary proportion mixtures of toluene, acetone, dimethyl formamide, 1-METHYLPYRROLIDONE, N-METHYLFORMAMIDE, carrene, chloroform; The adhesive of described film slurry is one or more arbitrary proportion mixtures in polyvinyl alcohol, cellulose acetate, methyl hydroxyethylcellulose, ethylhydroxyethylcellulose, methylhydroxypropylcellulose, Kynoar-hexafluoropropylene copolymer, polymethyl methacrylate solution or SBR emulsion, the sticking high-molecular organic material of tool; The inorganic particulate of described film slurry is one or more arbitrary proportion mixtures in micropore, mesopore or macropore class zeolite particles, alundum (Al2O3), silicon dioxide, zirconia, titanium oxide, magnesium oxide, inorganic particulate is Powdered, particle diameter is evenly distributed, and scope is 0.02 μ m～10.0 μ m; The additive of described film slurry is one or more arbitrary proportion mixtures of water, methyl alcohol, ethanol, isopropyl alcohol, cyclohexane, oxolane.
Described adhesion technique comprises: the technique that hot-rolling pressure viscosity is closed, applying glue is bonding etc. can be bonded into one materials at two layers.The solid content of described film slurry is 5wt%～60wt%, wherein the mass ratio 10:1～1:8 of inorganic particulate, adhesive.The described porous fibre of resistance to zinc-silver liquid-adsorption layer thickness is 20 μ m～500 μ m, and porosity is 30%～95%, and average pore size is 0.1 μ m～1000 μ m.Described porous counterdie thickness is 5 μ m～100 μ m, and porosity is 20%～90%, and average pore size is 0.02 μ m～50 μ m.
The preparation method of the described zinc-silver primary cell composite diaphragm with liquid-adsorption layer and functional layer, comprise liquid-adsorption layer modification, inoganic particle modified, prepare film slurry, process such as preparation functional layer, adhesive function layer and liquid-adsorption layer etc.Described is inoganic particle modified for carrying out surface treatment through silane coupler, and silane coupler comprises one or more arbitrary proportion mixtures of vinyl silanes, amino silane, methacryloxypropyl silane, 3-aminopropyl triethoxysilane, vinyltrimethoxy silane.The described film slurry of preparing, mixes solvent, adhesive, inorganic particulate and additive, and the hybrid mode of slurry adopts one or more cooperations in mechanical agitation, ball grinding stirring and ultrasound treatment patterns.Described preparation functional layer process using spray embrane method, scrape one or more in embrane method, the tape casting, rolling method and share, at porous counterdie surface-coated inorganic coating.Described preparation functional layer also comprises hydrophilic treatment process, adopts 25 DEG C～90 DEG C processing capacity layer 0.5h～10h of 5%～50% alkali lye.
In the present invention, except specializing, the percentage relating to is mass percent.
Below by embodiment, the present invention is described in further detail.
Embodiment 1
Configuration quality mark is 1.5% 3-aminopropyl triethoxysilane aqueous solution 100ml.(granularity 0.5 μ m) adds in above-mentioned solution 10g Zirconia particles, 90 DEG C of stirring in water bath 6h.After centrifugal after washing 4 times, the dry modified inorganic particle that obtains.0.3g cellulose acetate, 1.5g Zirconia particles, 0.5g water are joined in 50g acetone, and ultrasonic dissolution, until obtain uniform film slurry.
Taking polyvinyl alcohol nonwoven fabrics, (thickness 30 μ are m) as counterdie, and by infusion process, in its surface preparation coating, drying at room temperature 4h is placed on dry 6h in 80 DEG C of baking ovens, obtains functional layer.
By above-mentioned functions layer in the KOH of 10wt% solution at 60 DEG C alkali treatment 2h, be washed to neutral post-drying and obtain functional layer after modification.
Taking 1wt% poly-vinyl alcohol solution as adhesive, by above-mentioned modified function layer and cellulose acetate nonwoven fabrics, (thickness 70 μ m) are bonded into one, 100 DEG C of dry zinc-silver primary cell composite diaphragms that obtain.
Above-mentioned composite diaphragm is tested.
Thickness measuring result: composite diaphragm thickness is 105 μ m.
Absorbency test result: the rate of liquid aspiration of room temperature lower diaphragm plate in the KOH of 30wt% solution is that 45mm/5min pick up is about 320%.
Hot strength test result: horizontal, longitudinal tensile strength is all greater than 35N/mm
2.
Embodiment 2
Configuration quality mark is 5% vinyltrimethoxy silane aqueous solution 100ml.(granularity 1.0 μ m) add in above-mentioned solution 25g MFI zeolite particles, 90 DEG C of stirring in water bath 6h.After centrifugal washing 2 times, the dry modified inorganic particle that obtains.1.0g methyl hydroxyethylcellulose, 4.5gMFI zeolite particles, 0.4g ethanol are joined in 50g acetone, and ultrasonic dissolution, until obtain uniform film slurry.
Taking polyethylene nonwoven fabrics, (thickness 30 μ are m) as counterdie, and by rolling method, in its surface preparation coating, drying at room temperature 6h is placed on dry 4h in 80 DEG C of baking ovens, obtains functional layer.
By above-mentioned functions layer in the KOH of 25wt% solution at 50 DEG C alkali treatment 2h, be washed to neutral post-drying and obtain functional layer after modification.
Taking 2.5wt% cellulose acetate solution as adhesive, by above-mentioned modified function layer and cellulosic nonwoven fabric, (thickness 80 μ m) are bonded into one, 100 DEG C of dry zinc-silver primary cell composite diaphragms that obtain.
Above-mentioned composite diaphragm is tested.
Thickness measuring result: composite diaphragm thickness is 130 μ m.
Absorbency test result: the rate of liquid aspiration of room temperature lower diaphragm plate in the KOH of 30wt% solution is that 50mm/5min pick up is about 350%.
Hot strength test result: horizontal, longitudinal tensile strength is all greater than 40N/mm
2.
Embodiment 3
Configuration quality mark is 3.8% methacryloxypropyl silane aqueous solution 100ml.30g Al
2o
3(granularity 0.5 μ m) adds in above-mentioned solution particle, 90 DEG C of stirring in water bath 5h.After centrifugal washing 4 times, the dry modified inorganic particle that obtains.By 1.0g ethylhydroxyethylcellulose, 4.0g Al
2o
3particle, 1.5g methyl alcohol join in 50g acetone, and ultrasonic dissolution, until obtain uniform film slurry.
Taking polyethylene nonwoven fabrics, (thickness 35 μ are m) as counterdie, and by spraying process, in its surface preparation coating, drying at room temperature 6h is placed on dry 4h in 80 DEG C of baking ovens, obtains functional layer.
By above-mentioned functions layer in the KOH of 35wt% solution with 60 DEG C at alkali treatment 1h, be washed to neutral post-drying and obtain functional layer after modification.
The polystyrene microsphere of 1.5wt% is sprayed on to functional layer surface, and (thickness 100 μ m) are superimposed at 120 DEG C and are thermal bonding to one by roll squeezer, obtain zinc-silver primary cell composite diaphragm with porous cotton paper.
Above-mentioned composite diaphragm is tested.
Thickness measuring result: composite diaphragm thickness is 120 μ m.
Absorbency test result: the rate of liquid aspiration of room temperature lower diaphragm plate in the NaOH of 30wt% solution is that 40mm/5min pick up is about 300%.
Hot strength test result: horizontal, longitudinal tensile strength is all greater than 35N/mm
2.
Embodiment 4
Configuration quality mark is 2.5% 3-aminopropyl triethoxysilane aqueous solution 100ml.25g ZrO
2(granularity 0.05 μ m) adds in above-mentioned solution particle, 90 DEG C of stirring in water bath 5h.After centrifugal washing 4 times, the dry modified inorganic particle that obtains.By 2.0g Kynoar-hexafluoropropylene, 8.0g ZrO
2particle, 0.5g water join in 50g acetone, and ultrasonic dissolution, until obtain uniform film slurry.
Taking polyvinyl alcohol nonwoven fabrics, (thickness 35 μ are m) as counterdie, and by infusion process, in its surface preparation coating, drying at room temperature 6h is placed on dry 4h in 80 DEG C of baking ovens, obtains functional layer.
By above-mentioned functions layer in the KOH of 15wt% solution with 50 DEG C at alkali treatment 3h, be washed to neutral post-drying and obtain functional layer after modification.
Be adhesive by the poly-vinyl alcohol solution of 2.0wt%, by above-mentioned modified function layer and cellulosic nonwoven fabric, (thickness 80 μ m) are bonded into one, 100 DEG C of dry zinc-silver primary cell composite diaphragms that obtain.
Above-mentioned composite diaphragm is tested.
Thickness measuring result: composite diaphragm thickness is 112 μ m.
Absorbency test result: the rate of liquid aspiration of room temperature lower diaphragm plate in the KOH of 30wt% solution is that 55mm/5min pick up is about 360%.
Hot strength test result: horizontal, longitudinal tensile strength is all greater than 35N/mm
2.
Embodiment 5
Configuration quality mark is 4.0% 3-aminopropyl triethoxysilane aqueous solution 100ml.50g TiO
2(granularity 0.2 μ m) adds in above-mentioned solution particle, 90 DEG C of stirring in water bath 5h.After centrifugal washing 4 times, the dry modified inorganic particle that obtains.By 2.0g Kynoar-hexafluoropropylene, 8.0g TiO
2particle, 1.0g cyclohexane join in 50g acetone, and ultrasonic dissolution, until obtain uniform film slurry.
Taking polyamide nonwoven fabrics, (thickness 50 μ are m) as counterdie, and by scraping embrane method in its surface preparation coating, drying at room temperature 6h is placed on dry 4h in 100 DEG C of baking ovens, obtains functional layer.
By above-mentioned functions layer in the KOH of 45wt% solution with 40 DEG C at alkali treatment 1h, be washed to neutral post-drying and obtain functional layer after modification.
Be adhesive by the cellulose acetate acetone soln of 5wt%, by above-mentioned modified function layer and ceramic fiber paper, (thickness 250 μ m) are bonded into one, 100 DEG C of dry zinc-silver primary cell composite diaphragms that obtain.
Above-mentioned composite diaphragm is tested.
Thickness measuring result: composite diaphragm thickness is 280 μ m.
Absorbency test result: the rate of liquid aspiration of room temperature lower diaphragm plate in the KOH of 30wt% solution is that 32mm/5min pick up is about 450%.
Hot strength test result: horizontal, longitudinal tensile strength is all greater than 60N/mm
2.
Embodiment result shows, zinc-silver primary cell composite diaphragm with liquid-adsorption layer and functional layer provided by the invention and preparation method thereof, make a kind of film combine the advantage of two kinds of barrier films, overcome the shortcoming of traditional zinc-silver primary cell barrier film, have that filming technology is simple, cost is low, the features such as barrier film combination property is superior, easily extensive large scale is produced.
Claims (9)
1. one kind has the zinc-silver primary cell composite diaphragm of liquid-adsorption layer and functional layer, it is characterized in that, composite diaphragm is by the porous fibre of resistance to zinc-silver liquid-adsorption layer and be attached to its surperficial functional layer and form, functional layer comprises porous counterdie and inorganic coating, by the film slurry that contains inorganic particulate through coating process, dry after, on porous counterdie, form inorganic coating, obtain functional layer, by adhesion technique, liquid-adsorption layer and functional layer are combined;
Described porous fibre liquid-adsorption layer or porous counterdie are nonwoven fabrics or the paper-like materials that absorbency, oxidative resistance and resistance to zinc-silver are higher, the ceramic-like materials that described inorganic particulate is oxidative resistance, resistance to zinc-silver is high.
2. the zinc-silver primary cell composite diaphragm with liquid-adsorption layer and functional layer according to claim 1, it is characterized in that, nonwoven fabrics is polyolefin nonwoven fabrics or the polyester non-woven fabric of cellulosic nonwoven fabric, cellulose acetate nonwoven fabrics, polyvinyl alcohol nonwoven fabrics, hydrophilic treated, and paper-like materials is the porous paper structural material with high liquid-absorbing: crimped paper, porous cotton paper or ceramic fiber paper.
3. the zinc-silver primary cell composite diaphragm with liquid-adsorption layer and functional layer according to claim 1, it is characterized in that, the film slurry that contains inorganic particulate is made up of the raw material of following mass parts: 500～10000 mass parts solvents, 10～300 mass parts adhesives, 15～2400 mass parts inorganic particulates, 20～300 mass parts additives; Wherein,
Solvent is one or more arbitrary proportion mixtures of toluene, acetone, dimethyl formamide, 1-METHYLPYRROLIDONE, N-METHYLFORMAMIDE, carrene, chloroform;
Adhesive is one or more arbitrary proportion mixtures in polyvinyl alcohol, cellulose acetate, methyl hydroxyethylcellulose, ethylhydroxyethylcellulose, methylhydroxypropylcellulose, Kynoar-hexafluoropropylene copolymer, polymethyl methacrylate solution or SBR emulsion, the sticking high-molecular organic material of tool;
Inorganic particulate is one or more arbitrary proportion mixtures in micropore, mesopore or macropore class zeolite particles, alundum (Al2O3), silicon dioxide, zirconia, titanium oxide, magnesium oxide, inorganic particulate is Powdered, particle diameter is evenly distributed, and scope is 0.02 μ m～10.0 μ m;
Additive is one or more arbitrary proportion mixtures of water, methyl alcohol, ethanol, isopropyl alcohol, cyclohexane, oxolane.
4. the zinc-silver primary cell composite diaphragm with liquid-adsorption layer and functional layer according to claim 3, is characterized in that, the solid content of described film slurry is 5wt%～60wt%, wherein the mass ratio 10:1～1:8 of inorganic particulate, adhesive.
5. the zinc-silver primary cell composite diaphragm with liquid-adsorption layer and functional layer according to claim 1, is characterized in that, described adhesion technique is the technique that materials at two layers is bonded into one, and comprising: hot-rolling pressure viscosity close or applying glue bonding.
6. the zinc-silver primary cell composite diaphragm with liquid-adsorption layer and functional layer according to claim 1, it is characterized in that, the described porous fibre of resistance to zinc-silver liquid-adsorption layer thickness is 20 μ m～500 μ m, and porosity is 30%～95%, and average pore size is 0.1 μ m～1000 μ m.
7. the zinc-silver primary cell composite diaphragm with liquid-adsorption layer and functional layer according to claim 1, is characterized in that, described porous counterdie thickness is 5 μ m～100 μ m, and porosity is 20%～90%, and average pore size is 0.02 μ m～50 μ m.
8. a preparation method for the described zinc-silver primary cell composite diaphragm with liquid-adsorption layer and functional layer of one of claim 1-7, is characterized in that, comprise inoganic particle modified, prepare film slurry, preparation functional layer, adhesive function layer and liquid-adsorption layer; Wherein,
Described is inoganic particle modified for carrying out surface treatment through silane coupler, and silane coupler is one or more arbitrary proportion mixtures of vinyl silanes, amino silane, methacryloxypropyl silane, 3-aminopropyl triethoxysilane, vinyltrimethoxy silane;
The described film slurry of preparing, mixes solvent, adhesive, inorganic particulate and additive, and the hybrid mode of slurry adopts one or more cooperations in mechanical agitation, ball grinding stirring and ultrasound treatment patterns;
Described preparation functional layer process using spray embrane method, scrape one or more in embrane method, the tape casting, rolling method and share, at porous counterdie surface-coated inorganic coating.
9. the preparation method of the zinc-silver primary cell composite diaphragm with liquid-adsorption layer and functional layer according to claim 8, it is characterized in that: described preparation functional layer also comprises hydrophilic treatment process, adopt the alkali lye of 5wt%～50wt% in 25 DEG C～90 DEG C processing capacity layer 0.5h～10h.
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| CN105619991A (en) * | 2016-03-16 | 2016-06-01 | 东华大学 | Composite lithium-ion battery separator material and preparation method thereof |
| CN112803117A (en) * | 2021-01-05 | 2021-05-14 | 北京金羽新能科技有限公司 | Hydrophilic diaphragm and battery containing same |
| CN115677412A (en) * | 2022-11-18 | 2023-02-03 | 西安德农生物科技有限公司 | Fertilizer capable of protecting fruit surfaces of crops and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1588672A (en) * | 2004-08-27 | 2005-03-02 | 河南环宇集团有限公司 | Alkaline secondary cell diaphragm and its producing method |
| JP2006004732A (en) * | 2004-06-17 | 2006-01-05 | Kuraray Co Ltd | Separator for alkaline cell, and alkaline primary cell |
| CN103400953A (en) * | 2013-07-19 | 2013-11-20 | 中国科学院金属研究所 | Zinc-silver battery composite diaphragm with inorganic coating and preparation method of composite diaphragm |
-
2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006004732A (en) * | 2004-06-17 | 2006-01-05 | Kuraray Co Ltd | Separator for alkaline cell, and alkaline primary cell |
| CN1588672A (en) * | 2004-08-27 | 2005-03-02 | 河南环宇集团有限公司 | Alkaline secondary cell diaphragm and its producing method |
| CN103400953A (en) * | 2013-07-19 | 2013-11-20 | 中国科学院金属研究所 | Zinc-silver battery composite diaphragm with inorganic coating and preparation method of composite diaphragm |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104449011A (en) * | 2014-12-04 | 2015-03-25 | 中航锂电（洛阳）有限公司 | Lithium ion battery insulating coating, preparation method and pole piece and lithium ion battery using insulating coating |
| CN105619991A (en) * | 2016-03-16 | 2016-06-01 | 东华大学 | Composite lithium-ion battery separator material and preparation method thereof |
| CN112803117A (en) * | 2021-01-05 | 2021-05-14 | 北京金羽新能科技有限公司 | Hydrophilic diaphragm and battery containing same |
| CN115677412A (en) * | 2022-11-18 | 2023-02-03 | 西安德农生物科技有限公司 | Fertilizer capable of protecting fruit surfaces of crops and preparation method thereof |
| CN115677412B (en) * | 2022-11-18 | 2024-02-23 | 西安德农生物科技有限公司 | Fertilizer capable of protecting crop fruit surfaces and preparation method thereof |
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