CN104022244B - There is zinc-silver primary cell composite diaphragm and the preparation method of liquid-adsorption layer and functional layer - Google Patents
There is zinc-silver primary cell composite diaphragm and the preparation method of liquid-adsorption layer and functional layer Download PDFInfo
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- CN104022244B CN104022244B CN201410213667.XA CN201410213667A CN104022244B CN 104022244 B CN104022244 B CN 104022244B CN 201410213667 A CN201410213667 A CN 201410213667A CN 104022244 B CN104022244 B CN 104022244B
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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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Abstract
The present invention relates to zinc-silver oxide cell barrier film preparation field, particularly a kind of zinc-silver primary cell composite diaphragm and its preparation method with liquid-adsorption layer and functional layer. Composite diaphragm is made up of the porous fiber film of resistance to zinc-silver liquid-adsorption layer and the functional layer being attached to its surface, multiporous fiber rete ensures resistance to zinc-silver and the imbibition of barrier film, functional layer gives the high resistance silver of barrier film, certain scale resistance and alkali corrosion resistance, and the inorganic particulate in functional layer has the effect of regulation and control membrane pore size size. Being mixed with tackiness agent and additive etc. by inorganic particulate and obtain film slurry, in thin porous fiber film surface preparation coating, the techniques such as drying obtain functional layer; Again namely functional layer and porous fiber layer bonding are obtained a zinc-silver oxide cell barrier film. The present invention by liquid-adsorption layer and functional layer organic assembling, replaces main barrier film and auxiliary barrier film in conventional batteries, it is to increase battery efficiency of assembling, has the features such as filming technology is simple, cost is low, and barrier film over-all properties is superior, and easily extensive large size is produced.
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 and its preparation method with liquid-adsorption layer and functional layer.
Background technology
The history being developed so far existing more than 50 years of zinc-silver oxide cell, owing to it has other unrivaled advantages of kind battery, it is 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, in civilian, telephotography, news photography, walkie-talkie, portable communications machine etc. also widely use, and button formula zinc-silver primary cell can be applicable to electronic watch, osophone and schrittmacher etc.
Zinc-silver cell is made up of pole plate group, shell monomer, monomer lid, pole, vent plug etc. several, and pole plate group comprises positive plate, negative plate and barrier film three part, and the performance of whole battery is determined by above-mentioned three kinds of materials. Barrier film has isolation positive and negative electrode, it is provided that the effect of ion diffuse passage, and for a zinc-silver oxide cell, the performance of barrier film directly affects the rate of activation of battery and wet state life-span.
Based on the barrier film of the materials such as Mierocrystalline cellulose, modified-cellulose, modified polyvinyl alcohol, there is good resistance silver performance, low resistance and higher-strength, be current zinc-silver once, the material of secondary battery membrane widespread use. But, for primary cell barrier film, the imbibition of above-mentioned materials is not enough, also need to install additional auxiliary barrier film during assemble and help the requirement that main barrier film Electolyte-absorptive completes battery quick active, for battery assembling make troubles, and due to main barrier film be dense film, ion could be transmitted after only abundant Electolyte-absorptive is swelling preferably, cause the internal resistance of cell relatively big, affect the discharge performance of primary cell. In order to solve the problems referred to above of battery diaphragm, improving the imbibition of primary cell barrier film and wet state life-span, investigator has carried out a large amount of explorations simultaneously. Some investigators do not use main barrier film, only use goffered paper to carry out assemble as barrier film, although imbibition can reach requirement, but the wet state life-span of battery be difficult to ensure. And main barrier film and auxiliary barrier film to be organically integrated into one be an effective method, this kind of barrier film is unsymmetric structure, comprising liquid-adsorption layer and functional layer, liquid-adsorption layer plays the imbibition effect of original auxiliary barrier film, and the resistance silver that functional layer plays original main barrier film waits barrier film effect. Meanwhile, functional layer comprises inorganic particulate, both can stop silver migration, can limit again dendrite growth, meet zinc-silver primary cell requirement.
Summary of the invention
It is an object of the invention to provide a kind of zinc-silver primary cell composite diaphragm and its preparation method with liquid-adsorption layer and functional layer, this barrier film includes liquid-adsorption layer and functional layer, the battery diaphragm prepared by this method has the advantages such as electrolytic solution rate of liquid aspiration is fast, alkali corrosion resistance, scale resistance are strong, can significantly improve charge-discharge performance and the work-ing life of zinc-silver primary cell, meet high-performance zinc-silver primary cell to the strict demand of barrier film.
The 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 made up of the multiporous fiber of resistance to zinc-silver liquid-adsorption layer and the functional layer being attached to its surface, functional layer comprises perforated bottom film and inorganic coating, by the film slurry containing inorganic particulate after coating process, drying, perforated bottom film forms inorganic coating, obtain functional layer, by adhesion technique, liquid-adsorption layer and functional layer are combined;
Described multiporous fiber liquid-adsorption layer or perforated bottom film are the non-woven fabrics or paper-like materials that imbibition, scale resistance and resistance to zinc-silver are higher, the ceramic-like materials that described inorganic particulate is scale resistance, resistance to zinc-silver is high.
The described zinc-silver primary cell composite diaphragm with liquid-adsorption layer and functional layer, non-woven fabrics is cellulosic nonwoven fabric, cellulose acetate non-woven fabrics, polyvinyl alcohol non-woven fabrics, the polyolefine non-woven fabrics of hydrophilic treatment or polyester non-woven fabric, and paper-like materials is the porous paper structure material with high liquid-absorbing: the cotton paper of goffered paper, porous or ceramic fiber paper.
The described zinc-silver primary cell composite diaphragm with liquid-adsorption layer and functional layer, the film slurry containing inorganic particulate is made up of the raw material of following mass parts: 500��10000 mass parts solvents, 10��300 mass parts tackiness agents, 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, N-Methyl pyrrolidone, N-METHYLFORMAMIDE, methylene dichloride, trichloromethane;
Tackiness agent is polyvinyl alcohol, cellulose acetate, methyl hydroxyethylcellulose, Type 3U, methylhydroxypropylcellulose, polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer, polymethyl methacrylate solution or SBR emulsion, one or more arbitrary proportion mixtures of having in the organic polymer material of viscosity;
Inorganic particulate is one or more arbitrary proportion mixtures in micropore, middle hole or macropore class zeolite particles, aluminium sesquioxide, silicon-dioxide, zirconium white, titanium oxide, magnesium oxide, inorganic particulate is powder shape, even particle size distribution, scope is 0.02 ��m��10.0 ��m;
Additive is one or more arbitrary proportion mixtures of water, methyl alcohol, ethanol, Virahol, hexanaphthene, tetrahydrofuran (THF).
The solid content of described film slurry is 5wt%��60wt%, wherein the mass ratio 10:1��1:8 of inorganic particulate, tackiness agent.
Described adhesion technique is technique materials at two layers being bonded into one, and comprising: hot roll-in bonding or applying glue bonding.
The described multiporous fiber of resistance to zinc-silver liquid-adsorption layer thickness is 20 ��m��500 ��m, and porosity is 30%��95%, and mean pore size is 0.1 ��m��1000 ��m.
Described perforated bottom film thickness is 5 ��m��100 ��m, and porosity is 20%��90%, and mean pore size is 0.02 ��m��50 ��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 carry out surface treatment through silane coupling agent, and silane coupling agent is one or more arbitrary proportion mixtures of vinyl silanes, aminosilane, methacryloxypropyl silane, 3-aminopropyl triethoxysilane, vinyltrimethoxy silane;
Described prepares film slurry, and by solvent, tackiness agent, inorganic particulate and additive mixing, the hybrid mode of slurry adopts one or more cooperations in mechanical stirring, ball grinding stirring and ultrasound treatment patterns;
Described preparation functional layer technique adopts spray embrane method, scrapes embrane method, one or more in casting method, rolling method share, at perforated bottom film 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 and the useful effect of the present invention be:
1, based on the defect of tradition zinc-silver primary cell barrier film, the present invention proposes following idea: by integral to main for tradition barrier film and auxiliary barrier film organic combination, form new types of diaphragm by porous liquid sucting fiber layer and micropore functional layer, make full use of paper class, the imbibition of fiber-like material keep the high rate of liquid aspiration of barrier film. Meanwhile, utilizing micropore functional layer to regulate and control the resistance silver of whole composite membrane, obtain the composite diaphragm that absorbent, mechanical property and electric property are all good, the method can comprehensively improve the rate of activation of zinc-silver oxide cell and wet shelf-lifes.
2, the zinc-silver primary cell barrier film using technique of the present invention to prepare has the features such as production technique is simple, with low cost, excellent combination property, it may be achieved large-scale industrial production.
In a word, composite diaphragm of the present invention comprises porous liquid-adsorption layer and adheres to the functional layer on its surface. Liquid-adsorption layer ensures that composite diaphragm has the rate of liquid aspiration of original auxiliary barrier film, and functional layer gives the strong scale resistance of composite diaphragm and alkali corrosion resistance. Meanwhile, the inorganic particulate in functional layer also has the effect of regulation and control composite diaphragm aperture size. Being mixed with tackiness agent and additive etc. by inorganic particulate and obtain film slurry, be coated on perforated bottom film surface, the techniques such as drying obtain functional layer, then this functional layer and the liquid-adsorption layer bonding with fiber or paper class formation are obtained new types of diaphragm. The present invention is by main for 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 tradition zinc-silver primary cell barrier film, have that filming technology is simple, cost is low, the features such as barrier film over-all properties is superior, easily extensive large size is produced.
Embodiment
The present invention has the zinc-silver primary cell composite diaphragm of liquid-adsorption layer and functional layer, composite diaphragm is made up of the multiporous fiber of resistance to zinc-silver liquid-adsorption layer and the functional layer being attached to its surface, functional layer comprises perforated bottom film and inorganic coating, by the film slurry containing inorganic particulate after coating process, drying, perforated bottom film forms inorganic coating, obtain functional layer, by adhesion technique, liquid-adsorption layer and functional layer are combined; Described multiporous fiber liquid-adsorption layer or perforated bottom film are the non-woven fabrics or paper-like materials that imbibition, scale resistance and resistance to zinc-silver are higher, the ceramic-like materials that described inorganic particulate is scale resistance, resistance to zinc-silver is high.
Described multiporous fiber liquid-adsorption layer or the material of perforated bottom film comprise: the non-woven fabrics such as the polyolefine of cellulosic nonwoven fabric, cellulose acetate non-woven fabrics, polyvinyl alcohol non-woven fabrics, hydrophilic treatment, polyester, and goffered paper, porous cotton paper, ceramic fiber paper etc. have the porous paper structure material of high liquid-absorbing.
The described film slurry containing inorganic particulate is made up of the raw material of following mass parts: 500��10000 mass parts solvents, 10��300 mass parts tackiness agents, 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, N-Methyl pyrrolidone, N-METHYLFORMAMIDE, methylene dichloride, trichloromethane; The tackiness agent of described film slurry is polyvinyl alcohol, cellulose acetate, methyl hydroxyethylcellulose, Type 3U, methylhydroxypropylcellulose, polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer, polymethyl methacrylate solution or SBR emulsion, one or more arbitrary proportion mixtures of having in the organic polymer material of viscosity; The inorganic particulate of described film slurry is one or more arbitrary proportion mixtures in micropore, middle hole or macropore class zeolite particles, aluminium sesquioxide, silicon-dioxide, zirconium white, titanium oxide, magnesium oxide, inorganic particulate is powder shape, even particle size distribution, scope is 0.02 ��m��10.0 ��m; The additive of described film slurry is one or more arbitrary proportion mixtures of water, methyl alcohol, ethanol, Virahol, hexanaphthene, tetrahydrofuran (THF).
Described adhesion technique comprises: the technique that materials at two layers can be bonded into one by hot roll-in bonding, applying glue bonding etc. The solid content of described film slurry is 5wt%��60wt%, wherein the mass ratio 10:1��1:8 of inorganic particulate, tackiness agent. The described multiporous fiber of resistance to zinc-silver liquid-adsorption layer thickness is 20 ��m��500 ��m, and porosity is 30%��95%, and mean pore size is 0.1 ��m��1000 ��m. Described perforated bottom film thickness is 5 ��m��100 ��m, and porosity is 20%��90%, and mean pore size is 0.02 ��m��50 ��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, preparation functional layer, the process such as adhesive function layer and liquid-adsorption layer. Described is inoganic particle modified for carry out surface treatment through silane coupling agent, and silane coupling agent comprises one or more arbitrary proportion mixtures of vinyl silanes, aminosilane, methacryloxypropyl silane, 3-aminopropyl triethoxysilane, vinyltrimethoxy silane. Described prepares film slurry, and by solvent, tackiness agent, inorganic particulate and additive mixing, the hybrid mode of slurry adopts one or more cooperations in mechanical stirring, ball grinding stirring and ultrasound treatment patterns. Described preparation functional layer technique adopts spray embrane method, scrapes embrane method, one or more in casting method, rolling method share, at perforated bottom film surface-coated inorganic coating. Described preparation functional layer also comprises hydrophilic treatment process, adopts 5%��50% alkali lye, 25 DEG C��90 DEG C processing capacity layer 0.5h��10h.
In the present invention, unless specified otherwise, it relates to percentage ratio be mass percent.
Below by embodiment, the present invention is described in further detail.
Embodiment 1
Configuration quality mark is the 3-aminopropyl triethoxysilane aqueous solution 100ml of 1.5%. 10g Zirconia particles (granularity 0.5 ��m) adds in above-mentioned solution, 90 DEG C of stirring in water bath 6h. After washing 4 times after centrifugal, dry acquisition modified inorganic particle. 0.3g cellulose acetate, 1.5g Zirconia particles, 0.5g water are joined in 50g acetone, ultrasonic dissolution, until obtaining uniform film slurry.
Taking polyvinyl alcohol non-woven fabrics (thickness 30 ��m) as end film, by pickling process in its surface preparation coating, drying at room temperature 4h is placed in 80 DEG C of baking ovens dry 6h, obtains functional layer.
By above-mentioned functions layer in the KOH solution of 10wt% at 60 DEG C alkaline purification 2h, be washed to neutral post-drying and obtain modified functional layer.
Taking 1wt% polyvinyl alcohol solution as tackiness agent, above-mentioned modified function layer and cellulose acetate non-woven fabrics (thickness 70 ��m) are bonded into one, 100 DEG C of dry acquisition zinc-silver primary cell composite diaphragms.
Above-mentioned composite diaphragm is tested.
Thickness measuring result: composite diaphragm thickness is 105 ��m.
Imbibition test result: under room temperature, the rate of liquid aspiration of barrier film in the KOH solution of 30wt% is that 45mm/5min pick up is about 320%.
Tensile strength test result: horizontal, longitudinal tensile strength is all greater than 35N/mm2��
Embodiment 2
Configuration quality mark is the vinyltrimethoxy silane aqueous solution 100ml of 5%. 25gMFI zeolite particles (granularity 1.0 ��m) adds in above-mentioned solution, 90 DEG C of stirring in water bath 6h. After centrifugal washing 2 times, dry acquisition modified inorganic particle. 1.0g methyl hydroxyethylcellulose, 4.5gMFI zeolite particles, 0.4g ethanol are joined in 50g acetone, ultrasonic dissolution, until obtaining uniform film slurry.
Taking polyethylene non-woven fabrics (thickness 30 ��m) as end film, by rolling method in its surface preparation coating, drying at room temperature 6h is placed in 80 DEG C of baking ovens dry 4h, obtains functional layer.
By above-mentioned functions layer in the KOH solution of 25wt% at 50 DEG C alkaline purification 2h, be washed to neutral post-drying and obtain modified functional layer.
Taking 2.5wt% cellulose acetate solution as tackiness agent, above-mentioned modified function layer and cellulosic nonwoven fabric (thickness 80 ��m) are bonded into one, 100 DEG C of dry acquisition zinc-silver primary cell composite diaphragms.
Above-mentioned composite diaphragm is tested.
Thickness measuring result: composite diaphragm thickness is 130 ��m.
Imbibition test result: under room temperature, the rate of liquid aspiration of barrier film in the KOH solution of 30wt% is that 50mm/5min pick up is about 350%.
Tensile strength test result: horizontal, longitudinal tensile strength is all greater than 40N/mm2��
Embodiment 3
Configuration quality mark is the methacryloxypropyl silane aqueous solution 100ml of 3.8%. 30gAl2O3Particle (granularity 0.5 ��m) adds in above-mentioned solution, 90 DEG C of stirring in water bath 5h. After centrifugal washing 4 times, dry acquisition modified inorganic particle. By 1.0g Type 3U, 4.0gAl2O3Particle, 1.5g methyl alcohol join in 50g acetone, ultrasonic dissolution, until obtaining uniform film slurry.
Taking polyethylene non-woven fabrics (thickness 35 ��m) as end film, by spraying method in its surface preparation coating, drying at room temperature 6h is placed in 80 DEG C of baking ovens dry 4h, obtains functional layer.
By above-mentioned functions layer in the KOH solution of 35wt% with 60 DEG C at alkaline purification 1h, be washed to neutral post-drying and obtain modified functional layer.
The polystyrene microsphere of 1.5wt% is sprayed on functional layer surface, is thermal bonding to one by roll squeezer at being superimposed on 120 DEG C with the cotton paper (thickness 100 ��m) of porous, obtains zinc-silver primary cell composite diaphragm.
Above-mentioned composite diaphragm is tested.
Thickness measuring result: composite diaphragm thickness is 120 ��m.
Imbibition test result: under room temperature, the rate of liquid aspiration of barrier film in the NaOH solution of 30wt% is that 40mm/5min pick up is about 300%.
Tensile strength test result: horizontal, longitudinal tensile strength is all greater than 35N/mm2��
Embodiment 4
Configuration quality mark is the 3-aminopropyl triethoxysilane aqueous solution 100ml of 2.5%. 25gZrO2Particle (granularity 0.05 ��m) adds in above-mentioned solution, 90 DEG C of stirring in water bath 5h. After centrifugal washing 4 times, dry acquisition modified inorganic particle. By 2.0g polyvinylidene difluoride (PVDF)-R 1216,8.0gZrO2Particle, 0.5g water join in 50g acetone, ultrasonic dissolution, until obtaining uniform film slurry.
Taking polyvinyl alcohol non-woven fabrics (thickness 35 ��m) as end film, by pickling process in its surface preparation coating, drying at room temperature 6h is placed in 80 DEG C of baking ovens dry 4h, obtains functional layer.
By above-mentioned functions layer in the KOH solution of 15wt% with 50 DEG C at alkaline purification 3h, be washed to neutral post-drying and obtain modified functional layer.
Being tackiness agent by the polyvinyl alcohol solution of 2.0wt%, above-mentioned modified function layer and cellulosic nonwoven fabric (thickness 80 ��m) are bonded into one, 100 DEG C dry obtains zinc-silver primary cell composite diaphragms.
Above-mentioned composite diaphragm is tested.
Thickness measuring result: composite diaphragm thickness is 112 ��m.
Imbibition test result: under room temperature, the rate of liquid aspiration of barrier film in the KOH solution of 30wt% is that 55mm/5min pick up is about 360%.
Tensile strength test result: horizontal, longitudinal tensile strength is all greater than 35N/mm2��
Embodiment 5
Configuration quality mark is the 3-aminopropyl triethoxysilane aqueous solution 100ml of 4.0%. 50gTiO2Particle (granularity 0.2 ��m) adds in above-mentioned solution, 90 DEG C of stirring in water bath 5h. After centrifugal washing 4 times, dry acquisition modified inorganic particle. By 2.0g polyvinylidene difluoride (PVDF)-R 1216,8.0gTiO2Particle, 1.0g hexanaphthene join in 50g acetone, ultrasonic dissolution, until obtaining uniform film slurry.
Taking polymeric amide non-woven fabrics (thickness 50 ��m) as end film, by scraping embrane method in its surface preparation coating, drying at room temperature 6h is placed in 100 DEG C of baking ovens dry 4h, obtains functional layer.
By above-mentioned functions layer in the KOH solution of 45wt% with 40 DEG C at alkaline purification 1h, be washed to neutral post-drying and obtain modified functional layer.
Being tackiness agent by the cellulose acetate acetone soln of 5wt%, above-mentioned modified function layer and ceramic fiber paper (thickness 250 ��m) are bonded into one, 100 DEG C dry obtains zinc-silver primary cell composite diaphragms.
Above-mentioned composite diaphragm is tested.
Thickness measuring result: composite diaphragm thickness is 280 ��m.
Imbibition test result: under room temperature, the rate of liquid aspiration of barrier film in the KOH solution of 30wt% is that 32mm/5min pick up is about 450%.
Tensile strength test result: horizontal, longitudinal tensile strength is all greater than 60N/mm2��
Embodiment result shows, zinc-silver primary cell composite diaphragm and its preparation method with liquid-adsorption layer and functional layer provided by the invention, a kind of film is made to combine the advantage of two kinds of barrier films, overcome the shortcoming of tradition zinc-silver primary cell barrier film, have that filming technology is simple, cost is low, the features such as barrier film over-all properties is superior, easily extensive large size is produced.
Claims (7)
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 made up of the multiporous fiber of resistance to zinc-silver liquid-adsorption layer and the functional layer being attached to its surface, functional layer comprises perforated bottom film and inorganic coating, by the film slurry containing inorganic particulate after coating process, drying, perforated bottom film forms inorganic coating, obtains functional layer, by adhesion technique, liquid-adsorption layer and functional layer are combined;
Described multiporous fiber liquid-adsorption layer or perforated bottom film are the non-woven fabrics or paper-like materials that imbibition, scale resistance and resistance to zinc-silver are higher, the ceramic-like materials that described inorganic particulate is scale resistance, resistance to zinc-silver is high;
The described multiporous fiber of resistance to zinc-silver liquid-adsorption layer thickness is 20 ��m��500 ��m, and porosity is 30%��95%, and mean pore size is 0.1 ��m��1000 ��m;
Described perforated bottom film thickness is 5 ��m��100 ��m, and porosity is 20%��90%, and mean pore size is 0.02 ��m��50 ��m.
2. the zinc-silver primary cell composite diaphragm with liquid-adsorption layer and functional layer according to claim 1, it is characterized in that, non-woven fabrics is cellulosic nonwoven fabric, cellulose acetate non-woven fabrics, polyvinyl alcohol non-woven fabrics, the polyolefine non-woven fabrics of hydrophilic treatment or polyester non-woven fabric, and paper-like materials is the porous paper structure material with high liquid-absorbing: the cotton paper of goffered paper, porous 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 containing inorganic particulate is made up of the raw material of following mass parts: 500��10000 mass parts solvents, 10��300 mass parts tackiness agents, 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, N-Methyl pyrrolidone, N-METHYLFORMAMIDE, methylene dichloride, trichloromethane;
Tackiness agent is one or more arbitrary proportion mixtures in polyvinyl alcohol, cellulose acetate, methyl hydroxyethylcellulose, Type 3U, methylhydroxypropylcellulose, polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer, polymethyl methacrylate solution or SBR emulsion;
Inorganic particulate is one or more arbitrary proportion mixtures in micropore, middle hole or macropore class zeolite particles, aluminium sesquioxide, silicon-dioxide, zirconium white, titanium oxide, magnesium oxide, inorganic particulate is powder shape, even particle size distribution, scope is 0.02 ��m��10.0 ��m;
Additive is one or more arbitrary proportion mixtures of water, methyl alcohol, ethanol, Virahol, hexanaphthene, tetrahydrofuran (THF).
4. the zinc-silver primary cell composite diaphragm with liquid-adsorption layer and functional layer according to claim 3, it is characterised in that, the solid content of described film slurry is 5wt%��60wt%, wherein the mass ratio 10:1��1:8 of inorganic particulate, tackiness agent.
5. the zinc-silver primary cell composite diaphragm with liquid-adsorption layer and functional layer according to claim 1, it is characterised in that, described adhesion technique is technique materials at two layers being bonded into one, and comprising: hot roll-in bonding or applying glue bonding.
6. the preparation method of the zinc-silver primary cell composite diaphragm with liquid-adsorption layer and functional layer that one of claim 1-5 is described, it is characterised 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 carry out surface treatment through silane coupling agent, and silane coupling agent is one or more arbitrary proportion mixtures of vinyl silanes, aminosilane, methacryloxypropyl silane, 3-aminopropyl triethoxysilane, vinyltrimethoxy silane;
Described prepares film slurry, and by solvent, tackiness agent, inorganic particulate and additive mixing, the hybrid mode of slurry adopts one or more cooperations in mechanical stirring, ball grinding stirring and ultrasound treatment patterns;
Described preparation functional layer technique adopts spray embrane method, scrapes embrane method, one or more in casting method, rolling method share, at perforated bottom film surface-coated inorganic coating.
7. the preparation method of the zinc-silver primary cell composite diaphragm with liquid-adsorption layer and functional layer according to claim 6, 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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| 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 |
| CN105619991B (en) * | 2016-03-16 | 2018-10-23 | 东华大学 | A kind of composite lithium ion cell diaphragm 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 |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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| JP4739696B2 (en) * | 2004-06-17 | 2011-08-03 | 株式会社クラレ | Alkaline battery separator and alkaline primary battery |
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Patent Citations (2)
| 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 |
| 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 |
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