CN104073068A - Coating composition, battery diaphragm and preparation method of battery diaphragm - Google Patents
Coating composition, battery diaphragm and preparation method of battery diaphragm Download PDFInfo
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Abstract
The invention provides a coating composition, a battery diaphragm and a preparation method of the battery diaphragm. The coating composition provided by the invention comprises the following components in parts by weight: 1part of water-based adhesive based on the solid content, 1-30 parts of inorganic matter particles, 0.5-6 parts of wetting agent, 0-3 parts of leveling agent and 0-0.8 weight part of stabilizer. The battery diaphragm provided by the invention is obtained by forming the coating composition on at least one surface of a polymer-based membrane. The preparation method of the battery diaphragm comprises the following steps: adding water into the water-based adhesive and the stabilizer to obtain adhesive slurry with viscosity of 2,000-5,000mPa.s; uniformly mixing the inorganic matter particles with the adhesive slurry; adding water to adjust the viscosity to 10-1,500mPa.s to obtain diluted mixed slurry; and mixing the wetting agent and the leveling agent with the mixed slurry and coating at least one surface of the polymer-based membrane with the mixture and drying. The battery diaphragm provided by the invention has good heat resistance and air permeability and excellent safety in application.
Description
Technical field
The present invention relates to a kind of coating composition, battery diaphragm and preparation method thereof, belong to the energy storage devices such as battery, electrical condenser and manufacture field.
Background technology
Barrier film is to manufacture one of nonaqueous electrolyte energy storage device material as indispensable in lithium ion battery, lithium secondary battery and ultracapacitor etc., in battery, role is to prevent positive and negative electrode short circuit, and ion transportation electric channel is provided simultaneously in charge and discharge process.The performance of barrier film determines the interface structure, internal resistance of battery etc., directly affects capacity, cycle performance and the safety performance etc. of battery.
Diaphragm material for above-mentioned energy storage device mostly is polymer materials, also claim membrane for polymer, mainly be divided into polymer microporous film and non-woven fabrics etc., such as polypropylene (PP), polyethylene (PE) individual layer microporous membrane, by PP and the compound multilayer microporous film of PE and polyethylene terephthalate (PET) non-woven fabrics etc.In realizing the heavy body of lithium secondary battery and the research of high security, find, when only using polymer microporous film or non-woven fabrics, can not obtain enough performances, its main drawback is that thermotolerance is poor.Due to the characteristic of material itself, as lithium ion battery separator membrane for polymer, surpassing meeting demonstration thermal contraction behavior at the temperature of 100 ℃.When internal temperature of battery is over 150 ℃, although membrane for polymer produces fusing, micropore disappears and has blocked ionic conduction, but while occurring to melt due to membrane for polymer, must supervene a large amount of volumetric shrinkages, thereby make inside battery that direct short-circuit between positive and negative electrode likely occur, cause battery security problem as burning, the phenomenons such as blast.
In patent of invention CN101434708A, disclose and a kind ofly in the modification of polyalkene diaphragm surface coating, made composite diaphragm, to improve its stable on heating method.The coated material using is by 100 parts of water-soluble polymerss, hydrophobic monomer 30-500 part, hydrophilic monomer 0-200 part, the copolymerization of initiator 1-5 part obtains polymer latex precursor emulsion, by polymer latex precursor emulsion solid content in 100%, the slurries that add the mineral filler of 0-100% and the fluidizer of 20-100% to obtain, are coated in one side or the two-sided formation coating through the micropore polyolefin barrier diaphragm of surface modification by gained slurries, and drying obtains composite diaphragm.There are two problems in this technical scheme: the one, and not obvious to the thermotolerance raising effect of membrane for polymer, and the ventilation property of composite diaphragm can reduce a lot, and then the performance of battery worsens because of resistance increase; The 2nd, when membrane for polymer is polyolefins material, because it is nonpolar polymkeric substance, surface can be lower, water-based system wetting property is poor, needs polyolefins barrier film to carry out surface modification before coating, introduces polar group, therefore production stage, complicated operation have been increased.
Summary of the invention
The invention provides a kind of coating composition, make its surface in polymer-based film form coating, can solve the problem of membrane for polymer poor heat resistance in prior art, maintain the ventilation property that barrier film is good simultaneously,
The invention provides a kind of battery diaphragm, have good thermotolerance and ventilation property concurrently, be applied to can obtain satisfied effect in lithium secondary battery.
The invention provides a kind of method of preparing battery diaphragm, utilize described coating composition to form coating on polymer-based film surface, preparation technology is simple, and the battery diaphragm making has good thermotolerance and ventilation property concurrently.
The invention provides a kind of coating composition, its composition comprises:
Aqueous binder 1 weight part, particles of inorganic material 1-30 weight part, wetting agent 0.5-6 weight part, flow agent 0-3 weight part and stablizer 0-0.8 weight part in solid content.
According to coating composition provided by the invention, conventional aqueous binder all can be used, and its kind is such as being rubber-like aqueous binder, polyvinyl alcohol aqueous binder, polyacrylic aqueous binder, polyvinyl acetate class aqueous binder, polyurethanes aqueous binder, silicone resin class aqueous binder or epoxy aqueous binder etc.
According to coating composition provided by the invention, aqueous binder is rubber-like aqueous binder, and in described coating composition, described stablizer is 0.1-0.8 weight part.While being described aqueous binder selection rubber-like aqueous binder, in said composition, can also comprise stablizer, be more conducive to embody its coating performance, such as carboxymethyl cellulose, Xylo-Mucine or farinose etc.The content of stablizer is the more than 0.1 times of aqueous binder weight (in solid content), as 0.1-0.8 weight part.In a specific embodiment of the present invention, use carboxylic styrene-butadiene rubber latex as aqueous binder, Xylo-Mucine is as stablizer.
Coating composition provided by the invention, appropriate wetting agent can make particles of inorganic material more easily be soaked in water, by reduce particles of inorganic material with water termination tension force, make water can be deployed in the surface of particles of inorganic material.In the specific embodiment of the present invention, for example, can use alcohols wetting agent, as ethanol, propylene glycol, propyl carbinol, Virahol or glycerine etc.
According to battery diaphragm coating provided by the invention, described particles of inorganic material can be the metal oxide materials such as magnesium oxide, calcium oxide, silicon-dioxide, aluminum oxide and zirconium dioxide, or the carbonate of metal or nitrate, such as calcium carbonate etc.
The interpolation of proper amount of inorganic matter particle is beneficial to the resistance toheat of effective raising barrier film coating, and keeps good Gas permeability, but excessive particles of inorganic material can make the battery diaphragm coating cohesiveness variation of preparation, easily falls slag.Through contriver's research, when the content of particles of inorganic material is 1-30 times of aqueous binder weight (in solid content), the battery diaphragm coating making can obtain satisfied effect.In above-mentioned coating composition, from the comprehensive better angle of the battery diaphragm of preparation, consider, comprise particles of inorganic material 10-20 weight part.The particle diameter of described particles of inorganic material is preferably Nano grade, for example, can use the particles of inorganic material that particle diameter is 50-500nm.The particles of inorganic material of this particle diameter is conducive to that realization in coating is uniformly distributed and the resistance toheat that improves coating is also beneficial to and prevents that the hole of stopping up polymer-based film because of particles of inorganic material from causing permeability deterioration simultaneously.
Utilize coating composition provided by the invention to form battery diaphragm coating, the particles of inorganic material wherein containing, when guaranteeing that battery diaphragm coating cohesiveness is good, has improved its resistance toheat.This coating composition is coated on to polymer-based film and forms coating, because particles of inorganic material can play perforating action, the battery diaphragm Gas permeability making is good, the inorganic particle in addition with suitable particle diameter has and is beneficial to electrolytic solution sprawling on battery diaphragm surface in lithium cell, be beneficial to and improve the absorbency of battery diaphragm and protect fluidity, thereby be beneficial to seeing through of ion.
Further, in coating composition of the present invention, appropriate wetting agent is beneficial to the surface tension that reduces particles of inorganic material, improve the interface compatibility of coating and polymer-based film, be beneficial to the coating that forms and obtain even thickness, while operating, save this operation of polymer-based film surface treatment simultaneously, reduced production cost, improved production efficiency.
According to coating composition provided by the invention, wherein can also comprise flow agent.The use of flow agent is beneficial to and in drying and forming-film process, makes coating smooth, smooth and even.Can use any known and conventional flow agent, such as silicone based, fluorine carbon or polyurethanes flow agent etc.In above-mentioned coating composition, when using flow agent, its content is 0.2-3 weight part.
In the present invention, aqueous binder, particles of inorganic material, wetting agent, flow agent and stablizer all can be by commercially available.
The present invention also provides a kind of battery diaphragm, the coating that it has polymer-based film and utilizes above-mentioned coating composition to form at least one surface of this polymer-based film.
According to battery diaphragm provided by the invention, wherein, the thickness of described coating is 0.1-1 times of described polymer-based carbon film thickness.Coat-thickness can be adjusted according to the requirement of application conditions, to reach, has good thermotolerance and the object of ventilation property concurrently, for example, be 0.1-1 times of polymer-based carbon film thickness.The total thickness that coat-thickness is the coating that forms in polymer-based film herein, when it is formed at respectively on two surfaces of polymer-based film, coat-thickness is for being formed at respectively two lip-deep coat-thickness sums.Coat-thickness can, by controlling by conventional method when the painting slurry, for example, while using the coating of line rod, can be controlled coat-thickness by adjusting the model of line rod.
According to battery diaphragm provided by the invention, polymer-based film can be commercially available, and comprises polymer microporous film and non-woven fabrics etc., can prepare by dry method, wet method or method of electrostatic spinning.For example, at present for microporous polypropylene membrane (PP film), polyethene microporous membrane (PE film), microporous polypropylene membrane/polyethene microporous membrane/microporous polypropylene membrane sandwich diaphragm (PP/PE/PP film) of lithium-ion secondary cell, polyimide (PI) microporous membrane, and polyethylene terephthalate (PET) non-woven fabrics barrier film etc., be the known film raw material for battery diaphragm, the present invention is not particularly limited, as long as meet the essential property for battery diaphragm.Generally, the polymer film thickness of use for 7-30 μ m, porosity be 20-80%, Gas permeability is 100-700s/100c, under 105 ℃ and 1h condition, percent thermal shrinkage is 1-10%, vertical and horizontal tensile strength 60-400MPa, puncture intensity 200-700gf.In embodiments of the invention, use Shanghai Shuan Ao energy technology company limited to produce, the polyethene microporous membrane of preparing by wet method.
The present invention also provides a kind of method of preparing above-mentioned battery diaphragm, comprising:
Aqueous binder and stablizer and water are hybridly prepared into the tackiness agent slurries that viscosity is 2000-5000mPas;
Particles of inorganic material is mixed with described tackiness agent slurries, and dispersed, obtain mixed serum;
Adding water, to regulate the viscosity of described mixed serum be 10-1500mPas, obtains the mixed serum of dilution;
Wetting agent and flow agent are mixed with the mixed serum of dilution, and dispersed, obtain barrier film coating slurries;
Barrier film coating slurries are coated on at least one surface of polymer-based film upper, the dry rear coating that forms, obtains described battery diaphragm.
In the middle composition of coating composition, flow agent and stablizer are selectivity composition, are appreciated that in the barrier film coating slurries that obtain and can comprise or not comprise flow agent and/or stablizer.
According to method provided by the invention, at least one surface that barrier film coating slurries is coated on to polymer-based film is upper, heat-treats to coating dryly at 40-100 ℃, and the time of heat-treating can be for example 0.5-1h, obtains described battery diaphragm.
In the present invention, aqueous binder and stablizer and water are hybridly prepared into the tackiness agent slurries that viscosity is 2000-5000mPas, particles of inorganic material is mixed with it and obtain after mixed serum, the viscosity that again adds water adjusting mixed serum is 10-1500mPas, obtains the mixed serum of dilution.By using the hybrid technique of substep, object is to make tackiness agent slurries coated inorganic composition granule, can either guarantee that particles of inorganic material is uniformly dispersed in slurries, and then guarantees the even thickness of coating; Can make again the slurries of preparation stable, even after slurries are placed for some time there is a little sedimentation in particles of inorganic material, also be the sedimentation together of tackiness agent coated inorganic composition granule, and can not produce the phenomenon that particles of inorganic material is reunited, therefore through simple stirring, can use.While especially using nano grade inorganic composition granule, adopt above-mentioned substep hybrid technique preparation slurries, be more conducive to prevent the reunion of particle, and then control the homogeneity of coat-thickness.From the angle that battery diaphragm over-all properties is better, consider, the viscosity of tackiness agent slurries is 2000-3000mPas, and the viscosity of the mixed serum of dilution is 500-1200mPas.
According to method provided by the invention, barrier film coating slurries are coated in to polymer-based film and can use conventional coating method, for example dip-coating, intaglio plate coating or the coating of line rod etc.In the specific embodiment of the present invention, use the mode of line rod coating to be coated with.
According to preparation method provided by the invention, blending means is for being used colter stirrer, double planetary mixer or ball mill mix, by adjusting agitation condition for different types of aqueous binder, to reach the object that each component is mixed and do not affected tackiness agent bond properties, for example, rubber adhesive has larger molecular weight relatively, need to control the stirring of milder.
The enforcement of technical solution of the present invention, at least has the following advantages:
1, battery diaphragm coating provided by the invention is guaranteeing good with polymer-based film cohesiveness in the situation that, by controlling coordinating of particles of inorganic material and aqueous binder, make the resistance toheat raising of battery diaphragm, and Gas permeability is good;
2, in the present invention, be used in conjunction with the technique that substep mixes, particles of inorganic material is uniformly dispersed, the coat-thickness of preparation is more even, and the slurries that make are stable, and the shelf time is long;
3, battery diaphragm coating provided by the invention makes water as solvent, safety and environmental protection.
Accompanying drawing explanation
Fig. 1 is the electron scanning micrograph of the battery diaphragm prepared of one embodiment of the present of invention.
Embodiment
Below in conjunction with specific embodiment, embodiment of the present invention and technique effect are described more fully.Yet the present invention can multiple multi-form embodiment, should not be construed as and be limited to the embodiment of statement herein.
In following examples, use Shanghai Shuan Ao energy technology company limited to produce, the polyethene microporous membrane of preparing by wet method is as polymer-based film, and its thickness is 7-20 μ m, porosity 30-60%.
Embodiment 1
Consisting of of the present embodiment floating coat composition: polyvinyl alcohol 1 weight part, alumina particle 30 weight parts, propyl carbinol 0.91 weight part, dehydrated alcohol 4.55 weight parts.
First polyvinyl alcohol is added and in deionized water, be mixed with the tackiness agent slurries that viscosity is 3000mPas; Again alumina particle is added in the tackiness agent slurries of acquisition, use ball mill that alumina particle is uniformly dispersed, obtain mixed serum; Again adding deionized water to regulate the viscosity of described mixed serum is 1043mPas, obtains the mixed serum of dilution; Then propyl carbinol, dehydrated alcohol are mixed with the mixed serum of dilution, and dispersed, obtain barrier film coating slurries; Finally, use the mode of line rod coating to be coated in the one side of polyethene microporous membrane in barrier film coating slurries, and dry 50min form coating in 60 ℃ of baking ovens, obtains described battery diaphragm.
In the present embodiment, the viscosity of slurries is used the test of digital display viscometer, and following embodiment is identical.
The properties of battery diaphragm prepared by the present embodiment is as shown in table 1.Wherein:
Use thickness tester to measure respectively the thickness of battery diaphragm prepared by polyethene microporous membrane and the present embodiment, the difference of the two is the thickness of battery diaphragm coating;
Battery diaphragm prepared by the present embodiment is placed in air dry oven, at 105 ℃, 150 ℃ and 200 ℃, heat-treat 1h respectively, and measure respectively the length of horizontal (TD) and longitudinal (MD) of battery diaphragm before and after thermal treatment, calculate accordingly battery diaphragm at horizontal and vertical percent thermal shrinkage.
Use the Gurley permeating degree tester Gas permeability of test battery barrier film at normal temperatures and pressures;
Tensile strength and the puncture intensity of battery diaphragm prepared by use microcomputer controlled electronic universal tester test the present embodiment.
Fig. 1 is the electron scanning micrograph of the battery diaphragm prepared of the present embodiment.As can be seen from Figure 1, particles of inorganic material forms even and fine and close coating on polyethene microporous membrane surface, and this is conducive to improve thermotolerance and the ventilation property of battery diaphragm.
In the present embodiment, use polyvinyl alcohol as aqueous binder, the battery diaphragm of preparation meets application requiring, and has good ventilation property and excellent thermotolerance.
Embodiment 2
Consisting of of the present embodiment floating coat composition: polyvinyl alcohol 1 weight part, alumina particle 30 weight parts, propyl carbinol 0.91 weight part, dehydrated alcohol 4.55 weight parts and silicone based flow agent 2.83 weight parts.
First polyvinyl alcohol is added and in deionized water, be mixed with the tackiness agent slurries that viscosity is 2800mPas; Again alumina particle is added in the tackiness agent slurries of acquisition, use ball mill that alumina particle is uniformly dispersed, obtain mixed serum; Again adding deionized water to regulate the viscosity of described mixed serum is 1200mPas, obtains the mixed serum of dilution; Then propyl carbinol, dehydrated alcohol and silicone based flow agent are mixed with the mixed serum of dilution, and dispersed, obtain barrier film coating slurries; Finally, use the mode of line rod coating to be coated in the one side of polyethene microporous membrane in barrier film coating slurries, and be dried and form coating under the condition identical with embodiment 1, obtain described battery diaphragm.
The properties of battery diaphragm prepared by the present embodiment is as shown in table 1, and testing method is identical with embodiment 1.
In the present embodiment, the same polyvinyl alcohol that uses is as aqueous binder.Compare with embodiment 1, contain silicone based flow agent in the coating composition of the present embodiment, the battery diaphragm surface of preparation is more smooth, and thermotolerance and Gas permeability are also slightly improved simultaneously.
Embodiment 3
Consisting of of the present embodiment floating coat composition: LA series aqueous binder (in solid content) 1 weight part, alumina particle 15 weight parts, Virahol 2.5 weight parts and silicone based flow agent 2.5 weight parts.
First LA series aqueous binder is added and in deionized water, be mixed with the tackiness agent slurries that viscosity is 2460mPas; Again alumina particle is added in the tackiness agent slurries of acquisition, use ball mill that alumina particle is uniformly dispersed, obtain mixed serum; Again adding deionized water to regulate the viscosity of described mixed serum is 592mPas, obtains the mixed serum of dilution; Then Virahol and silicone based flow agent are mixed with the mixed serum of dilution, and dispersed, obtain barrier film coating slurries; Finally, use the mode of line rod coating to be coated in the one side of polyethene microporous membrane in barrier film coating slurries, and be dried and form coating under the condition identical with embodiment 1, obtain described battery diaphragm.
The properties of battery diaphragm prepared by the present embodiment is as shown in table 1, and testing method is identical with embodiment 1.
Compare with 2 with embodiment 1, in the present embodiment, use LA series aqueous binder, belong to acrylic acid or the like aqueous binder.In the present embodiment, the mixed serum viscosity of dilution is less, makes to be formed at the lip-deep coating of polyethene microporous membrane thinner, and in the situation that thermotolerance meets service requirements, the ventilation property of barrier film is higher; Silicone based flow agent in coating composition, makes the battery diaphragm surface of preparation comparatively smooth simultaneously.
Embodiment 4
Consisting of of the present embodiment floating coat composition: LA series aqueous binder (in solid content) 1 weight part, alumina particle 5 weight parts, propyl carbinol 0.58 weight part and dehydrated alcohol 0.232 weight part.
First LA series aqueous binder is added and in deionized water, be mixed with the tackiness agent slurries that viscosity is 2650mPas; Again alumina particle is added in the tackiness agent slurries of acquisition, use ball mill that alumina particle is uniformly dispersed, obtain mixed serum; Again adding deionized water to regulate the viscosity of described mixed serum is 800mPas, obtains the mixed serum of dilution; Then propyl carbinol and dehydrated alcohol are mixed with the mixed serum of dilution, and dispersed, obtain barrier film coating slurries; Finally, use the mode of line rod coating to be coated in the one side of polyethene microporous membrane in barrier film coating slurries, and be dried and form coating under the condition identical with embodiment 1, obtain described battery diaphragm.
The properties of battery diaphragm prepared by the present embodiment is as shown in table 1, and testing method is identical with embodiment 1.
In the present embodiment, the same LA series aqueous binder that uses, belongs to acrylic acid or the like aqueous binder.The content of alumina particle is reduced to 5 weight parts, at Gas permeability and other performances, meet under the prerequisite of application requiring, resistance toheat is still significantly improved with respect to the polyethene microporous membrane without coating modified.
Embodiment 5
Consisting of of the present embodiment floating coat composition: LA series aqueous binder (in solid content) 1 weight part, alumina particle 20 weight parts, propyl carbinol 1.5 weight parts and dehydrated alcohol 1.5 weight parts.
First LA series aqueous binder is added and in deionized water, be mixed with the tackiness agent slurries that viscosity is 2600mPas; Again alumina particle is added in the tackiness agent slurries of acquisition, use ball mill that alumina particle is uniformly dispersed, obtain mixed serum; Again adding deionized water to regulate the viscosity of described mixed serum is 630mPas, obtains the mixed serum of dilution; Then propyl carbinol and dehydrated alcohol are mixed with the mixed serum of dilution, and dispersed, obtain barrier film coating slurries; Finally, use the mode of line rod coating to be coated in the one side of polyethene microporous membrane in barrier film coating slurries, and under the condition identical with embodiment 1, be dried the described battery diaphragm of acquisition.
The properties of battery diaphragm prepared by the present embodiment is as shown in table 1, and testing method is identical with embodiment 1.
In the present embodiment, the same LA series aqueous binder that uses, belongs to acrylic acid or the like aqueous binder.Than embodiment 3 and 4, the content of alumina particle is increased to 20 weight parts, comprise that as can be seen from Table 1 the properties of thermotolerance and Gas permeability all increases.
Embodiment 6
Consisting of of the present embodiment floating coat composition: aqueous double-component polyurethane emulsion (in solid content) 1 weight part, alumina particle 20 weight parts, Virahol 1 weight part and polyurethanes flow agent 3 weight parts.
First polyurethanes aqueous binder is added and in deionized water, be mixed with the tackiness agent slurries that viscosity is 4500mPas; Again alumina particle is added in the tackiness agent slurries of acquisition, use ball mill that alumina particle is uniformly dispersed, obtain mixed serum; Again adding deionized water to regulate the viscosity of described mixed serum is 1400mPas, obtains the mixed serum of dilution; Then Virahol and polyurethanes flow agent are mixed with the mixed serum of dilution, and dispersed, obtain barrier film coating slurries; Finally, use the mode of line rod coating to be coated in the one side of polyethene microporous membrane in barrier film coating slurries, and be dried 1h under 100 ℃ of conditions, obtain described battery diaphragm.
The properties of battery diaphragm prepared by the present embodiment is as shown in table 1, and testing method is identical with embodiment 1.
In the present embodiment, use polyurethanes aqueous binder, and regulate the mixed serum viscosity of dilution larger, make to be formed at the lip-deep coating of polyethene microporous membrane thicker, further improve the thermotolerance of the battery diaphragm of preparation, in coating composition, also contain polyurethanes flow agent, the battery diaphragm surface of preparation is comparatively smooth simultaneously.
Embodiment 7
Consisting of of the present embodiment floating coat composition: carboxylic styrene-butadiene rubber latex (in solid content) 1 weight part, Xylo-Mucine 0.5 weight part, silica dioxide granule 25 weight parts, propylene glycol 0.75 weight part and fluorine carbon flow agent 0.075 weight part.
First carboxylic styrene-butadiene rubber latex and Xylo-Mucine are dissolved in deionized water, be mixed with the tackiness agent slurries of pasty state, viscosity is 3000mPas, then silica dioxide granule is added in the tackiness agent slurries of acquisition, use ball mill that silica dioxide granule is uniformly dispersed, obtain mixed serum; Again adding deionized water to regulate the viscosity of described mixed serum is 800mPas, obtains the mixed serum of dilution; Then propylene glycol and fluorine carbon flow agent are mixed with the mixed serum of dilution, and dispersed, obtain barrier film coating slurries; Finally, use the mode of line rod coating to be coated in the one side of polyethene microporous membrane in barrier film coating slurries, and under the condition identical with embodiment 1, be dried the described battery diaphragm of acquisition.
The properties of battery diaphragm prepared by the present embodiment is as shown in table 1, and testing method is identical with embodiment 1.
In the present embodiment, use carboxylic styrene-butadiene rubber latex as aqueous binder, Xylo-Mucine is as stablizer.At Gas permeability and other performances, meet under the prerequisite of application requiring, resistance toheat is significantly improved with respect to the polyethene microporous membrane without coating modified.
Comparative example 1
Polyethene microporous membrane in use embodiment 1-7, directly as battery diaphragm, is tested its resistance toheat and Gas permeability.The properties of the battery diaphragm in the present embodiment is as shown in table 1, and testing method is identical with embodiment 1.
With in comparative example 1, do not have cated polyethene microporous membrane and compare, the thermotolerance of the battery diaphragm making in embodiment 1-7 obviously improves, at 105 ℃ without thermal contraction, at 150 ℃, percent thermal shrinkage is not higher than 10%, be significantly less than 50% the shrinking percentage of being greater than that does not have cated polyethene microporous membrane, while testing the percent thermal shrinkage of barrier film at 200 ℃, do not have cated polyethene microporous membrane to melt completely, and the battery diaphragm making in embodiment 1-7 still can guarantee good integrity.Therefore when battery temperature reaches 200 ℃, the battery diaphragm making in embodiment 1-7 can be avoided positive and negative electrode directly to contact and cause short circuit, guarantees the security of battery.The battery diaphragm making in embodiment 1-7 can be applied in power truck, and motor vehicle driven by mixed power, in the medium-sized and large-scale power-supply battery of plug-in grade.
Table 1
Finally it should be noted that: each embodiment, only in order to technical scheme of the present invention to be described, is not intended to limit above; Although the present invention is had been described in detail with reference to aforementioned each embodiment, those of ordinary skill in the art is to be understood that: its technical scheme that still can record aforementioned each embodiment is modified, or some or all of technical characterictic is wherein equal to replacement; And these modifications or replacement do not make the essence of appropriate technical solution depart from the scope of various embodiments of the present invention technical scheme.
Claims (14)
1. a coating composition, its composition comprises:
Aqueous binder 1 weight part, particles of inorganic material 1-30 weight part, wetting agent 0.5-6 weight part, flow agent 0-3 weight part and stablizer 0-0.8 weight part in solid content.
2. coating composition according to claim 1, wherein, described aqueous binder is selected from rubber-like aqueous binder, polyvinyl alcohol aqueous binder, polyurethanes aqueous binder or polyacrylic aqueous binder.
3. coating composition according to claim 1, wherein, in described coating composition, described stablizer is 0.1-0.8 weight part.
4. coating composition according to claim 3, described aqueous binder is rubber-like aqueous binder.
5. coating composition according to claim 1, wherein, described wetting agent is alcohols wetting agent.
6. coating composition according to claim 1, described particles of inorganic material comprises a kind of or its arbitrary combination in calcium carbonate, magnesium oxide, calcium oxide, silicon-dioxide, aluminum oxide and zirconium dioxide.
7. according to the coating composition described in claim 1 or 6, the particle diameter of described particles of inorganic material is 50-500nm.
8. according to the coating composition described in claim 1 or 6, it forms and comprises particles of inorganic material 10-20 weight part.
9. according to the coating composition described in claim 1-8 any one, it forms and comprises flow agent 0.2-3 weight part.
10. a battery diaphragm, the coating that it has polymer-based film and utilizes the coating composition described in claim 1-9 any one to form at least one surface of described polymer-based film.
11. battery diaphragms according to claim 10, wherein, the thickness of described coating is 0.1-1 times of described polymer-based carbon film thickness.
12. 1 kinds of methods of preparing the battery diaphragm as described in claim 10 or 11, comprising:
Aqueous binder and stablizer and water are hybridly prepared into the tackiness agent slurries that viscosity is 2000-5000mPas;
Particles of inorganic material is mixed with described tackiness agent slurries, and dispersed, obtain mixed serum;
Adding water, to regulate the viscosity of described mixed serum be 10-1500mPas, obtains the mixed serum of dilution;
Wetting agent and flow agent are mixed with the mixed serum of dilution, and dispersed, obtain barrier film coating slurries;
At least one surface that barrier film coating slurries is coated on to polymer-based film is upper, and the dry rear coating that forms, obtains described battery diaphragm.
13. methods according to claim 12, wherein, at least one surface that barrier film coating slurries is coated on to polymer-based film is upper, the dry rear described battery diaphragm that obtains at 40-100 ℃.
14. according to the method described in claim 12 or 13, and wherein, blending means is for being used colter stirrer, double planetary mixer or ball mill to mix.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105176150A (en) * | 2015-10-27 | 2015-12-23 | 华北电力大学（保定） | Preparing method for transparent super-hydrophobic coating resistant to cutting and acid and alkaline corrosion |
| CN109411678A (en) * | 2018-10-16 | 2019-03-01 | 苏州捷力新能源材料有限公司 | A kind of high security ceramic diaphragm and preparation method for lithium ion battery |
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| CN105176150B (en) * | 2015-10-27 | 2017-10-10 | 华北电力大学（保定） | A kind of resistance to knife cuts the preparation method of the transparent hydrophobic coating of acid-alkali-corrosive-resisting |
| CN109411678A (en) * | 2018-10-16 | 2019-03-01 | 苏州捷力新能源材料有限公司 | A kind of high security ceramic diaphragm and preparation method for lithium ion battery |
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