CN105713228A - Manufacture method and applications of high temperature resistant and deformation resistant composite microporous membrane - Google Patents
Manufacture method and applications of high temperature resistant and deformation resistant composite microporous membrane Download PDFInfo
- Publication number
- CN105713228A CN105713228A CN201410736006.5A CN201410736006A CN105713228A CN 105713228 A CN105713228 A CN 105713228A CN 201410736006 A CN201410736006 A CN 201410736006A CN 105713228 A CN105713228 A CN 105713228A
- Authority
- CN
- China
- Prior art keywords
- polyethylene
- adhesive
- microporous membrane
- polymer
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Landscapes
- Cell Separators (AREA)
Abstract
The invention discloses a manufacture method and applications of a high temperature resistant and deformation resistant composite microporous membrane. The manufacture method comprises the following steps: (a) providing a polymer microporous membrane; (b) dispersing ceramic nano particles into an aqueous adhesive to form aqueous slurry; (c) painting the aqueous slurry on the surface of the polymer microporous membrane to form a composite microporous membrane; wherein the aqueous adhesive comprises a main adhesive and an interlayer adhesive, the main adhesive is prepared from cellulose ether, natural polymer and derivatives thereof, or a mixture of cellulose ether and natural polymer and derivatives thereof; the interlayer adhesive is prepared from polyacrylamide, poly(vinyl amide), polyvinylpyrrolidone, polymethyl methacrylate, polycarboxylic acid, modified paraffin resin, carbomer, polyacrylic acid, urethane acrylate, polyacrylate copolymer emulsion, cis-polybutadiene, butadiene styrene rubber, polyurethane, carbamate, and liquid glue made of part of acrylic epoxy resin, isobornyl acrylate, starch, modified polyurea, and low molecular polyvinyl wax, and the weight ratio of the main adhesive to the interlayer adhesive is 20:55-65:5.
Description
Technical field
The present invention relates to a kind of aqueous ceramic slurry, this slurry is advantageously used for preparing the high temperature resistant resistance to deformation composite micro porous film being suitable as lithium ion battery separator.It is smooth and resistant to high temperature deformation that the lithium ion battery separator prepared with aqueous ceramic slurry of the present invention has dimensionally stable, outward appearance, uses this film as the durability of the lithium ion battery of barrier film and stability thus improve.
Background technology
Consumption day by day along with non-renewable resources, the particularly consumption of petroleum resources, energy security problem has become as the problem that China must solve, people have to take into account that and tap a new source of energy to replace traditional energy, and developing new forms of energy is also the important means building resource-conserving with friendly environment society with regenerative resource.
The industry that automobile industry develops as a state key support, under the impact of current situation, certainly will move towards road for development light, simple and direct, environmental protection.Therefore, new-energy automobile will become the Developing mainstream of 21st century previous decades, and wherein the core of new-energy automobile is exactly accumulator.Lithium ion battery has the highest energy density, service life cycle, superior performance as automobile energy storage battery, therefore also more and more causes people's interest widely and research.
Along with the demand of lithium ion battery is constantly expanded by people, in use also expose inevitable safety problem, the organic polymer barrier film being such as used for battery plus-negative plate to separate is to prevent short circuit, polyolefin structure due to itself, producing contraction distortion when being subject to external high temperature effect, result may result in the security incidents such as both positive and negative polarity short circuit or blast.
For solving the safety problem of short circuit generation, prior art have employed multinomial measure.Such as, US Patent No. 6,432,586B1 is open a kind of adopts PVDF as binding agent in polymeric membrane, the battery diaphragm being coated on polyolefin film surface to be formed inorganic particulate.This film can effectively prevent short circuit or suppress the growth of dendrite, but the binding agent of this method selection has certain corrosivity, can destroy the structure of polymeric substrate, reduces the mechanical property of material.
The open a kind of lithium rechargeable battery dividing plate of Japan Patent 200980157377.5 and lithium rechargeable battery, be coated in film surface by Non-conductive particles by binding agent, improve flatness and the non-oxidizability of film.
But, prior art does not all mention the resistance to elevated temperatures how improving battery diaphragm.
Current lithium ion battery applications is very extensive, is especially applicable to electrokinetic cell, because its energy density is high and the time of recycling is long.But common polymer separators is due to himself structure, it uses temperature not high, is typically in more than 145 DEG C and arises that melting phenomenon.In this case, inside battery dividing plate can shrink and cause battery short circuit, brings unnecessary potential safety hazard.Therefore, improve lithium ion battery safety in use to seem very for important.
Organic group (oiliness) ceramic size is widely used in lithium ion battery separator coating, organic group slurry method for making is mostly in reference to the politef (PVDF that will mix in the Bellcore technique in lithium ion battery, main material) and pottery (a small amount of backing material) mixed slurry be coated in the method on pole piece, being ceramic as main material using its method improvement, PVDF is only used as adhesive-coated on lithium ion battery separator.Its method is added to by ceramic particle with PVDF for binding agent and the glue that configures with NMP, acetone etc. for organic solvent, uses the technique of power mixing to make slurry.Although this method has the advantage that processing technique is relatively simple, but because the solvent of its use is the organic solvent that dissolubility is stronger, it is easy to barrier film being produced certain corrosiveness, causes barrier film mechanical strength to reduce, pore structure is damaged.Additionally, due to the solvent of its use, environment having bigger destruction, environment friendly is poor and belongs to the material of national regulatory, it is, thus, sought for the water-based system of organic system can be substituted.
Prior art is referring also to lithium ion battery negative binder system, propose and use general Binary water paste, its processing method processing method with oil slurry substantially is identical, it is join ceramic particle in aqueous binders to be made by power mix and blend, because the water paste adopting Binary at present is less costly, part manufacturer is had to begin to use this processing method, but it is soft to there is barrier film base material in the coating barrier film adopting the method processing, the situation that coating is harder, cause interlayer conformability poor, pliability cannot meet, easily cause overall peeling, the phenomenon of dry linting, be there is bigger hidden danger in battery processing and safety.
Above-mentioned condition in view of prior art, it is desirable to provide the preparation method of a kind of high temperature resistant resistance to deformation composite micro porous film, this method environmental friendliness, and the composite micro porous film prepared have good high-temperature stability and mechanical performance.
Summary of the invention
The preparation method that it is an object of the present invention to provide a kind of high temperature resistant resistance to deformation composite micro porous film, this method environmental friendliness, and the composite micro porous film prepared have good high-temperature stability and mechanical performance.
Therefore, the preparation method that it is an aspect of the invention to provide a kind of high temperature resistant resistance to deformation composite micro porous film, it comprises the steps:
A () provides polymer microporous film；
B ceramic nanoparticles is dispersed in aqueous binder to be formed water-soluble serous by ()；With
C () on the described water-soluble serous surface being coated in described polymer microporous film, will form composite micro porous film；
Described aqueous binder includes the primary binder being selected from cellulose ether, natural polymer and derivant or their mixture, and selected from polyacrylamide, polyvinyl lactam, polyvinylpyrrolidone, polymethyl methacrylate, polycarboxylic acids, modified paraffin resin, carbomer, polyacrylic acid, urethane acrylate, Polyacrylate Emulsion, butadiene rubber, butadiene-styrene rubber, polyurethane, carbamate and part acrylic acid epoxy resin, acrylic acid norbornene ester, starch, modified polyurea, low-molecular polyethylene wax the interlayer adhesive of glue；
The weight ratio of described primary binder and interlayer adhesive is 20:55-65:5.
Accompanying drawing explanation
Fig. 1 is the polymer microporous film prepared in one example of the present invention and the microphotograph of the composite micro porous film with ceramic coating；
Fig. 2 is the polymer microporous film prepared in another example of the present invention and the microphotograph of the composite micro porous film with ceramic coating；
Detailed description of the invention
The preparation method of the present invention is high temperature resistant resistance to deformation composite micro porous film comprises the steps:
A () provides polymer microporous film；
Inventive polymers microporous membrane (also known as porous membranes) is the material expanded owing to electrolytical limitation is difficult to absorb, its at least one in following polymer: ultra-high molecular weight polyethylene, linear polyethylene, branched polyethylene, high density polyethylene (HDPE), Low Density Polyethylene, polypropylene, polyvinyl alcohol, polyvinyl acetate, politef, Kynoar, polyethylene terephthalate, polyurethane, polyimides, polyacrylonitrile, polymethyl methacrylate, butyl polyacrylate, polystyrene and copolymer thereof, polrvinyl chloride, polyimides, Nomex, nylon, polysulfones, Merlon, polyacrylamide, PMAm, polyformaldehyde, polysulfones, polyether sulfone, polyvinylpyrrolidone, polydimethylsiloxane, and their copolymer.
The preferred high density polyethylene (HDPE) of Inventive polymers microporous membrane material, ultra-high molecular weight polyethylene or both mixture.In an example of the present invention, the molecular weight of described high density polyethylene (HDPE) be 500,000 or more than, for instance 50 ten thousand to 500 ten thousand, better 80 ten thousand to 300 ten thousand, better 100 ten thousand to 200 ten thousand；Density is 0.92-0.97g/cm3, preferably 0.94-0.96g/cm3。
The method that Inventive polymers microporous membrane can adopt the present invention conventional prepares.In an example of the present invention, described polymer microporous film adopts blending extrusion technique to prepare, preferably employ twin-screw extrusion method to prepare, the mode that its screw rod is advanced is selected from the same direction, incorgruous traveling etc., preferentially engages in the same direction, and the die head that twin-screw extrusion method adopts is selected from straight material head, side charging head, biasing head, many control multimembrane mouth heads, co-extrusion machine is first-class.
The thickness of Inventive polymers microporous membrane is generally 1～50 μm, it is preferred to 5～30 μm, more preferably 9～25 μm, and within the scope of this, the volume of battery can reduce a lot, and the internal resistance of cell also can reduce simultaneously, and battery energy density significantly improves.
In an example of the present invention, described high temperature resistant resistance to deformation composite micro porous film is to be prepared by the mixture of polyolefin (A) and (B), the weight average molecular weight of polyolefin (A) be 2,000,000 or more than, for instance 300 ten thousand to 600 ten thousand, better 400 ten thousand to 500 ten thousand；The weight average molecular weight of polyolefin (B) is about 1,000,000, melt index is 0.5～2g/10min；Two kinds of polyolefinic mass ratioes are between 20/60～60/30, more fortunately between 30/50-70/50.
In another example of the present invention, described polymer microporous film adopts Thermal inactive (TIPS) method to prepare, and it comprises the steps:
A polymeric components is dissolved in the solvent of high boiling point, low volatility at high temperature and forms homogeneous liquid by ()；
B () cooling down, makes solution produce liquid-solid phase and separates or liquid-liquid phase separation；
C described high boiling solvent is extracted by () with volatile reagent, through the dried porous membranes obtaining and having pore structure shape；
In a better example of the present invention, before solvent extraction, the microporous membrane formed is carried out unidirectional or biaxial tension, and carry out qualitative rolling after the extraction, carry out trimming, rolling and the step such as cut.
The porosity of Inventive polymers microporous membrane is 30-46%, preferably 35-45%, more preferably 38-42%, it is preferable that 39-40%；Longitudinal tensile strength is 180-260MPa, preferably 190-250MPa, more preferably 200-240MPa, it is preferable that 210-230MPa；Transverse tensile strength is 110-160MPa, preferably 120-150MPa, more preferably 130-140MPa.
The air permeability of Inventive polymers microporous membrane is 150-260sec/100ml, preferably 180-250sec/100ml, more preferably 190-230sec/100ml.
In an example, Inventive polymers microporous membrane is microporous polyolefin film, it is by polyolefin or polyolefin component, addition if desired gives the resin components such as the polymer of low temperature closedown effect and is mixed with organic liquid or solid, extrusion molding after melting mixing, by stretching, remove solvent, dry, heat treatment and obtain.The preferred method of the present invention, it is in polyolefin or in polyolefin composition, add polyolefinic fine solvent, configuration polyolefin or polyolefin composition solution, by the mold pressing extruding layer tablet of this solution extruder, cooling, form gelatinous mixture, this gelatinous mixture is heated, stretches, finally remove solvent, after drying, porous membranes is obtained after thermal finalization.
B ceramic nanoparticles is dispersed in aqueous binder and forms serosity by ()
Aqueous binder of the present invention includes (i) primary binder and (ii) interlayer adhesive
(i) primary binder
Primary binder suitable in the inventive method is selected from cellulose ether, natural polymer and derivant thereof or their mixture.
Can enumerate as cellulose ether: the mixture of methylcellulose, hydroxypropyl methyl cellulose, sodium carboxymethyl cellulose, hydroxyethyl cellulose, hydroxyethylmethyl-cellulose, hydroxypropyl cellulose, sulfoethyl cellulose, carboxy methyl cellulose ammonium salt, gelatin, sodium alginate, chitin, chitosan or its two or more formation.
In aqueous binder of the present invention, the major function of primary binder is thickening and powder adhesion, and it can be effectively ensured the slurry made and reduce sedimentation or the function of layering in longer-term storage process, is effectively reduced the situation that powder body comes off simultaneously.
In an example of the present invention, with the gross weight gauge of aqueous binder, described primary binder accounts for the 20%～65% of binding agent total amount, better accounts for 25%-60%, better accounts for 30-55%, it is preferable that account for 35-50%.
(ii) interlayer adhesive
Suitable in the inventive method interlayer adhesive selected from polyacrylamide, polyvinyl lactam, polyvinylpyrrolidone, polymethyl methacrylate, polycarboxylic acids, modified paraffin resin, carbomer, polyacrylic acid, urethane acrylate, Polyacrylate Emulsion, butadiene rubber, butadiene-styrene rubber, polyurethane, carbamate and part acrylic acid epoxy resin, acrylic acid norbornene ester, starch, modified polyurea, low-molecular polyethylene wax glue, or the mixture of its two or more formation.
In the methods of the invention, the major function of interlayer adhesive is increase the adhesive property between coat and barrier film, it is prevented that the phenomenon of coating layer flaking, simultaneously the slight polarity changing entire slurry.
In an example of the present invention, with the gross weight gauge of aqueous binder, the amount of described interlayer adhesive accounts for the 5%～55% of binding agent total amount, preferably 10-50%, more preferably 15-45%, it is preferable that 20-40%.
The preparation method of interlayer cling-materials of the present invention is without particular limitation, it is possible to for example be by polymerisation in solution, suspension polymerisation, polymerisation in bulk, emulsion polymerization prepare, it is preferred to use emulsion polymerisation process prepare.
In an example of the present invention, adopting metering system ester type compound as interlayer adhesive, its preparation method is as follows:
In the voltage-resistant reactor with self-poking arrangement, add the Butyl Acrylate Monomer 60-80 part as methacrylic acid monomer, as unsaturated carboxylic acid body acrylic acid 24-28 part, as being the rare propyl ester 3-6 part of methacrylic acid containing unsaturated (methyl) acrylic monomers, dodecylbenzene sodium sulfonate 1-3 part as emulsifying agent, ion exchange water 150-250 part, initiator as polymerization adopts potassium peroxydisulfate a, after being sufficiently stirred for, it is heated to 60 DEG C and causes polymerization, after conversion ratio reaches 98%, stopped reaction, obtain the macromolecule emulsion of containing water-soluble polymer.
Ceramic nanoparticles of the present invention is selected from silicon dioxide, titanium dioxide, aluminium oxide, calcium oxide, calcium carbonate, aluminium nitride, boron nitride, brium carbonate etc., it is preferable that silicon dioxide, aluminium oxide.The reason selecting above-mentioned inorganic nanoparticles is owing to itself is high temperature resistant, and can stir in the solution and have good dispersibility, it is easy to long storage time not easily precipitates and caking property is good.
The mean diameter of ceramic nanoparticles of the present invention more than 2nm less than 12 μm, more preferably more than 20nm less than 4 μm.When the particle diameter of inorganic nano ceramic particle is when about 200nm, easily, interparticle space is also relatively easy to control in dispersion coating.
Present slurry also optionally includes other additive, for instance adhesion promoter, surfactant, polarity corrector etc..
The not limiting example of the adhesion promoter being suitable for the inventive method has, for instance the mixture etc. of polyoxyethylene (PEO), Polyethylene Glycol (PEG), polyvinylpyrrolidone (PVP) or its two or more formation.Described adhesion promoter generally has better adhesive property than described main binder, and after being stirred by high speed dispersor, its long-chain molecule structure cross-links entangled with the network molecular structure of main binder, forms network structure, it is possible to play better adhesive effect.
In an example of the present invention, by the gross weight gauge of aqueous binder, the consumption of described adhesion promoter accounts for 3-15%, better accounts for 2%～10%, better accounts for 4-6%.
Present slurry also optionally includes surfactant.Not limiting example suitable in the surfactant of the inventive method has, such as sodium n-alkylbenzenesulfonate (LAS), polyoxyethylenated alcohol sodium sulfate (AES), AESA (AESA), sodium laurylsulfate (K12 or SDS), Nonyl pheno (10) ether (TX-10), gelatin, diglycollic amide (6501) glycerol stearate monoesters, lignosulfonates, heavy alkylbenzene sulfonate, alkylsulfonate (petroleum sulfonate), dispersing agent NNO, dispersing agent MF, alkyl, polyether (PO-EO copolymer), sodium polyacrylate, aliphatic alcohol polyethenoxy (3) ether (AEO-3) PESA poly-epoxy succinic acid (sodium), or the mixture of its two or more formation.
Add the effect that surfactant contributes to preventing ceramic nanoparticles flocculation sediment, disperseing not open, it is ensured that the suspension of ceramic particle and dispersion, extend the storage period of ceramic size.
In an example of the present invention, by the gross weight gauge of described aqueous binder, the consumption of described surfactant accounts for the 0%～15% of binding agent gross weight, better accounts for 2-13%, better accounts for 5-10%, it is preferable that 6-8%.
Present slurry also optionally includes polarity and adjusts component, it is non-polar solven that modal polarity adjusts component, such as benzene, toluene, dimethylbenzene, oxolane, carbon tetrachloride, ethyl acetate, acetonitrile, methanol, ethanol, butanol, isopropanol, 1, 3 butanediols, gamma-butyrolacton, dichloromethane, chloroform, Ketohexamethylene, acetone, butanone, N-Methyl pyrrolidone (NMP), preferred N-Methyl pyrrolidone (NMP) or 1, 3-dimethyl-2-imidazolinone (DMI), preferably ethyl acetate, isopropyl myristate, DMI, NMP and part ketone.Add this material minimal amount of and can effectively change the polarity of slurry, ensure its enhancing with organic barrier film adhesive attraction simultaneously.
In an example of the present invention, by the gross weight gauge of described aqueous binder, it is 0-5% that described polarity adjusts the consumption of component, preferably 0.01%～3%, and more preferably 0.05-2%, it is preferable that 0.08-1.2%.
The preparation method of present slurry is without particular limitation, it is possible to be any conventional method known in the art, for instance each component (including the water as disperse medium) stirring mixed.Ceramic size mixing arrangement suitable in the inventive method is without particular limitation, it is possible to be any common mixing device known in the art, as long as can be mixed by mentioned component.The not limiting example of described mixing arrangement has, for instance hypervelocity dispersion machine, ball mill, puddle mixer, planetary mixer etc..
In an example of the present invention, described serosity is adopted and is prepared with the following method:
1. weigh: weigh main binder, help the mixture of binding agent and surfactant, wherein main binder: interlayer cling-materials: adhesion promoter: the weight ratio of surfactant is 25-35:10-15:4-6:2-4, preferably 28-32:12-14:4.5-5.5:2.5-3.5, more preferably 30:13:5:3.By the weighing scale of mixture, add the water of 20%～60%；Wherein hydroxypropyl cellulose selected by primary binder, and interlayer cling-materials selects SBR emulsion or methacrylate emulsions, helps binding agent to select polyoxyethylene (PEO) or Polyethylene Glycol (PEG).
2. gluing: mixture mixing roll obtained above or blender are stirred more than 1 hour, the glue clarification of generation, wherein without solid particle；
3. filter: the above-mentioned glue accomplished fluently is carried out vacuum filtration by 200 mesh sieve；
4. the mixing of nano-particle: joined by the nano-particle weighed up in the glue prepared, stirs 1 hour through mixing roll or blender；
5. high speed dispersion: use high speed dispersor to disperse in the above-mentioned slurry mixed；
6. the addition of interlayer cling-materials: add interlayer cling-materials in the 5%～55% of total binding agent ratio；
7. polarity regulates: in the 1%～8% of total binding agent ratio, carries out polarity adjustment, makes the dyne power of aqueous binders closer to the surface dynes power with barrier film, play good bonding effect；
8. vacuum defoamation: blender is adjusted to low rate mixing, evacuation 30min, carries out deaeration；
9. filter: slurry good for above-mentioned deaeration is carried out vacuum filtration by 150 mesh sieve, obtains final slurry.
The aqueous ceramic slurry prepared by the inventive method has performance:
(1) solid content is 35～45%, preferably 38-42%；
(2) range of viscosities of slurry is at 60～120mPa S-1, preferably 80～110mPa S-1, more preferably 90～100mPa S-1；
(3) stability and reliability: there is stable ageing, excellent coating pull-out capacity and good caking property:
C () on the described water-soluble serous surface being coated in described polymer microporous film, will form composite micro porous film.
The preparation method of the high temperature resistant resistance to deformation composite micro porous film of the present invention is that ceramic nanoparticles of the present invention is configured to certain density ceramic size, by aqueous binder nontoxic, eco-friendly as ply adhesion, pass through coating technique, solution is coated in the single or double of polymeric support layer, process through thermal finalization, this kind of ceramic layer also forms certain micropore, is unlikely to reduce the breathability of microporous membrane.
The method being suitable for being coated with pottery serosity of the present invention is without particular limitation, as long as it can form a kind of nano ceramic coat on described polymer microporous film.The not limiting example of suitable painting method has, for instance rubbing method, infusion process, rolling method, spraying process, rotary coating etc., considers from stability, uniformity and operability, it is preferable that rubbing method.
The not limiting example of suitable rubbing method has, for instance doctor blade method, direct rod method etc..
The moisture in serosity can be removed after coating.There is no specific method from the coated film aspect that dewaters, dewater usually by dry, infrared exoelectron can be enumerated as drying means and dry, or adopt heat temperature forced air drying.
In an example of the present invention, in dry run or dried also optionally the film obtained is carried out pressurized treatments, such as mold pressing or roll-in；So that the adaptation of perforated membrane and ceramic layer can be improved.
The ceramic membrane that the inventive method is formed at the one or both sides of polymer microporous film, this ceramic membrane is a kind of high temperature resistant resistance to deformation coat, wherein polymer micro rete is as the supporting layer of ceramic film, bond completely between water paste layer and microporous film layers, and without interlayer spacings, the specific composite micro porous film of this performance can be obtained after Overheating Treatment.
The inventive method also includes coating is dried heat treated step after application, and applicable baking temperature is without particular limitation, it is possible to be ordinary temperature known in the art.
In an example of the present invention, the method as preparing high temperature resistant resistance to deformation composite micro porous film: aqueous inorganic particle slurry is coated on perforated membrane and is coated and adopts the method for infrared drying to obtain the regulatable composite micro porous film of thickness.
In another example of the present invention, the method that the aqueous ceramic slurry configured is coated on porous membranes, it is possible to enumerate scraper for coating method, directly it is coated with rod method, extrusion molding.Air-dry dry, the infrared ray of infrared vacuum drying, warm braw, hot blast, low humidity or electron beam etc. can be utilized as drying means.As long as baking temperature can so that the temperature of moisture vaporization in film, pottery coating microporous film has following structure: by binding agent by inorganic nano ceramic particle, thus forming Non-conductive particles space, electrolyte can pass through space normal reaction.
The inventive method adopts a kind of nontoxic, environmental friendliness interlayer cling-materials, it is coated on the surface of polyalcohol stephanoporate basement membrane together with the slurry being mixed with inorganic nanoparticles so that the composite membrane obtained has possessed more excellent mechanical property, ionic conductance, long-term cycle characteristics and good face flatness.Composite membrane of the present invention can be used on lithium ion battery and manufactures, and can improve lithium ion battery safety in utilization, recycle characteristic, chemical stability etc..
Embodiment
The present invention is further illustrated below in conjunction with embodiment.
Test method
1. thickness
Ma Er THICKNESS GAUGE FOR THE MEASUREMENT OF THIN FOILS is adopted to measure
2. air permeability
Gurley permeating degree tester 4110 is adopted to measure
3. hole content
The full-automatic mercury injection apparatus of health tower Poremaster-33 is adopted to measure
4. thermal contraction
Sample is measured respectively along machine direct of travel original length L0 under room temperature constant temperature, it is perpendicular to machine direct of travel T0, by sample in constant temperature and humidity controllable oven, it is cooled under original test condition heat the experiment of 1h with 105 DEG C after, measuring now that sample is along machine direct of travel length L1 and crossmachine direct of travel length T1, computing formula is as follows:
MD%=(L1-L0)/L0 × 100%
TD%=(T1-T0)/T0 × 100%
5. puncture strength
Japan's KES-G5 manual compression experimental machine is adopted to measure
6. hot strength
Shanghai Xiang Jie instrument and meter Science and Technology Co., Ltd. is adopted to measure.
7. moisture content test
Full-automatic prunus mume (sieb.) sieb.et zucc. Teller-Tuo benefit HX204 Moisture Meter is adopted to measure.
8. circulating battery test
Shenzhen 6 DOF Science and Technology Ltd. 5V2A type battery cycle life tester is adopted to measure.
Embodiment 1
1. prepare polymer porous film
It is 2 × 10 to molecular weight-6The polyethylene of g/mol adds, by the weighing scale of this polyethylene, the antioxidant 2 of 0.3%, 6 tert-butyl group-4 methylphenols and phosphite ester (both weight ratios are 1:1), add after mixing in screw extruder, extrusion pusher side material mouth supply crude mineral oils is as solvent, and the addition of this solvent accounts for the 65% of polyethylene gross weight.
At 210 DEG C mixing, speed with 75 turns/min, in screw rod transmission section, stirring is sheared and is formed polyethylene gel, the stretched film of 745 μm is extruded from the T-shaped die head on extruder top, through biaxial tension (longitudinal stretching ratio is 5, and cross directional stretch ratio is 7.8), after oil removing, 125 DEG C of thermal finalizations, the ultra-high molecular mass polyethylene micropore film of 12 μm can be obtained.
2. prepare ceramic size
Weigh main binder, help binding agent and surfactant；Described main binder and the gross weight helping binding agent are 1.5 kilograms, main binder: adhesion promoter: surfactant component presses the weight ratio proportioning of 30:5:3, described primary binder is hydroxypropyl cellulose, described to help binding agent be polyethylene glycol oxide (PEO), and described surfactant is sodium laurylsulfate.Being added by above-mentioned material in 24.79 kg of water, stirring, clarification obtain the serosity without solid particle.Above-mentioned serosity is carried out vacuum filtration by 200 mesh sieve, obtains glue.
Joining in above-mentioned glue by 23 kilograms of alumina ceramic grains (VK-L30, purchased from Hangzhou Wanjing New Material Co., Ltd.), stirring is high speed dispersion also.Adding 0.56 kilogram of interlayer cling-materials butadiene-styrene rubber, add 0.15 kilogram of polar modifier N-Methyl pyrrolidone (NMP) and carry out polarity adjustment after stirring, stirring final vacuum 30min carries out deaeration.The slurry of above-mentioned deaeration is carried out vacuum filtration by 150 mesh sieve, obtains water paste.
Above-mentioned water paste is coated with on microporous membrane obtained above by coating machine (MCD type ultraprecise coating machine, purchased from Fuji Mechanical industry Co., Ltd.), the dried nano ceramic coat forming a layer 2 μm, test water content 200ppm through Moisture Meter.
Adopting said method to evaluate its performance, result is listed in table 1 (heat-shrinkable result of the test is listed in the table below 4):
Table 1:
As can be seen from Table 1, in basic unit after coated ceramic granule, there is not significant change in breathability, illustrates that this coated separator does not result in considerable influence to making battery core.Porosity is significantly greater, illustrate that the ceramic coating of coating has bigger porosity, the memory space of more electrolyte can be provided, the cycle performance of battery had good help, it is improved with hour hands intensity and hot strength, improves battery resistance to sparking energy in use and security performance.
With the SEM photograph of the prepared barrier film of said method of the present invention as shown in Figure 1.
Embodiment 2
1. prepare polymer porous film
To molecular weight 2.5 × 10-6In the polyethylene of g/mol, by the weighing scale of this polyethylene, add 0.32% mixing antioxidant 2,6 tert-butyl group-4 methylphenols and phosphite ester (both weight ratios are 1:1), adding after mixing in screw extruder, extrusion pusher side material mouth adds by the crude mineral oils of polyethylene and total amount of antioxidants 66%.At 210 DEG C mixing, speed with 70 turns/min, in screw rod transmission section, stirring is sheared and is formed polyethylene gel, the stretched film of 780 μm is extruded from the T-shaped die head on extruder top, through biaxial tension (longitudinal stretching ratio is 5.2, and cross directional stretch ratio is 7.7), after oil removing, 120 DEG C of thermal finalizations, obtain the ultra-high molecular mass polyethylene micropore film of 12 μ m-thick.
2. prepare ceramic membrane
Weigh main binder that gross weight is 1.4 kilograms, help binding agent and surfactant (main binder: adhesion promoter: the weight ratio of surfactant is 30:4:3), described primary binder is hydroxypropyl cellulose, described to help binding agent be polyethylene glycol oxide (PEO), and described surfactant is dodecylbenzene sodium sulfonate.Being added by above-mentioned material in 24.65 kg of water, stirring, clarification obtain the serosity without solid particle.Above-mentioned serosity is carried out vacuum filtration by 200 mesh sieve, is subsequently added 23.28 parts of alumina ceramic grains (VK-L30, purchased from Hangzhou Wanjing New Material Co., Ltd.), stirs and use high speed dispersor to disperse.
In the serosity after above-mentioned dispersion, add 0.42 kilogram of butadiene-styrene rubber as interlayer cling-materials, add 0.25 kilogram of polar modifier DMI (DMI) and carry out polarity adjustment.Stirring evacuation 30min carry out deaeration.Slurry good for above-mentioned deaeration is carried out vacuum filtration by 150 mesh sieve, obtains final water paste.
By above-mentioned water paste by coating machine (MCD type ultraprecise coating machine, purchased from Fuji Mechanical industry Co., Ltd.) it is coated on porous membranes obtained above, the dried nano ceramic coat forming a layer 2 μm on microporous membrane, tests water content 180ppm through Moisture Meter.
Measuring the performance of this product in aforementioned manners, result is (heat-shrinkable result of the test is listed in the table below 4) as listed in table 2.
Table 2:
As can be seen from Table 2, in basic unit after coated ceramic granule, there is not significant change in breathability, illustrates that this coated separator does not result in considerable influence to making battery core.Porosity is significantly greater, illustrates that the ceramic coating that the present invention is coated with has bigger porosity, using the teaching of the invention it is possible to provide the memory space of more electrolyte, and the cycle performance of battery is had good help.
The SEM photograph of the present embodiment film is as shown in Figure 2.
Embodiment 3
1. prepare polymer porous film
With the weight ratio of 60:40 by molecular weight 1.5 × 10-6The ultra-high molecular weight polyethylene of g/mol and molecular weight are 2.2 × 10-6The ultra-high molecular weight polyethylene mix homogeneously of g/mol.By the gross weight gauge of this mixture, add 0.28% mixing antioxidant 2,6 tert-butyl group-4 methylphenol and phosphite ester (both weight ratios are 1:1).Adding after mixing in screw extruder, extrusion pusher side material mouth addition accounts for polymer and the crude mineral oils of total amount of antioxidants 64%.At 210 DEG C mixing, speed with 80 turns/min, in screw rod transmission section, stirring is sheared and is formed polyethylene gel, the stretched film of 580 μm is extruded from the T-shaped die head on extruder top, through biaxial tension (longitudinal stretching ratio is 4.2, and cross directional stretch ratio is 8.8), after oil removing, 118 DEG C of thermal finalizations, the ultra-high molecular mass polyethylene micropore film of 9 μm can be obtained.
2. prepare ceramic membrane
Weigh 2.5 kilograms of main binder hydroxypropyl celluloses, help the mixture of binding agent polyethylene glycol oxide (PEO) and surfactant sodium laurylsulfate, wherein main binder: adhesion promoter: the weight ratio of surfactant is 30:5:6.Being added by said mixture in 22.55 kg of water, stirring, clarification obtain the serosity without solid particle.Above-mentioned serosity is carried out vacuum filtration by 200 mesh sieve, obtains serosity.
Joining in above-mentioned glue by 23.5 kilograms of silicon oxide ceramics granules (LF25, purchased from Xiushan Mountain Long Fei new material company limited), stirring is high speed dispersion also.It is added thereto to 0.875 kilogram of methacrylate emulsions as interlayer cling-materials, adds 0.575 kilogram of DMI (DMI) after mixing and carry out polarity adjustment.After stirring, evacuation 30min carries out deaeration, carries out vacuum filtration by 150 mesh sieve, obtains final water paste.
Polymer sheet layer is formed by Screw Extrusion, the water paste configured is passed through coating machine (MCD type ultraprecise coating machine, purchased from Fuji Mechanical industry Co., Ltd.) it is coated with on above-mentioned porous membranes, through heat drying, microporous membrane is formed the nano ceramic coat of one layer of 3 μ m-thick, tests water content 115ppm through Moisture Meter.
Measuring its performance in aforementioned manners, result is listed in table 3 (heat-shrinkable result of the test is listed in the table below 4):
Table 3
As can be seen from Table 3, in basic unit after coated ceramic granule, there is not significant change in breathability, illustrates that this coated separator does not result in considerable influence to making battery core.Porosity is significantly greater, illustrates that the ceramic coating that the present invention is coated with has bigger porosity, using the teaching of the invention it is possible to provide the memory space of more electrolyte, and the cycle performance of battery is had good help.
Table 4
*: ND12, purchased from Shanghai En Jie material Science and Technology Co., Ltd.
It can be seen that commercially available basement membrane is after overheat contraction experiment test from upper table 4, along with the rising of temperature, Heat Shrinkage value becomes larger, and cuddles up in a heap time more than 140 DEG C.Thermal dimensional stability is poor.But composite micro porous film of the present invention is after overheat contraction is tested, after toasting 1 hour under 180 DEG C of high temperature, Heat Shrinkage value is less.Comparatively speaking, therefore, composite micro porous film of the present invention has better thermal dimensional stability, and security performance is more excellent.
Embodiment 4
(preparation method and the material of lithium ion battery)
The preparation method of lithium ion battery in this example, being in that lithium ion battery described in its feature is made up of positive pole system, negative pole system, electrolyte system, wherein positive level adopts LiMn2O4, and negative pole adopts graphite, electrolyte adopts system to be EC/EMC system, and lithium salt is (LiPF6) for 1mol/L.Preparation section: positive pole is by LiMn2O4, PVDF is by weight 100:3 composition, negative pole is by graphite, carboxymethyl cellulose (CMC), butadiene-styrene rubber presses 100:2:3 weight ratio composition, positive pole adopts NMP to be solvent, negative pole adopts water as solvent, it is respectively prepared anode and cathode slurry, barrier film adopts the prompt 12 μm of basement membranes of grace, with 12+2 μm, 12+3 μm, 9+3 μm of composite micro porous film, laminated aluminum film is used after curling for the pole piece cut getting well, organic electrolyte is added when nitrogen, by battery vacuum-pumping an envelope, then after battery room temperature ageing 3h, both lithium ion battery it had been shaped to.
Table 5. barrier film is used for manufacturing lithium rechargeable battery electric performance test table
It is used for manufacturing lithium rechargeable battery electric performance test from barrier film, adopts the compare battery of conventional separator of the secondary cell of the present invention this composite micro porous film manufacture to be in discharge and recharge, energy density or recycle number of times all has very big advantage.
Claims (10)
1. a preparation method for composite micro porous film, it comprises the steps:
A () provides polymer microporous film；
B ceramic nanoparticles is dispersed in aqueous binder to be formed water-soluble serous by ()；With
C () on the described water-soluble serous surface being coated in described polymer microporous film, will form composite micro porous film；
Described aqueous binder includes the primary binder being selected from cellulose ether, natural polymer and derivant or their mixture, and selected from polyacrylamide, polyvinyl lactam, polyvinylpyrrolidone, polymethyl methacrylate, polycarboxylic acids, modified paraffin resin, carbomer, polyacrylic acid, urethane acrylate, Polyacrylate Emulsion, butadiene rubber, butadiene-styrene rubber, polyurethane, carbamate and part acrylic acid epoxy resin, acrylic acid norbornene ester, starch, modified polyurea, low-molecular polyethylene wax the interlayer adhesive of glue；
The weight ratio of described primary binder and interlayer adhesive is 20:55-65:5.
2. the method for claim 1, it is characterized in that described polymer microporous film is at least one in following polymer: ultra-high molecular weight polyethylene, linear polyethylene, branched polyethylene, high density polyethylene (HDPE), Low Density Polyethylene, polypropylene, polyvinyl alcohol, polyvinyl acetate, politef, Kynoar, polyethylene terephthalate, polyurethane, polyimides, polyacrylonitrile, polymethyl methacrylate, butyl polyacrylate, polystyrene and copolymer thereof, polrvinyl chloride, polyimides, Nomex, nylon, polysulfones, Merlon, polyacrylamide, PMAm, polyformaldehyde, polysulfones, polyether sulfone, polyvinylpyrrolidone, polydimethylsiloxane, and their copolymer.
3. method as claimed in claim 1 or 2, it is characterised in that described polymer micro membrane material is high density polyethylene (HDPE), ultra-high molecular weight polyethylene or both mixture.
4. method as claimed in claim 3, it is characterised in that the molecular weight of described high density polyethylene (HDPE) be 500,000 or more than, density is at 0.92-0.97g/cm3。
5. method as claimed in claim 1 or 2, it is characterised in that the air permeability of described polymer microporous film is 150-260sec/100ml, preferably 180-250sec/100ml, more preferably 190-230sec/100ml.
6. method as claimed in claim 1 or 2, it is characterised in that with the gross weight gauge of aqueous binder, described primary binder accounts for the 20%～65% of binding agent total amount, better accounts for 25%-60%, better accounts for 30-55%, it is preferable that account for 35-50%.
7. method as claimed in claim 1 or 2, it is characterised in that with the gross weight gauge of aqueous binder, the amount of described interlayer adhesive accounts for the 5%～55% of binding agent total amount, preferably 10-50%, more preferably 15-45%, it is preferable that 20-40%.
8. method as claimed in claim 1 or 2, it is characterised in that described ceramic nanoparticles is selected from silicon dioxide, titanium dioxide, aluminium oxide, calcium oxide, calcium carbonate, aluminium nitride, boron nitride, brium carbonate etc., it is preferable that silicon dioxide, aluminium oxide.The reason selecting above-mentioned inorganic nanoparticles is owing to itself is high temperature resistant, and can stir in the solution and have good dispersibility, it is easy to long storage time not easily precipitates and caking property is good.
9. method as claimed in claim 1 or 2, it is characterized in that described water-soluble serous in also include polarity adjust component, it selected from benzene,toluene,xylene, oxolane, carbon tetrachloride, ethyl acetate, acetonitrile, methanol, ethanol, butanol, isopropanol, 1,3 butanediols, gamma-butyrolacton, dichloromethane, chloroform, Ketohexamethylene, acetone, butanone, N-Methyl pyrrolidone (NMP), preferred N-Methyl pyrrolidone (NMP) or DMI (DMI).
10. the composite micro porous film that method as according to any one of claim 1-9 prepares is as the purposes in battery diaphragm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410736006.5A CN105713228A (en) | 2014-12-04 | 2014-12-04 | Manufacture method and applications of high temperature resistant and deformation resistant composite microporous membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410736006.5A CN105713228A (en) | 2014-12-04 | 2014-12-04 | Manufacture method and applications of high temperature resistant and deformation resistant composite microporous membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105713228A true CN105713228A (en) | 2016-06-29 |
Family
ID=56143782
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410736006.5A Pending CN105713228A (en) | 2014-12-04 | 2014-12-04 | Manufacture method and applications of high temperature resistant and deformation resistant composite microporous membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105713228A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106207059A (en) * | 2016-08-12 | 2016-12-07 | 联想(北京)有限公司 | A kind of lithium ion battery separator, its preparation method and application |
| CN107895765A (en) * | 2017-10-13 | 2018-04-10 | 深圳市旭然电子有限公司 | Inorganic/organic composite porous barrier film, preparation method and its lithium ion battery |
| CN108987649A (en) * | 2018-07-16 | 2018-12-11 | 怀化学院 | Battery ceramic slurry and preparation method thereof, application, battery diaphragm and battery |
| WO2019015671A1 (en) * | 2017-07-21 | 2019-01-24 | Shanghai Energy New Materials Technology Co., Ltd. | Processes and apparatus for preparation of separators of electrochemical devices |
| CN109411679A (en) * | 2018-10-22 | 2019-03-01 | 乐凯胶片股份有限公司 | Ceramic slurry, ceramic diaphragm and lithium ion battery |
| CN109952026A (en) * | 2016-07-22 | 2019-06-28 | 智利圣地亚哥大学 | The polymer comprising CaO nano particle for food packaging |
| CN110581247A (en) * | 2018-06-08 | 2019-12-17 | 上海恩捷新材料科技股份有限公司 | Ceramic composite diaphragm and preparation method thereof |
| CN111682213A (en) * | 2020-06-08 | 2020-09-18 | 广州市乐基智能科技有限公司 | Preparation method of binder for lithium battery |
| CN111900460A (en) * | 2020-08-28 | 2020-11-06 | 常州赛得能源科技有限公司 | Solid electrolyte with self-supporting structure, preparation method and application |
| CN112980118A (en) * | 2021-02-07 | 2021-06-18 | 浙江汉丞科技有限公司 | Fluorine-containing polymer mixture for high-moisture-permeability super-breathable microporous membrane and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103618059A (en) * | 2013-12-10 | 2014-03-05 | 深圳市星源材质科技有限公司 | Lithium ion battery diaphragm with polymer inorganic coating and preparation method for lithium ion battery diaphragm |
| CN103915591A (en) * | 2014-04-09 | 2014-07-09 | 深圳市星源材质科技股份有限公司 | Water-based ceramic coating lithium ion battery diaphragm and processing method thereof |
| CN104868081A (en) * | 2014-12-22 | 2015-08-26 | 上海恩捷新材料科技股份有限公司 | Water-based multi-layer membrane for lithium ion battery |
-
2014
- 2014-12-04 CN CN201410736006.5A patent/CN105713228A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103618059A (en) * | 2013-12-10 | 2014-03-05 | 深圳市星源材质科技有限公司 | Lithium ion battery diaphragm with polymer inorganic coating and preparation method for lithium ion battery diaphragm |
| CN103915591A (en) * | 2014-04-09 | 2014-07-09 | 深圳市星源材质科技股份有限公司 | Water-based ceramic coating lithium ion battery diaphragm and processing method thereof |
| CN104868081A (en) * | 2014-12-22 | 2015-08-26 | 上海恩捷新材料科技股份有限公司 | Water-based multi-layer membrane for lithium ion battery |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109952026A (en) * | 2016-07-22 | 2019-06-28 | 智利圣地亚哥大学 | The polymer comprising CaO nano particle for food packaging |
| CN106207059A (en) * | 2016-08-12 | 2016-12-07 | 联想(北京)有限公司 | A kind of lithium ion battery separator, its preparation method and application |
| CN106207059B (en) * | 2016-08-12 | 2020-02-21 | 联想(北京)有限公司 | Lithium ion battery diaphragm, preparation method and application thereof |
| WO2019015671A1 (en) * | 2017-07-21 | 2019-01-24 | Shanghai Energy New Materials Technology Co., Ltd. | Processes and apparatus for preparation of separators of electrochemical devices |
| CN107895765A (en) * | 2017-10-13 | 2018-04-10 | 深圳市旭然电子有限公司 | Inorganic/organic composite porous barrier film, preparation method and its lithium ion battery |
| CN110581247A (en) * | 2018-06-08 | 2019-12-17 | 上海恩捷新材料科技股份有限公司 | Ceramic composite diaphragm and preparation method thereof |
| CN108987649A (en) * | 2018-07-16 | 2018-12-11 | 怀化学院 | Battery ceramic slurry and preparation method thereof, application, battery diaphragm and battery |
| CN109411679A (en) * | 2018-10-22 | 2019-03-01 | 乐凯胶片股份有限公司 | Ceramic slurry, ceramic diaphragm and lithium ion battery |
| CN111682213A (en) * | 2020-06-08 | 2020-09-18 | 广州市乐基智能科技有限公司 | Preparation method of binder for lithium battery |
| CN111900460A (en) * | 2020-08-28 | 2020-11-06 | 常州赛得能源科技有限公司 | Solid electrolyte with self-supporting structure, preparation method and application |
| CN112980118A (en) * | 2021-02-07 | 2021-06-18 | 浙江汉丞科技有限公司 | Fluorine-containing polymer mixture for high-moisture-permeability super-breathable microporous membrane and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105713228A (en) | Manufacture method and applications of high temperature resistant and deformation resistant composite microporous membrane | |
| CN110444718B (en) | Preparation method of ceramic composite diaphragm with high-cohesiveness polymer coating film | |
| CN108878751B (en) | Conductive ceramic composite diaphragm and solid-state battery | |
| EP3159163B1 (en) | Polyolefin multilayer microporous film, method for producing same, and cell separator | |
| WO2022227345A1 (en) | Composite separator and preparation method therefor and use thereof | |
| WO2020000164A1 (en) | Composite lithium battery separator and preparation method therefor | |
| TWI629176B (en) | Porous membranes and multilayer porous membranes | |
| WO2018018870A1 (en) | Separator for electrochemical device and preparation method therefor | |
| JP5612217B2 (en) | Porous separation membrane using cellulose nanofiber and method for producing the same | |
| JP5525193B2 (en) | Multilayer porous membrane and coating solution | |
| TWI700851B (en) | Polyolefin microporous membrane, separator for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery | |
| JP7458494B2 (en) | Composition, composite separator and method for producing the same, and lithium ion battery | |
| CN111116963B (en) | Preparation method of ceramic coating diaphragm, diaphragm and ceramic coating slurry | |
| CN108550764B (en) | Superfine diamond coating isolating membrane and lithium ion battery applying same | |
| JP2017050149A (en) | Separator for secondary battery | |
| CN112350028B (en) | Barium sulfate diaphragm and preparation method thereof | |
| WO2019235112A1 (en) | Multilayer separator | |
| CN112635916A (en) | Ceramic composite diaphragm, preparation method thereof and battery | |
| CN113113731A (en) | Diaphragm, preparation method thereof and lithium ion battery | |
| JP6346986B1 (en) | Electric storage device separator and laminate, wound body and secondary battery using the same | |
| KR102190691B1 (en) | Separator coating material for secondary battery of electric vehicle or energy storage system and coating separator manufacturing method using the same, middle or large sized secondary battery of electric vehicle or energy storage system | |
| CN112038549A (en) | PMMA crosslinked spherical micro powder coating diaphragm and preparation method thereof and application of PMMA crosslinked spherical micro powder coating diaphragm in lithium ion battery | |
| CN110854345A (en) | High-performance lithium-sulfur battery diaphragm and preparation method and application thereof | |
| JP6574602B2 (en) | Power storage device separator, power storage device, and lithium ion secondary battery | |
| JP2020084084A (en) | Polyolefin microporous film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160629 |