CN101209609A - Polyolefin composite thin film and preparation and application thereof - Google Patents
Polyolefin composite thin film and preparation and application thereof Download PDFInfo
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- CN101209609A CN101209609A CNA2006101722975A CN200610172297A CN101209609A CN 101209609 A CN101209609 A CN 101209609A CN A2006101722975 A CNA2006101722975 A CN A2006101722975A CN 200610172297 A CN200610172297 A CN 200610172297A CN 101209609 A CN101209609 A CN 101209609A
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Abstract
The invention relates to a polyolefin compound film, comprising a polyolefin layer and a refractory coating which are adhered together. The refractory coating comprises a refractory material and vents distributed on the material, wherein, an average diameter of the vents on the material is not greater than 1 micron. The polyolefin compound film provided by the invention is provided with high strength and independent film layer structure can be preserved even after the polyolefin layer is melted and collapses. If the polyolefin compound film provided by the invention is used as a diaphragm of a lithium ion battery, the refractory layer of the compound film can avoid a contact between an anode and a cathode of the battery and prevent short circuit of the battery even though the polyolefin layer of the diaphragm is melted and collapses so as to really enhance the thermal security capability of the lithium ion battery. The polyolefin compound film provided by the invention has the advantages that the refractory capability is excellent; heat-shrinking is little and the strength is high. By being adopted as the diaphragm of a lithium ion secondary battery, the invention can effectively enhance the thermal security capability and circulation capability of the battery.
Description
Technical field
The invention relates to a kind of polyolefin composite thin film and its production and use.
Background technology
Lithium rechargeable battery has obtained huge development with advantages such as its high-energy-density, high voltage, little, in light weight, the memoryless property of volume over past ten years, become one of main energy sources of communication class electronic product.But because under abuse conditions, lithium rechargeable battery occurs easily smoldering, catch fire, exploding even causes potential safety hazard such as injury to personnel, makes high power capacity and power lithium-ion battery also not have extensive use.Therefore, improve the key that lithium ion battery security is the research and development lithium ion battery.
The liquid electrolyte lithium rechargeable battery generally comprises pole piece, battery container and electrolyte, described pole piece and electrolyte are sealed in the battery container, described pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, and described electrolyte comprises electrolyte and the electrolytical solvent of dissolving.Barrier film has storage fluidity and insulating properties, is used for intercepting anodally contacting with negative pole, thereby prevents the short circuit of battery.Barrier film commonly used at present is a MIcroporous polyolefin film, as microporous polypropylene membrane, polyethene microporous membrane, polypropylene-polyethylene composite micro porous film etc., fusing point generally is lower than 200 ℃, is that 130-140 ℃, the closed temperature of polypropylene (PP) microporous barrier are about 170 ℃ as the closed temperature of polyethylene (PE) microporous barrier.This MIcroporous polyolefin film has gas permeability and liquid permeability under the normal operating position of battery, can satisfy electrolyte and the gas that produces by electrode arrive the requirement of another utmost point of battery from a utmost point of battery.But, when battery at higher temperature as near the melt temperature of MIcroporous polyolefin film the time, fusion can take place in the polyolefin of MIcroporous polyolefin film, thereby causes the microcellular structure of barrier film to be closed, impedance increases sharply and make electric current blocking, plays battery explosion or the effect of catching fire of preventing.This temperature is called blocking (Shut-Down) temperature of barrier film, claims closed temperature again.Yet, in some cases, even after the loose structure of above-mentioned barrier film cuts out, because the other reasons battery temperature continues to raise, surpass the heat resisting temperature of barrier film and make barrier film take place to melt fully, destroy, cause positive pole, negative pole directly to contact and short circuit, thereby cause battery explosion or catch fire.This temperature is called destruction (break-out) temperature of barrier film.
This shows that barrier film plays the effect that stops the direct contact short circuit of both positive and negative polarity in lithium ion battery.In order to improve the security of battery, not only require battery diaphragm can stop the direct contact short circuit of both positive and negative polarity at normal temperatures, also requiring at high temperature simultaneously, this battery diaphragm also can stop the direct contact short circuit of both positive and negative polarity.But battery diaphragm commonly used now as polyethylene, the very difficult integrality that guarantees under the high temperature of polypropylene, often occurs in the safety tests such as stove heat shrinking the problem that causes internal short-circuit, initiation thermal runaway because of battery diaphragm.Therefore, the resistance to elevated temperatures of raising barrier film is to improve the key of lithium rechargeable battery high temperature safe performance.
JP-A-63-308866 discloses by lamination and has comprised that low-melting-point polyethylene and the polyacrylic single thin film acquisition of high-melting-point have the method for the microporous membrane of high strength and hot properties.Yet the barrier film internal resistance raises because of lamination, so the gained barrier film is not suitable for the heavy-duty battery of high output.
JP-A-10-298325 discloses a kind of preparation method of porous membrane, and described porous membrane contains low molecular weight polyethylene, low-molecular-weight polypropylene and High molecular weight polyethylene.This porous membrane bad mechanical strength, thermal shock resistance are poor.In addition because the barrier film mechanical strength is low, when the inside battery electrolyte owing to during the very strong pressure of hot gas generation, make film breaks easily.Still dangerous property when the porous membrane that therefore, makes in this way is used for lithium rechargeable battery.
JP 2001-59036A has proposed a kind of perforated membrane that has excellent balance between shutdown characteristic (SD characteristic) and hear resistance, and this perforated membrane will gather bornylene with sheet or lobate being distributed in the matrix polymer.Yet, although this invention has obtained to have the porous membrane of high-fire resistance and high mechanical properties, use polynorbornene not only to increase cost, but also because perforated membrane is synthetic by special reaction, therefore there is byproduct, causes the electrolyte that uses in the battery influenced.In addition, owing to be difficult to fully control reaction condition, make that polynorbornene may be crosslinked with single gelinite, so the hear resistance of perforated membrane and mechanical strength still may be relatively poor.
CN 1512607A provides a kind of improved perforated membrane on the basis of the perforated membrane that JP 2001-59036A proposes, this perforated membrane contains ethylene-propylene-ethylidene norbornene terpolymer, by three's crosslinked action raising intensity and heat resistance.But it is same because used ultra-high molecular weight polyethylene and ENB to improve cost; and be that the traditional thermoplastic PE/PP of employing is main; percent thermal shrinkage is relatively large; can not fundamentally solve the equilibrium relation of shutting down between characteristic and the heat resistance well; from its described content, adopt the super high molecular weight material also can cause so-called " static " phenomenon simultaneously.
For this reason, CN 1725524A discloses a kind of separator for non-aqueous electrolyte battery, this barrier film is the separator for non-aqueous electrolyte battery that the micro-porous film by the stacked laminated refractory layer of polyolefin constitutes, described refractory layer is to be that polyamide, polyimides or polyamidoimide more than 180 ℃ forms by fusing point, thickness is the 1-4 micron, (polyolefin layer: refractory layer) greater than 1, the air permeability of described barrier film is below 200 seconds to the ratio of the thickness of described polyolefin layer and refractory layer.And the disclosure is the thickness during greater than polyolefin layer thickness that further specifies refractory layer of the mode by Comparative Examples also, and the non-constant of the air permeability of barrier film dropped to 230 seconds by 190 seconds, and fall is up to 21%.This barrier film is by applying the polymer solution (for example polyamide, polyimides or polyamidoimide) of higher melt on the polyolefin top layer and making it have specific thickness, be immersed in the water then, Xiang Shuizhong discharges the solvent in the resin coating film, polymer film is separated out, thereby prepare at polyolefin surfaces formation polymer film.Though can improve the hear resistance of polyolefin film on this theoretical method to a certain extent, yet, when the temperature on acting on this barrier film surpasses the fusing point (as about 180 ℃) of polyolefine material, polyolefine material melts, the refractory layer polymer that causes depending on polyolefin substrate comes off thereupon, therefore still dangerous property.
Summary of the invention
The objective of the invention is still can not really effectively improve the shortcoming of lithium ion battery security, provide a kind of and can really effectively improve polyolefin composite membrane of lithium ion battery security and its production and use for the polyolefin composite membrane that overcomes prior art.
The present inventor is by discovering, the security why disclosed polyolefin composite membrane of CN 1725524A can not really effectively improve lithium ion battery, be because when the temperature in the battery is increased to fusing point above polyolefin layer, since refractory layer by painting method attached to forming on the polyolefin layer, and the air-vent on the refractory layer is to obtain by the solvent of removing on the refractory layer, thereby the air-vent diameter on the refractory layer that forms is big and skewness, the intensity of refractory layer is very low, average pore size is up to the 2-5 micron, and hot strength is low to moderate below 20 MPas.When the polyolefin layer fusion, refractory layer itself can not form independently film layer structure, thereby comes off with the fusion of polyolefin layer, can not really play and improve the stable on heating effect of barrier film.In addition, the polymer solution of the higher melt that the disclosed polyolefin of CN 1725524A top layer applies is necessary for polyamide, polyimides and the polyamidoimide of solubility, the vitrification point of itself is lower, generally be lower than 300 ℃, more insoluble polyamide, polyimides and polyamidoimide are low, thereby the also more insoluble polyamide of hear resistance, polyimides and polyamidoimide are poor.Thereby, can not obtain vitrification point according to the method for CN 1725524A and surpass 300 ℃ of refractory layers that especially surpass 400 ℃.
Polyolefin composite membrane provided by the invention comprises polyolefin layer and the refractory layer that is attached together, and described refractory layer comprises heat proof material and the air-vent that is distributed on this material, and wherein, the described average diameter that is distributed in the air-vent on this material is no more than 1 micron.
The preparation method of polyolefin composite membrane provided by the invention comprises refractory layer and polyolefin layer is attached together, described refractory layer comprises heat proof material and the air-vent that is distributed on this material, wherein, the described average diameter that is distributed in the air-vent on this material is no more than 1 micron.
The application of polyolefin composite membrane provided by the invention in lithium ion secondary battery membrane.
Polyolefin composite membrane provided by the invention is because the average diameter of air-vent on the refractory layer is no more than 1 micron, thereby this refractory layer has higher intensity, even still can keep independently film layer structure in the polyolefin layer fusion, after caving in.Therefore, when polyolefin composite membrane provided by the invention is used as the barrier film of lithium ion battery, even the polyolefin layer fusion of barrier film, cave in, the refractory layer of this composite membrane still can play and prevent the battery plus-negative plate contact, prevent the iris action of battery short circuit, thereby really improve the thermal safety energy of lithium ion battery.Polyolefin composite membrane provided by the invention has excellent heat resistance, thermal contraction is little, intensity is high advantage, can effectively improve the thermal safety and the cyclicity of battery during as the barrier film of lithium rechargeable battery.
The preparation method of polyolefin composite membrane provided by the invention by with refractory layer as base material, polyolefin layer is formed on refractory layer, thereby can effectively improve the thickness and the intensity of refractory layer.In addition,, can make the average diameter of air-vent of the refractory layer of acquisition be no more than 1 micron, and air-vent evenly distributes, thereby further improve the intensity of refractory layer by adopting the preferred refractory layer preparation method of the present invention.
The specific embodiment
According to polyolefin composite membrane provided by the invention, as long as can realize purpose of the present invention although the average diameter of the air-vent on the refractory layer is no more than 1 micron, but under the preferable case, the average diameter of the air-vent on the refractory layer is the 0.01-0.1 micron, so both can guarantee that refractory layer had higher intensity, and can guarantee the gas permeability of composite membrane again.More preferably under the situation, in the described air-vent that is distributed on this material, diameter is no more than 1 micron air-vent and accounts for more than 90% of air-vent total quantity.The porosity of described refractory layer is 10-90 volume %.
Described refractory layer can be the layer that various vitrification points are not less than 180 ℃ insulating materials formation in the prior art, is preferably the layer that vitrification point is not less than 400 ℃ insulating materials formation.For example, but in described insulating materials polyamide, polyimides and the polyamidoimide one or more.Be that the present invention will be described for example with the polyimides in the specific embodiment of the invention.Described polyimides is preferably the polymer that contains imide group in the various repetitives, and under the preferable case, described polyimides is the polyimides with following structural formula:
Wherein, R
1And R
2Identical or different, can be various substituted alkyls, substituted aryl, the feasible vitrification point that contains the refractory layer of this polyimides of the value of polymerization degree n is not less than 180 ℃, preferably is not less than 400 ℃, for example 400-580 ℃.
Under the preferable case, R
1And R
2Be the group that contains aromatic ring, and carbonyl and R
1The direct key of aromatic ring connect; Nitrogen-atoms on the imide and R
2The direct key of aromatic ring connect, the value of polymerization degree n makes the refractory layer vitrification point that contains this polyimides be not less than 400 ℃.In this case, the polyolefin composite membrane has better hear resistance and bigger hot strength.
Described aromatic ring can be phenyl ring, naphthalene nucleus.More under the preferable case, R
1Be selected from substituted-phenyl, substituted biphenyl base, the substituted diphenylamine ketone group one or more, at least four hydrogen in described substituted-phenyl, substituted biphenyl base, the substituted diphenylamine ketone group on the phenyl ring are by the carbonyl substituted on the imide group, and two carbonyls on the same imide group are positioned at the adjacent position of phenyl ring; R
2Be selected from substituted-phenyl, substituted biphenyl base, the substituted diphenylamine ether one or more, at least two hydrogen in described substituted-phenyl, substituted biphenyl base, the substituted diphenylamine ether on the phenyl ring are replaced by the nitrogen-atoms on the acylimino.
Except that being replaced by carbonyl or imino group, other hydrogen on the phenyl ring also can be replaced by other various functional groups in the above-mentioned phenyl ring, and described functional group can be one or more in halogen, nitro, alkyl, amino, the sulfonic group, is preferably C
4-C
10Straight chain and/or branched alkyl.
Preferred described polyimides is one or more in PMMI, poly-biphenyl tetracarboxylic acid imide, the poly-benzophenone tetramethyl acid imide in the specific embodiment of the invention.Above-mentioned polyimides can be used following structural formula (1), (2) and (3) expression respectively:
In the above-mentioned formula, the preferably feasible vitrification point that contains the refractory layer of this polyimides of the value of n is 400-580 ℃, R
3, R
4, R
5, R
6, R
7And R
8Be independently selected from hydrogen, halogen, amino, nitro, the alkyl one or more respectively, described halogen can be fluorine, chlorine, bromine or iodine, and described alkyl is preferably C
4-C
10Straight chained alkyl and/or branched alkyl.
R
2Can be the substituted aryl of following structural formula:
R wherein
3, R '
4, R '
5, R '
6, R '
7And R '
8Be independently selected from hydrogen, halogen, amino, nitro, the alkyl one or more respectively, described halogen can be fluorine, chlorine, bromine or iodine, and described alkyl is preferably C
4-C
10Straight chained alkyl and/or branched alkyl.Under the preferable case, R '
3, R '
4, R '
5, R '
6, R '
7And R '
8Be hydrogen, such R
2Low and and the acquisition easily of cost.
In addition, two imide groups on the repetitive also can be positioned on other position of phenyl ring, for example for structural formula (2), described imide can be positioned on 2,3 and/or 2 ', the 3 ' position of biphenyl (according to the IUPCA nomenclature, the positions that two phenyl ring keys connect are 1,1 ' number position).Since the position of imide on phenyl ring do not influence battery diaphragm of the present invention hear resistance, air permeability, pierce through intensity and thermal contraction performance, therefore polyimides of the present invention is not done requirement to the position of imide, can be said structure formula (1), all places isomers of (2) and (3) described structure or their mixture.
Although it is soluble that the part polyimides is arranged, because most of polyimides is an insoluble polymer, can't accurately measure the degree of polymerization of polyimides, therefore, the present invention only characterizes polyimides with the vitrification point of the refractory layer that the present invention was concerned about.Among the present invention, be not less than 180 ℃, preferably be not less than 400 ℃ and can reach purpose of the present invention as long as contain the vitrification point of the refractory layer of polyimides.
Described refractory layer can obtain by the prepared in various methods of routine, for example, can in solvent, carry out polymerisation by the tetracarboxylic dianhydride and the diamine that will form polyimides, obtain polyamic acid solution, then the gained polyamic acid solution is coated on the release film, the release film that will be coated with polyamic acid under the imidizate condition heats, make polyamic acid be dehydrated into polyimides, promptly get polyimide film after removing the solvent in the polyamic acid solution, further heating is come out to form required air-vent the solvent evaporates that is wrapped in the polyimide film, can obtain to have the Kapton of air-vent like this, refractory layer promptly of the present invention.Yet,, especially be difficult to guarantee the pore size of air-vent by the distribution of the air-vent on the very difficult control of the said method gained polyimide film.Generally, the largest hole diameter of the air-vent on the polyimide film that is obtained by said method can reach the 1-5 micron, and diameter accounts for the 90-100% of air-vent total quantity greater than the quantity of 1 micron air-vent, thereby causes the polyimides film strength to reduce greatly.Because it is inhomogeneous that air-vent distributes, and also causes usually cooperating the gas permeability of the polyolefin composite membrane that obtains to reduce greatly with polyolefin layer; On the other hand, the hole that forms by solvent flashing is difficult to guarantee to be the through hole that runs through the polyimides film thickness direction, thereby can not satisfy the needs of battery diaphragm.Polyimides refractory layer thickness is less than the one of the main reasons of polyolefin layer thickness in this also present just polyolefin composite membrane.
According to a kind of optimal way of the present invention, the method of described formation refractory layer comprises heat proof material and pore-forming material is dissolved in the solvent, obtain containing the solution of heat proof material and pore-forming material, then this solution is coated on the release film, is being lower than under the heat proof material vitrification point except that desolvating and the pore-forming material again.When described heat proof material is polyimides, the method of described formation refractory layer comprises and being dissolved in the solvent forming the tetracarboxylic dianhydride of polyimides and diamine and pore-forming material, obtain containing the solution of polyamic acid and pore-forming material, then this solution is coated on the release film, is being lower than under the polyimides glass temperature except that desolvating and the pore-forming material again.Described remove desolvated and the method for pore-forming material comprises removing under lower temperature earlier and desolvates, under the imidizate condition, make polyamic acid be dehydrated into polyimides then, the last pore-forming material of under the decomposition temperature of pore-forming material, removing, make the pore-forming material resolve into little molecule and from film, evaporate to form required air-vent, can obtain to have the Kapton of air-vent like this, refractory layer promptly of the present invention.
Described pore shaping object is of fine quality elects the polymer that decomposition temperature is higher than the boiling point of solvent and is lower than polyimides glass temperature as.Under the preferable case, it is 1000-50000 one or more in polycaprolactone, PPOX, polymethylstyrene, polystyrene and the polyurethane of 10000-20000 more preferably that this new pore-forming material is selected from weight average molecular weight.Above-mentioned pore-forming material can obtain by the whole bag of tricks, for example can be purchased, and also can obtain by prepared in various methods.
In order to increase pore-forming material and polyimides or to form the compatibility of the material of polyimides, an end of the more preferred polymeric chain at least of described pore-forming material is by in above-mentioned polycaprolactone, PPOX, polymethylstyrene, polystyrene and the polyurethane of amino functional one or more.One end of described polymeric chain can be commercially available by the above-mentioned polymer of amino functional, and also can in all sorts of ways prepares.The concrete operation method of described amino functional has been conventionally known to one of skill in the art, does not repeat them here.
Described tetracarboxylic dianhydride can be aromatic series tetracarboxylic dianhydride and/or aliphatic tetracarboxylic dianhydride, and the concrete example of described aromatic series tetracarboxylic dianhydride can be pyromellitic acid anhydride (PMDA), 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (BPDA), 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 1,2,4,5-naphthalene tetracarboxylic acid dianhydride, 1, two (trifluoromethyl)-2 of 4-, 3,5,6-benzene tertacarbonic acid dianhydride (P6GDA), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 1,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 2,6-dichloronaphtalene-1,4,5, the 8-tetracarboxylic dianhydride, 2,7-dichloronaphtalene-1,4,5, the 8-tetracarboxylic dianhydride, 2,3,6,7-Tetrachloronaphthalene-2,4,5, the 8-tetracarboxylic dianhydride, luxuriant and rich with fragrance-1,8,9, the 10-tetracarboxylic dianhydride, benzene-1,2,3, the 4-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, wherein preferred all benzene tertacarbonic acid's dianhydrides (PMDA), 3,3, ' 4,4 '-biphenyl tetracarboxylic dianhydride (BPDA), 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4, one or more in 4 '-benzophenone tetracarboxylic dianhydride.
Described diamine can be aromatic diamine and/or aliphatic diamine; for example can be 4; 4 '-diaminodiphenyl ether (ODA); 4; 4 '-diaminobenzophenone; 3; 3 '-dimethyl-4; 4 '-diaminobenzophenone; 3; 3 '-two chloro-4,4 '-diaminobenzophenone; m-phenylene diamine (MPD); p-phenylenediamine (PPD); 4 '-di-2-ethylhexylphosphine oxide (neighbour-chloroaniline); 3,3 '-dichloro diphenylamine; 3; 3 '-sulfonyl diphenylamines; 1; the 5-diaminonaphthalene; 2,2 '-two (4-amino-phenols); 4,4 '-benzidine; 4; 4 '-methylene dianiline (MDA); 4; 4 '-sulfenyl diphenylamines; 4,4 '-isopropylidene diphenylamines; 3,3 '-dimethylbenzidine; 3; 3 '-dimethoxy benzidine; 3; 3 '-dicarboxylate biphenyl amine; 2, the 4-diaminotoluene; 2, the 5-diaminotoluene; 2; 4-diaminourea-5-chlorotoluene; 2, one or more in 4-diaminourea-6-chlorotoluene.Preferred 4,4 '-diaminodiphenyl ether (ODA), 4,4 '-diaminobenzophenone, p-phenylenediamine (PPD), 4, one or more in 4 '-benzidine.
The mol ratio of described tetracarboxylic dianhydride and diamine total amount can be 0.8-1.5: 1, be preferably 0.9-1.2: and 1,0.95-1.05 more preferably: 1.Such proportioning can make acid anhydrides and diamine complete reaction generation polyamic acid as far as possible, by further obtaining polyimides required for the present invention behind the imidizate.
Described solvent can be the various solvents that can dissolve the material that forms polyimides and pore-forming material simultaneously and be easy to volatilize and remove.Among the present invention, described solvent can be to be various strong polarity nonionic solvent commonly used, be preferably N-2-methyl pyrrolidone (NMP), N, N-dimethylacetylamide (DMAC), N, in dinethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), m-cresol, oxolane, the methyl alcohol one or more, more preferably one or more among NMP, DMAC, the DMF.
There is no particular limitation to the feeding quantity of pore-forming material in the present invention, specifically according to the hole density of required polyolefin composite membrane and the size decision in hole.Under the preferable case, it is 1-9 that the addition of described pore-forming material makes the weight ratio of polyimides and pore-forming material: 1.There is no particular limitation to the addition of described solvent in the present invention, forms uniform solution as long as the material that forms polyimides and pore-forming material are dissolved fully, and under the preferable case, described solvent and the substance weight that forms polyimides are than being 4.5-10.
The condition of described polymerisation can be conventional acid anhydrides and the imido reaction condition of amine prepared in reaction, for example, reaction temperature generally can be-20 ℃ to 99 ℃, be preferably-10 ℃ to 50 ℃, more preferably 20-40 ℃, that is to say that tetracarboxylic dianhydride of the present invention and diamine prepared in reaction polyimides can carry out smoothly under common environment temperature, need not extra heating or cooling; The time of polymerisation is to get final product in the acid anhydrides of routine and the reaction time of amine prepared in reaction amic acid, and for example, the time of polymerisation can be 0.1-24 hour.Described temperature of carrying out imidization reaction is 250-450 ℃, and the time is 0.1-10 hour.Described temperature of removing the pore-forming material is decided on concrete pore-forming material, as long as the general vitrification point that is not less than the decomposition temperature of pore-forming material and is not higher than polyimide film.
The method of described film forming can adopt conventional method such as dried film build method and wet film build method.For example, can obtain except that after desolvating by solution is applied into desired thickness.Described coating can realize by the whole bag of tricks, for example can use spreader.The same with conventional film build method, solution applied into desired thickness after, again solvent is removed, obtain non-porous film, then the pore-forming material in the non-porous film is removed the refractory layer that promptly gets polyolefin composite membrane of the present invention.Describedly remove the method desolvate and concrete operations for conventionally known to one of skill in the art, the preferred method of heating that adopts is removed solvent, and the temperature of heating is decided on the boiling point of solvent.Among the present invention, removing the temperature of desolvating is the temperature of removing that is lower than the boiling temperature of solvent and is lower than the pore-forming material, more is lower than the vitrification point of base material.
Can make the polyimide film of all thickness scope by said method.According to polyolefin composite membrane of the present invention, the thickness of refractory layer is generally the 10-35 micron, and the thickness of refractory layer and polyolefin layer is than being 1-7: 1.
Described polyolefin layer can be the layer that various polyolefin substrate of the prior art forms, for example described polyolefin substrate can be the homopolymers of ethene, propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene monomer or in copolymer or their mixture one or more, is preferably fusing point and is 110-135 ℃ polyethylene.Described polyethylene can be one or more in low density polyethylene (LDPE) (LDPE), linear low density of polyethylene (LLDPE), high density polyethylene (HDPE) (HDPE), the ultra-high molecular weight polyethylene (UHMWDPE), and further preferred described poly weight average molecular weight is 1 * 10
4-1 * 10
6Be preferably 5 * 10
4-3 * 10
5
The requirement that conventional polyolefin composite membrane is satisfied in the pore size of the air-vent on the described polyolefin layer and the distribution in hole gets final product, and generally requires the distribution in hole more even, and the average diameter of air-vent is generally the 1-5 micron.
Preparation method according to polyolefin composite membrane provided by the invention, although can be by with direct laminated the obtaining of said polyolefins layer and refractory layer, but under the preferable case, a preferred embodiment of the invention, the preparation method of described polyolefin composite membrane comprises the preparation refractory layer, on refractory layer, apply the polyolefin substrate solution that forms polyolefin layer then, behind the drying and forming-film, obtain the composite heat resistance layer of load polyolefin film, then this composite heat resistance layer be impregnated in the extractant, go out solvent in the polyolefin film with extracting, obtain being distributed with the composite heat resistance layer of air-vent, this composite heat resistance layer that is distributed with air-vent is polyolefin composite membrane provided by the invention.Described extractant is for dissolving the solvent that forms vistanex solution but the insoluble solvent of separating polyolefin-based material and refractory layer, for example can be in pentane, hexane, decane, the chloralkane one or more, described chloralkane can be one or more in the chloromethanes, chloroethanes, chloropropane of a chloro, dichloro-or many chloros, be preferably chloromethanes, as in monochloro methane, carrene and the chloroform one or more.Solvent is promptly stayed the hole in the position of original solvent after the extracting from polyolefin resin film, this hole is the required air-vent of polyolefin layer.Can adjust the porosity (being the percentage that the cumulative volume of air-vent accounts for the polyolefin layer cumulative volume) of polyolefin layer by the concentration of adjusting polyolefin substrate solution.Under the preferable case, the concentration of polyolefin substrate solution is 20-40 weight %, and in above-mentioned concentration range, the porosity of polyolefin layer can reach more than 90%.
The solvent that forms polyolefin substrate solution can be one or more in atoleine, nonane, decane, hendecane, the dodecane, preferably is difficult to the atoleine that volatilizees.
The polyolefin composite membrane that adopts said method to make can be as the barrier film of lithium rechargeable battery, and concrete using method has been conventionally known to one of skill in the art.
The following examples will the present invention is further illustrated.
Embodiment 1
This embodiment is used to illustrate polyolefin composite membrane provided by the invention and preparation method thereof.
Mixture (mol ratio 1: 1), the 1.8 weight portion weight average molecular weight that 10.2 weight portions are made up of benzophenone tetracarboxylic dianhydride (analyzing pure) and diaminodiphenyl ether (analyzing pure) are 22000 EU and 82 weight portion N-methyl pyrrolidones (NMP) 10 ℃ of following stirring reactions 10 hours, obtain inherent viscosity η
IntThe thick polyamic acid solution of=220 milliliters/gram (condition determination: Ubbelohde viscometer, it is 0.005 grams per milliliter that 30 ℃ of constant temperature, solution are diluted to solid content).Then above-mentioned solution is coated on the clean smooth glass plate uniformly with the QTG type spreader of filming, put into 90 ℃ of drying boxes dry 1 hour, temperature programming to 300 ℃ was carried out imidizate 1 hour then, obtain Kapton, be warmed up to 350 ℃ afterwards again and keep making in 2 hours EU to decompose, obtain thickness as refractory layer thus and be 15 microns polyimides porous membrane.The vitrification point that records this refractory layer with the DSC method is 480 ℃, is 0.05 micron by nitrogen absorption/desorption type specific area/distribution of pores tester ASAP2010 of being made by Shimadzu Corp according to the average diameter that the pore diameter distribution curve of BJH method acquisition records air-vent, diameter is no more than 1 micron air-vent and accounts for 90% of air-vent total quantity, and porosity is 50 volume %.
Filming with the QTG type, will to contain 27 weight portion weight average molecular weight be that 270000 HDPE, 3 weight portion weight average molecular weight are that 3400000 the UHMWPE and the polyethylene base material solution single face of 70 weight portion atoleines are coated on the above-mentioned refractory layer that obtains to spreader, after 70 ℃ down heating obtained area load in 10 minutes the refractory layer of polyethylene film is arranged, this refractory layer was flooded 15 minutes in monochloro methane solution, extract the atoleine in the polyvinyl resin layer, drying obtains polyolefin composite membrane S1 of the present invention after removing surface solvent, and wherein the thickness of polyethylene layer is 5 microns.
Embodiment 2
This embodiment is used to illustrate polyolefin composite membrane provided by the invention and preparation method thereof.
Is that 18000 polymeric chain one end contains amino PPOX and 82 weight portion DMAc 10 ℃ of following stirring reactions 10 hours with 10.2 weight portions by bibenzene tetracarboxylic dianhydride (analyzing pure) with to mixture (mol ratio 1: 1), 1.8 weight portion weight average molecular weight that diamino-benzene (analyzing pure) is formed, obtains inherent viscosity η
IntThe thick polyamic acid solution of=220 milliliters/gram (condition determination: Ubbelohde viscometer, it is 0.005 grams per milliliter that 30 ℃ of constant temperature, solution are diluted to solid content).Then above-mentioned solution is coated on the clean smooth glass plate uniformly with the QTG type spreader of filming, put into 90 ℃ of drying boxes dry 1 hour, temperature programming to 300 ℃ was carried out imidizate 1 hour then, obtain Kapton, be warmed up to 350 ℃ afterwards again and keep making in 2 hours PPOX to decompose, obtain thickness as refractory layer thus and be 15 microns polyimides porous membrane.The vitrification point that records this refractory layer with the DSC method is 580 ℃, is 0.05 micron by nitrogen absorption/desorption type specific area/distribution of pores tester ASAP2010 of being made by Shimadzu Corp according to the average diameter that the pore diameter distribution curve of BJH method acquisition records air-vent, diameter is no more than 1 micron air-vent and accounts for 90% of air-vent total quantity, and porosity is 40 volume %.
Filming with the QTG type, will to contain 27 weight portion weight average molecular weight be that 270000 HDPE, 3 weight portion weight average molecular weight are that 3400000 the UHMWPE and the polyethylene base material solution single face of 70 weight portion atoleines are coated on the above-mentioned refractory layer that obtains to spreader, after 70 ℃ down heating obtained area load in 10 minutes the refractory layer of polyethylene film is arranged, this refractory layer was flooded 15 minutes in monochloro methane solution, extract the atoleine in the polyvinyl resin layer, drying obtains polyolefin composite membrane S2 of the present invention after removing surface solvent, and wherein the thickness of polyethylene layer is 7 microns.
Embodiment 3
This embodiment is used to illustrate polyolefin composite membrane provided by the invention and preparation method thereof.
Mixture (mol ratio 1: 1), the 1.8 weight portion weight average molecular weight that 10.2 weight portions are made up of pyromellitic acid anhydride and p-phenylenediamine (PPD) are 10000 polymethylstyrene and 82 weight portion N, dinethylformamide obtains inherent viscosity η 10 ℃ of following stirring reactions 10 hours
IntThe thick polyamic acid solution of=180 milliliters/gram (condition determination: Ubbelohde viscometer, it is 0.005 grams per milliliter that 30 ℃ of constant temperature, solution are diluted to solid content).Then above-mentioned solution is coated on the clean smooth glass plate uniformly with the QTG type spreader of filming, put into 90 ℃ of drying boxes dry 1 hour, temperature programming to 300 ℃ was carried out imidizate 1 hour then, obtain Kapton, be warmed up to 350 ℃ afterwards again and keep making in 2 hours polymethylstyrene to decompose, obtain thickness as refractory layer thus and be 15 microns polyimides porous membrane.The vitrification point that records this refractory layer with the DSC method is 550 ℃, is 0.03 micron by nitrogen absorption/desorption type specific area/distribution of pores tester ASAP2010 of being made by Shimadzu Corp according to the average diameter that the pore diameter distribution curve of BJH method acquisition records air-vent, diameter is no more than 1 micron air-vent and accounts for 90% of air-vent total quantity, and porosity is 30 volume %.
Filming with the QTG type, will to contain 27 weight portion weight average molecular weight be 270000 HDPE to spreader, 3 weight portion weight average molecular weight are that 3400000 the UHMWPE and the polyethylene base material solution single face of 70 weight portion atoleines are coated on the above-mentioned refractory layer that obtains, after 70 ℃ down heating obtained area load in 10 minutes the refractory layer of polyethylene film is arranged, this refractory layer was flooded 15 minutes in monochloro methane solution, extract the atoleine in the polyvinyl resin layer, drying obtains polyolefin composite membrane S3 of the present invention after removing surface solvent, and wherein the thickness of polyethylene layer is 10 microns.
Embodiment 4-6
Following embodiment is used to measure the performance of polyolefin composite membrane of the present invention.
The average diameter in polyolefin composite membrane S1, S2 that adopts following method to measure respectively to be made by embodiment 1-3 and the porosity of S3, hole, distribution, hot strength, the air permeability in hole, pierce through intensity, hear resistance and heat-shrinkable, measurement result is as shown in table 1 below.
Porosity: adopt the method for testing test of this area routine: from the square sample that the polyolefin composite membrane downcuts certain-length, measure it volume (centimetre
3) and weight (gram), calculate by following formula: porosity (%)=100 * (1-weight/(polyolefin composite film material * volume));
The average diameter in hole: determine according to the pore diameter distribution curve that the BJH method obtains by the nitrogen absorption/desorption type specific area/distribution of pores tester ASAP2010 that makes by Shimadzu Corp;
The distribution in hole: the polyolefin composite membrane that makes with embodiment 1-3 is that barrier film is made the LP043450 size battery, above-mentioned battery is carried out 4.3-2.75 volt cycle charge-discharge, circulate and take battery apart after 100 times, observe the distribution of white zinc dendrite on the polyolefin composite membrane, if white zinc dendrite is evenly distributed, the pore size distribution that barrier film is described is even, and vice versa;
Hot strength: the polyolefin composite membrane of 5 mm wides, d millimeters thick is stretched the maximum pull F that tensiometer shows before the record fracture on puller system with 5 mm/second
Max(ox) calculated by following formula: hot strength (MPa)=F
Max/ (5 * d);
Air permeability: measure according to JIS P8117;
Closed temperature: in the gas permeability test process, keep admission pressure constant, the temperature of the polyolefin composite membrane that slowly raises (less than 5 ℃/minute), the transmission rates of measurement gas.Temperature when almost not having gas permeation is exactly the closed temperature of film.
Pierce through intensity: fixing polyolefin composite membrane, with diameter be 1 millimeter, bent at its tip radius be 0.5 millimeter pin with the speed motion of 2 cels, pierce through maximum, force in the polyolefin composite membrane process and count and pierce through intensity;
Heat-shrinkable: with lateral length is L
0Polyolefin composite membrane nature be placed in the baking oven of 150 ℃ and 400 ℃ and kept respectively 1 hour, measure lateral length L then
1, then
Hear resistance (be film broken temperature): adopt the hear resistance of the described heat-pesistant thin film disruption method test of CN 1512607A polyolefin composite membrane, the heating rate of different is battery is 10 ℃/minute, is warming up to 400 ℃.
Table 1
The result who from last table 1, provides as can be seen, the polyolefin composite membrane resistance to elevated temperatures excellence that obtains in the embodiment of the invention is heated to 400 ℃ of high temperature and does not also break; The polyolefin composite membrane less than 0.5%, all is not more than 1.5% at 400 ℃ percent thermal shrinkages at 150 ℃ percent thermal shrinkage; The average diameter in hole and porosity all satisfy the conductance requirement, and good air permeability is arranged.In addition, the distribution experiment by the hole as can be seen, the distributing very evenly of the compound fenestra of polyolefin provided by the invention.
Claims (17)
1. polyolefin composite membrane, this polyolefin composite membrane comprises polyolefin layer and the refractory layer that is attached together, described refractory layer comprises heat proof material and the air-vent that is distributed on this material, it is characterized in that the described average diameter that is distributed in the air-vent on this material is no more than 1 micron.
2. polyolefin composite membrane according to claim 1, wherein, the described average diameter that is distributed in the air-vent on this material is the 0.01-0.5 micron.
3. polyolefin composite membrane according to claim 1, wherein, in the described air-vent that is distributed on this material, diameter is no more than 1 micron air-vent and accounts for more than 90% of air-vent total quantity.
4. polyolefin composite membrane according to claim 1, wherein, the porosity of described refractory layer is 10-90 volume %.
5. polyolefin composite membrane according to claim 1, wherein, the thickness of described refractory layer is the 10-35 micron.
6. polyolefin composite membrane according to claim 5, wherein, described refractory layer is 1-7 with the thickness ratio of polyolefin layer: 1.
7. polyolefin composite membrane according to claim 1, wherein, described heat proof material is that vitrification point is not less than 180 ℃ insulating materials, and described polyolefin layer is by the homopolymers of ethene, propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene monomer or one or more perforated membranes that form in copolymer or their mixture.
8. polyolefin composite membrane according to claim 7, wherein, described heat proof material is one or more in mute amine of polyamide, polyamides and the polyamidoimide.
9. the preparation method of a polyolefin composite membrane, this method comprises refractory layer and polyolefin layer is attached together, described refractory layer comprises heat proof material and the air-vent that is distributed on this material, it is characterized in that the described average diameter that is distributed in the air-vent on this material is no more than 1 micron.
10. method according to claim 9, wherein, the described method that refractory layer and polyolefin layer are attached together comprises the formation refractory layer, then at the surface-coated polyolefin substrate solution of refractory layer, behind the drying and forming-film, obtain the composite heat resistance layer of load polyolefin film, this composite heat resistance layer be impregnated in the extractant, go out solvent in the polyolefin film with extracting.
11. method according to claim 10, wherein, the method of described formation refractory layer comprises heat proof material and pore-forming material is dissolved in the solvent, obtain containing the solution of heat proof material and pore-forming material, then this solution is coated on the release film, is being lower than under the heat proof material vitrification point except that desolvating and the pore-forming material again.
12. method according to claim 11, wherein, the weight ratio of described heat proof material and pore-forming material is 1-9: 1.
13. method according to claim 11, wherein, described heat proof material is a polyimides, the method of described formation refractory layer comprises and being dissolved in the solvent forming the tetracarboxylic dianhydride of polyimides and diamine and pore-forming material, obtain containing the solution of polyamic acid and pore-forming material, then this solution is coated on the release film, is being lower than under the polyimides glass temperature except that desolvating and the pore-forming material again.
14. according to any described method among the claim 11-13, wherein, described pore-forming material is that decomposition temperature is higher than the boiling point of solvent and is lower than the polymer of polyimides glass temperature.
15. method according to claim 14, wherein, described pore-forming material is selected from one or more in polycaprolactone, PPOX, polymethylstyrene, polystyrene and the polyurethane that weight average molecular weight is 1000-50000.
16. method according to claim 15, wherein, described pore-forming material is that an end of polymeric chain at least is by in the polycaprolactone of amino functional, PPOX, polymethylstyrene, polystyrene and the polyurethane one or more.
17. the application of any described polyolefin composite membrane in being used as lithium ion battery separator among the claim 1-8.
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