CN1771616A - Adhesive-carrying porous film for cell separator and its application - Google Patents

Adhesive-carrying porous film for cell separator and its application Download PDF

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Publication number
CN1771616A
CN1771616A CNA2004800095580A CN200480009558A CN1771616A CN 1771616 A CN1771616 A CN 1771616A CN A2004800095580 A CNA2004800095580 A CN A2004800095580A CN 200480009558 A CN200480009558 A CN 200480009558A CN 1771616 A CN1771616 A CN 1771616A
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China
Prior art keywords
perforated membrane
electrode
bonding agent
battery
make
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CNA2004800095580A
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CN100346506C (en
Inventor
市川智昭
喜井敬介
植谷庆裕
山本一成
萨摩道夫
山口睦子
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Nitto Denko Corp
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Nitto Denko Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Cell Separators (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention provides an adhesive-carrying porous film for use as a battery separator, which comprises: a substrate porous film such that when a probe of a probe penetrating thermomechanical analyzer, said probe having a diameter of 1 mm, is placed on the porous film under a load of 70 g to measure a thickness thereof while heating the porous film from room temperature at a rate of 2 DEG C./minute, a temperature at which the thickness of the porous film decreases to a half of the thickness of the porous film when the probe was initially placed thereon is 200 DEG C. or more; and a partially crosslinked adhesive carried on the substrate porous film, the partially crosslinked adhesive being prepared by reacting a reactive polymer having a functional group capable of reacting with an isocyanate group therein with a polyfunctional isocyanate so that the reactive polymer is partially crosslinked. Such a porous film (a separator) is temporarily bonded to an electrode to provide an electrode/separator laminate. In manufacturing a battery, the use of the laminate makes it possible to manufacture a battery efficiently with no mutual slip movement between the electrode and the separator, and is addition, the porous film (the separator) itself, after manufacturing a battery, functions as a separator which does not melt or break, and has a small heat shrinkage under high temperatures.

Description

The perforated membrane and the utilization thereof of the load bonding agent that battery separator is used
Technical field
The present invention relates to the following battery separator (perforated membrane of the load bonding agent of usefulness of セ パ レ-) and use the manufacture method of battery of the perforated membrane of such load bonding agent, the perforated membrane of this load bonding agent can be used to make battery, simultaneously in the battery of making like this, even the perforated membrane of this load bonding agent can not fuse or break yet under hot environment, and, play the function of the little dividing plate of thermal contraction, thereby be good aspect fail safe.
Background technology
In the past, manufacture method as battery, for example the spy open flat 09-161814 communique or the spy open described in the flat 11-329439 communique like that, known have a following method: clamp between positive pole and negative pole and the stacked dividing plate that is used to prevent these inter-electrode short-circuits, or stack gradually and reel and just (bear) utmost point, dividing plate, negative (just) utmost point and dividing plate, make electrode/dividing plate duplexer, after in battery case that this electrode/dividing plate duplexer is packed into, in this battery case, inject electrolyte and seal.
But in such cell manufacturing method, electrode and dividing plate cause slippage between mutually easily in the keeping of electrode/dividing plate duplexer or when transporting, and its result exists the productivity of battery manufacturing low and be easy to generate problem such as substandard product.In addition, electrode expansion or contraction when the battery that obtains like this uses at it, the adaptation variation between electrode and the dividing plate, battery behavior descends or produces internal short-circuit, the battery heating up, according to circumstances, even existence is fused, the danger of film rupture.
In the past, the known manufacture method that the perforated membrane that the multiple this dividing plate that uses in the battery manufacturing uses is arranged.As a kind of method, for example, as the spy opened described in the flat 09-012756 communique, the known useful gel-form composition that is made of extrahigh-molecular weight polyolefins resin and the wide vistanex of molecular weight distribution (weight-average molecular weight/number-average molecular weight) was made thin slice and it is carried out the method that high magnification stretches.But, by like this with high magnification stretch battery separator that the perforated membrane obtain constitutes battery because of unusual high temperature environment such as situation that heat up such as internal short-circuits under, its heat-shrinkable is still remarkable, and fuse sometimes, film rupture, existence can not be brought into play the problem as the function in interelectrode next door.
Therefore, in order to improve the fail safe of battery, taking into account of the reduction of stable on heating raising of battery separator and percent thermal shrinkage becomes important problem under such hot environment.About this point, in order to be suppressed at the thermal contraction of the battery separator under the hot environment, for example, as open described in the flat 05-310989 communique the spy, also known have melting mixing ultra-high molecular weight polyethylene and plasticizer and extrude with sheet from mould, and the method that plasticizer is manufactured on the perforated membrane that uses in the battery separator is removed in extraction then.
Even the perforated membrane that utilizes this method to obtain does not cause fusion, film rupture yet under hot environment, good aspect thermal endurance, but opposite with above-mentioned method, because unstretched in its manufacturing process, thus its insufficient strength, and do not improve the problem of thermal contraction.That is, do not know the dividing plate perforated membrane that does not cause that under hot environment fusion, film rupture and thermal contraction are little in the past as yet.
The present invention carries out for the problems referred to above that solve in the battery manufacturing in the past, its purpose is to provide the perforated membrane of the load bonding agent that following battery separator uses: electrode/dividing plate duplexer of making electrode temporarily bonding with dividing plate (Provisional is followed) when the manufacturing of battery, can make battery and electrode and dividing plate efficiently and not have slippage each other, and, after the manufacturing of battery, itself at high temperature can not fuse or film rupture, and brings into play the function of the little dividing plate of thermal contraction.In addition, the object of the present invention is to provide the method for using above-mentioned bonding agent perforated membrane to make battery.
Summary of the invention
The invention provides the perforated membrane of the load bonding agent that a kind of battery separator uses, it is characterized in that, use pin to go into probe-type thermo-mechanical analysis device (analytical equipment of pin ス Block ロ one Block Shi Hot Machine tool), probe with diameter 1mm under the loading of 70g is placed on the perforated membrane, heat this perforated membrane from room temperature for 2 ℃/minute with programming rate on one side, measure its thickness on one side, the thickness of this perforated membrane reaches 1/2 o'clock temperature of the thickness when having placed above-mentioned probe (more than or equal to 200 ℃ perforated membranes as the basis material perforated membrane with this moment, on this basis material perforated membrane load make the polyfunctional isocyanate with have can with the reactive polymer reaction of the functional group of isocyanates radical reaction, make the partial cross-linked and partial cross-linked bonding agent that forms of one.
Particularly, according to the present invention, above-mentioned basis material perforated membrane preferably is at least the polyolefine resin composition that has the bridging property rubber of two keys in 500,000 vistanex and the strand by weight average molecular weight and constitutes, and makes above-mentioned bridging property rubber cross and forms.
In addition, according to the present invention, provide electrode is pressed on the perforated membrane adhere to above-mentioned load bonding agent and the electrode/porous membrane laminated body that forms, with the reactive polymer reaction that makes in polyfunctional isocyanate and this electrode/porous membrane laminated body, make partial cross-linked bonding agent further crosslinked, electrode is bonded on the perforated membrane and electrode/perforated membrane adherend (conjugant) of forming.
In addition, according to the present invention, a kind of cell manufacturing method is provided, it is characterized in that, after in battery case that above-mentioned electrode/porous membrane laminated body is packed into, in above-mentioned battery case, inject the electrolyte and the heating that comprise the polyfunctional isocyanate, make unreacted reactive polymer and above-mentioned polyfunctional isocyanate reaction in the partial cross-linked bonding agent that loads on the perforated membrane, thereby make it further crosslinked, electrode is bonded on the perforated membrane, form electrode/perforated membrane adherend, and obtain comprising the battery of the perforated membrane in this electrode/perforated membrane adherend as dividing plate.
Thereby the load on the basis material perforated membrane of the perforated membrane of the load bonding agent that battery separator of the present invention is used makes the polyfunctional isocyanate and has and can constitute as partial cross-linked bonding agent with the reactive polymer of the partial cross-linked formation of reactive polymer reaction carrying out of the functional group of isocyanates radical reaction.At this, above-mentioned basis material perforated membrane is at least the polyolefine resin composition that has the bridging property rubber of two keys in 500,000 vistanex and the strand by weight average molecular weight and constitutes, and makes above-mentioned bridging property rubber cross and form.
Like this, load the perforated membrane of partial cross-linked reactive polymer have cementability because of this partial cross-linked bonding agent, so by making electrode along this perforated membrane, preferably pressurization under heating, can easily temporarily bond to electrode on the perforated membrane, like this, in the manufacturing of battery, electrode/perforated membrane (dividing plate) duplexer that can be used as the slippage that does not have electrode and perforated membrane (dividing plate) uses, thereby can make battery efficiently.
And, even pack into such duplexer in the battery case and in battery case, inject electrolyte, also keep the temporarily bonding of electrode and perforated membrane (dividing plate), and, because the reactive polymer in the partial cross-linked bonding agent is partial cross-linked, so can prevent or reduce the stripping in the electrolyte, and, when making battery, utilize the further crosslinked of unreacted reactive polymer in the partial cross-linked bonding agent, form electrode and well, firmly and stably bonded to electrode/dividing plate adherend on the perforated membrane (dividing plate) by adaptation.
In addition, according to the present invention, perforated membrane in the perforated membrane of load bonding agent preferably is at least the polyolefine resin composition that has the bridging property rubber of two keys in 500,000 vistanex and the strand by weight average molecular weight and constitutes and make above-mentioned bridging property rubber cross and the perforated membrane that forms, because heat resisting temperature is more than or equal to 200 ℃, so after the manufacturing of battery, itself at high temperature can not fuse or break, and, the function of the dividing plate that the performance thermal contraction is little, like this, the perforated membrane of the load bonding agent of the application of the invention can obtain the good battery of fail safe at high temperature.
Specific embodiments
The perforated membrane of the load bonding agent that battery separator of the present invention is used is to constitute like this: use pin to go into probe-type thermo-mechanical analysis device, probe with diameter 1mm under the loading of 70g is placed on the perforated membrane, heat this perforated membrane from room temperature for 2 ℃/minute with programming rate on one side, measure its thickness on one side, with this moment this perforated membrane thickness become the thickness (the following original depth that this thickness is called this perforated membrane) when having placed above-mentioned probe 1/2 o'clock temperature (the following heat resisting temperature that this temperature is called this film) more than or equal to 200 ℃ perforated membranes as the basis material perforated membrane, on this basis material perforated membrane load make the polyfunctional isocyanate with have can with the reactive polymer reaction of the functional group of isocyanates radical reaction, make the partial cross-linked and partial cross-linked bonding agent that forms of one.
Above-mentioned basis material perforated membrane preferably is at least the polyolefine resin composition that has the bridging property rubber of two keys in 500,000 vistanex and the strand by weight average molecular weight and constitutes, and makes above-mentioned bridging property rubber cross and forms.
Promptly, according to the present invention, if have load on the basis material perforated membrane of above-mentioned thermal characteristic make the polyfunctional isocyanate with have can with the reactive polymer reaction of the functional group of isocyanates radical reaction, make it the crosslinked and partial cross-linked bonding agent that forms of a part, make the perforated membrane of the load bonding agent that battery separator uses, make this perforated membrane as described later and play the battery of spacer function, then because even this dividing plate at high temperature also is not easy fusion, break, keep its thickness, thermal contraction simultaneously is little, prevent interelectrode short circuit well, so can improve the fail safe of battery.
At this, illustrate and use pin to go into the thickness that probe-type thermo-mechanical analysis device is measured the basis material perforated membrane.At first, be placed on the perforated membrane if will be applied in the front end of probe of the diameter 1mm of loading, then this perforated membrane with the part of the preceding end in contact of this probe in because of cause from the loading of probe, its thickness reduces.The thickness of perforated membrane at this moment is called original depth.Thereafter, along with the temperature of perforated membrane rises, its thickness reduces a little gradually, but when the resin that constitutes perforated membrane becomes fusion or semi-molten state, the minimizing that produces big thickness, and next because of the cause of thereafter contraction, can see the phenomenon that thickness is replied a little.Further, if continue the heating perforated membrane, then after the thickness that causes because of above-mentioned contraction increases, begin the minimizing of thickness once more.Therefore, according to the present invention, the thickness continuous decrease of perforated membrane and the temperature that becomes 1/2 o'clock perforated membrane of above-mentioned original depth is defined as the heat resisting temperature of this perforated membrane.If this heat resisting temperature height, then perforated membrane can not fuse, break before arriving higher temperature, can keep its thickness, thereby, by such perforated membrane is used as dividing plate, can obtain the good battery of fail safe under hot environment.
Thereby, according to the present invention, if perforated membrane is except having above-mentioned thermal characteristic, also have solvent resistance or resistance to oxidation reproducibility, then be not particularly limited the perforated membrane that for example can use vistanexes such as polyethylene, polypropylene, polybutene, polyamide, cellulose acetate, polyacrylonitrile etc. to constitute.
But, according to the present invention, as the basis material perforated membrane, preferred especially the use is at least the polyolefine resin composition that has the bridging property rubber of two keys in 500,000 vistanex and the strand by weight average molecular weight and constitutes and make above-mentioned bridging property rubber cross and the perforated membrane that forms.The said polyolefins resin combination also can comprise weight average molecular weight as required than 500,000 little vistanex or thermoplastic elastomer (TPE)s.
More than or equal to 500,000 vistanex, for example can enumerate vistanexes such as polyethylene, polypropylene as above-mentioned weight average molecular weight.The weight average molecular weight upper limit of this vistanex is not particularly limited, but normally about 8,000,000.These vistanexes can separately or mix more than 2 kinds and use.But according to the present invention, in these materials, weight average molecular weight has high strength more than or equal to 500,000 the resulting perforated membrane of extrahigh-molecular weight polyolefins resin, so especially preferably use.
In addition, as above-mentioned bridging property rubber, preferably use in the such molecule of the diolefinic polymer that has two keys in polybutadiene, the polyisoprene equimolecular or ethylene-propylene-diene monomers to have terpolymer of two keys etc.In ethylene-propylene-diene monomer terpolymer,, can enumerate bicyclopentadiene, ENB, hexadiene etc., but in these diene monomers, ENB is preferably used in the crosslinkable reactivity aspect as diene monomers.That is, be that the terpolymer cross-linking reaction of constituent is fine with the ENB, can improve the thermal endurance of resulting perforated membrane more reliably.In addition, for example be that the terpolymer of constituent has alicyclic structure and the two key that derives from diene monomers with the ENB, therefore also can use the terpolymer of hydrogenation in the part of its pair key.In addition, these terpolymers can be any one in random copolymer, block copolymer, the graft copolymer etc.Such terpolymer is sold on market as various EPDM.
In order to make such terpolymer crosslinked fully, in the terpolymer diene monomers components in proportions be preferably ethene, propylene and diene monomers total weight 3 weight % or more than, the scope of preferred especially 4～20 weight %.Particularly, according to the present invention, preferably using the ethylene/propylene/diene monomer components in proportions is the terpolymer of 0.5～0.75/0.05～0.47/0.03～0.2 by weight.
In addition, the ring-opening polymerization polymer polynorbornene of norborene is that the glass transition temperature that has two keys in the molecule is about 35 ℃ polymer, itself not elastomeric, but cooperate the glass transition temperature of the composition of fragrant same clan oil, cycloalkane oil, the formation of paraffin class wet goods oils to be about-60 ℃, possess elastomeric character, can be used as the modifier of various rubber, but in the present invention, owing to also can be used as the bridging property polymer suitably, so be included in the above-mentioned bridging property rubber.
Than 500,000 little vistanexes, can enumerate modified polyolefin resins such as vistanexes such as polyethylene, polypropylene, ethylene-acrylic acid monomer copolymer, vinyl-vinyl acetate copolymer as weight average molecular weight.As thermoplastic elastomer (TPE), can enumerate thermoplastic elastomer (TPE)s such as polystyrene type or TPO, polydienes, polyvinyl chloride, polyesters.Than 500,000 little vistanexes, the lower limit of its weight average molecular weight is not particularly limited about such weight average molecular weight, but is about 20,000 usually.These vistanexes or thermoplastic elastomer (TPE) can use separately, also can merge use more than 2 kinds or 2 kinds.In addition, also can will in molecule, have the material of two keys in the above-mentioned thermoplastic elastomer (TPE) as bridging property rubber.
According to the present invention, as weight average molecular weight than 500,000 little vistanexes, in above-mentioned resin, low-melting polyvinyl resin, to have crystalline TPO elastomer, bringing on low closing temperature (the シ ヤ Star ト ダ ウ Application temperature) this point at the graft copolymer that has the low polymethacrylate of melt temperature on the side chain be particularly preferred.
According to the present invention, as mentioned above, preferred use by weight average molecular weight constitute more than or equal to the polyolefine resin composition that has the bridging property rubber of two keys in 500,000 vistanex and the strand and make above-mentioned bridging property rubber cross and the perforated membrane that forms as the basis material perforated membrane, but at this, weight average molecular weight is more than or equal to the ratio of 500,000 vistanex in the said polyolefins resin combination, if consider the porous film strength that obtains by this polyolefine resin composition or with the balance of other composition, the scope of then preferred 5～95 weight %, the scope of preferred especially 10～90 weight %.On the other hand, in the said polyolefins resin combination, the ratio of bridging property rubber is more than or equal to 3 weight %, the scope of preferred especially 5～35 weight %.
In the said polyolefins resin combination, the ratio of bridging property rubber is utilized the crosslinked of this bridging property rubber, the danger that the thermal endurance aspect of resulting perforated membrane can not be improved fully less than 3 weight % even exist.
Further, according to the present invention, the polyolefine resin composition that the manufacturing perforated membrane is used also can comprise weight average molecular weight as required than 500,000 little vistanex or thermoplastic elastomer (TPE)s, in this case, these components in proportions in polymer composition by the total amount preferably in the scope of 1～50 weight %.By making the basis material perforated membrane have such composition, resulting perforated membrane has closing function (シ ヤ Star ト ダ ウ ン Machine energy) under lower temperature.
Secondly, illustrate that being at least the polyolefine resin composition that has the bridging property rubber of two keys in 500,000 vistanex and the strand by weight average molecular weight constitutes and make above-mentioned bridging property rubber cross and the manufacturing of the perforated membrane that forms.For such perforated membrane, utilize suitable methods such as known up to now dry type system embrane method, film by wet method to carry out the system film after, can obtain by making the bridging property rubber cross in the film.
Promptly, for example with said polyolefins resin combination and solvent, mixing, heating for dissolving, after making the mixing thing of pulpous state, use suitable method to be shaped to sheet, this tablet is rolled, and then carry out single shaft or biaxial stretch-formed, make film, extract and remove solvent in this film then, then can obtain perforated membrane.Secondly, utilize two keys of the bridging property rubber that this perforated membrane has,, can make perforated membrane have needed thermal endurance by making this bridging property rubber cross.
In the manufacturing of perforated membrane, as obtaining the solvent that the mixing thing of above-mentioned pulpous state is used, for example, except aliphat such as nonane, decane, hendecane, dodecane, naphthalane, atoleine or alicyclic, can use the boiling point mineral oil fraction corresponding etc., but wherein preferably use atoleine etc. to comprise alicyclic nonvolatile solvent in a large number with these solvents.
The ratio of said polyolefins resin combination is preferably the scope of 5～30 weight % in the mixing thing of pulpous state, and more preferably the scope of 10～30 weight % then most preferably is 10～25 weight %.That is, from improving the viewpoint of gained porous film strength, the ratio of said polyolefins resin combination is preferably greater than or equals 5 weight % in the mixing thing of pulpous state.On the other hand, preferably be less than or equal to 30 weight %, so that weight average molecular weight is dissolved in the solvent fully more than or equal to 500,000 vistanex, can be mixing to the state that approaches to be stretched over the limit (stretch び and cut り Zhuan ), thereby can obtain polymer chain fully twine knob.In addition, in above-mentioned mixing thing, as required, in the scope of not damaging purpose of the present invention, can cooperate antioxidant, ultra-violet absorber, dyestuff, make additives such as nuclear agent, pigment, antistatic agent.
Mix and mixing said polyolefins resin combination and solvent, make the mixing thing of pulpous state,, can use known up to now suitable method for it is shaped to sheet.For example, use one hundred li mixing roll of spot, kneader etc. with mixing said polyolefins resin combination of intermittent mode and solvent, can between chilled pair of rolls, roll resulting mixing thing, or be clipped between chilled pair of metal plate and cool off, laminate by quick cooling crystallization, in addition, also can use the extruder that the T punch die has been installed to be shaped to sheet.Mixing temperature is not particularly limited, but preferred in 100～200 ℃ scope.
Thickness as the sheet that obtains like this is not particularly limited, but usually preferred in the scope of 3～20mm, and, also can use hot pressing etc. that resulting thin slice is rolled, become the thickness of 0.5～3mm.Usually, this calendering is preferably carried out under 100～140 ℃ temperature.In addition,,, the combination of common stenter method, roll-in method, film blow moulding or these methods be can use, in addition, uniaxial tension, any one mode such as biaxial stretch-formed also can be adopted though be not particularly limited for the resulting thin slice that stretches.Under biaxial stretch-formed situation, can be stretch simultaneously in length and breadth or step drawing in any one.The temperature of stretch processing is preferably 100～140 ℃ scope.
It is to remove to desolvate to form the processing of porous structure from thin slice that desolventizing is handled, for example, and can be by with the solvent clean thin slice and remove residual solvent and carry out this processing.As solvent, can use hydro carbons such as pentane, hexane, heptane, decane, chlorohydrocarbons such as carrene, carbon tetrachloride, fluorohydrocarbons such as HFC-143a, ethers such as ether, diox, alcohols such as methyl alcohol, ethanol, effumability solvents such as ketone such as acetone, butanone.These solvents can separately or mix use more than 2 kinds or 2 kinds.For example thin slice being immersed in the solvent or to thin slice spray solvent uses the desolventizing of the thin slice of such solvent to handle.
According to the present invention, after obtaining perforated membrane by the said polyolefins resin combination like this,, preferably heat-treat in order to reduce its heat-shrinkable.This heat treatment can be the one-level heat treatment once of heating perforated membrane, in addition, also can be initial with lower temperature heating, the multistage heat treatment of heating with higher temperature then.In addition, also can be the temperature lifting type heat treatment that perforated membrane is heated up and heats on one side on one side.But, preferably carry out this heat treatment in the mode of not damaging desirable characteristics that perforated membrane had originally, for example venting quality etc.
Under the heat treated situation of above-mentioned one-level, its heating-up temperature is different because of the composition of perforated membrane, but preferred 40～140 ℃ scope.In addition, by begin to heat, improve thereafter the temperature lifting type or the multistage heat treatment of heating-up temperature from lower temperature, can take into account the crosslinked of bridging property rubber in the perforated membrane, little by little improve the thermal endurance of perforated membrane, so can under the situation of the required character that perforated membranes such as not damaging venting quality because of heating had originally, heat-treat.And can carry out needed heat treatment at short notice.Particularly in multistage heat treatment, initial heating-up temperature is different because of the composition of perforated membrane, but preferred 40～90 ℃ scope, the 2nd grade heating-up temperature is different because of the composition of perforated membrane, but preferred 90～140 ℃ scope.
According to the present invention, in above-mentioned heat treatment step or before and after it,, as mentioned above, make the bridging property rubber cross in the perforated membrane in order to improve the thermal endurance of resulting perforated membrane.Utilize the crosslinked of such bridging property rubber, can significantly improve resulting perforated membrane thermal endurance (fracture-resistant) at high temperature.As mentioned above, the heat treatment of double as perforated membrane, to make the way of the bridging property rubber cross in the perforated membrane be preferred from the productivity aspect, like this, heat treatment by the double as perforated membrane, make the bridging property rubber cross in the perforated membrane, in the heat-shrinkable that reduces perforated membrane, can significantly improve the thermal endurance of perforated membrane.
At this, in order to make the bridging property rubber cross in the resulting perforated membrane, can be in the presence of oxygen, ozone, oxygen compound the heating perforated membrane so that bridging property rubber carries out cross-linking reaction, but wherein, in the presence of oxygen, for example in air, heat perforated membrane or irradiation ultraviolet radiation or electron ray so that the bridging property rubber cross is preferred.In addition, as required, merge and use known up to now peroxide, also can promote the purpose cross-linking reaction.Certainly, also can merge the multiple cross-linking method of use as required.
In the present invention, because the basis material perforated membrane plays dividing plate after the manufacturing of battery, so thickness is in the scope of 1～60 μ m, the particularly thickness scope at 5～50 μ m.When Film Thickness Ratio 1 μ m was thin, intensity was inadequate, when being used as dividing plate in battery, had the danger that causes internal short-circuit.On the other hand, when surpassing 60 μ m, interelectrode distance is excessive, and the internal resistance of battery is excessive.In addition, pore, its voidage that the basis material perforated membrane has average pore size 0.01～5 μ m are in 20～80% scope, particularly are in 25～75% the scope.In addition, the venting quality that the basis material perforated membrane is obtained according to JIS P 8117 is in the scope of 100～1000 seconds/100cc, particularly is in the scope of 100～900 seconds/100cc.
The perforated membrane of the load bonding agent of using for battery separator of the present invention, make the polyfunctional isocyanate with have can be with the reactive polymer reaction of the functional group of isocyanates radical reaction, to make it a part crosslinked, above-mentioned reactive polymer is made partial cross-linked bonding agent, on above-mentioned basis material perforated membrane, preferably at this partial cross-linked bonding agent of scope load of 5～95% of surface area, in the present invention, the gel percentage of preferred especially above-mentioned partial cross-linked bonding agent with 5～80% scopes.
Like this, according to the present invention, by making a part of reactive polymer crosslinked, reactive polymer can be made partial cross-linked bonding agent with cementability, therefore, if make the so partial cross-linked bonding agent of perforated membrane load, electrode/porous membrane laminated the body that utilizes this partial cross-linked bonding agent to make electrode temporarily bonded on the perforated membrane and form, even then when the manufacturing of battery, this duplexer is contacted with electrolyte, also can prevent or reduce the reactive polymer stripping in electrolyte, can effectively reactive polymer be used for the bonding of perforated membrane and electrode, like this, can more firmly electrode be bonded on the perforated membrane.
In addition, according to the present invention, above-mentioned reactive polymer preferably have carboxyl or hydroxyl as have can with the functional group of NCO reactive activity hydrogen, specifically, especially preferably comprise the polymer of reactive monomer composition with above-mentioned functional group with (methyl) acrylate composition.
In more detail, concrete example as above-mentioned reactive monomer, can enumerate the co-polymerized monomer that (methyl) acrylic acid, itaconic acid, maleic acid etc. contain carboxyl, preferably (methyl) acrylic acid or 2-ethoxy (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, 4-hydroxyl butyl (methyl) acrylate etc. contain the co-polymerized monomer of hydroxyl, preferred hydroxyalkyl (methyl) acrylate.But in addition, also available have amino co-polymerized monomer as reactive monomer.
As above-mentioned (methyl) acrylate, preferably using carbon number in the alkyl such as ethyl (methyl) acrylate, butyl (methyl) acrylate, propyl group (methyl) acrylate, iso-octyl (methyl) acrylate, 2-hydroxyethyl (methyl) acrylate, dodecyl (methyl) acrylate for example is 1～12 Arrcostab.
In the present invention, special preferred reactive polymer comprises the above-mentioned reactive monomer composition of 0.1～20 weight % scope, comprise (methyl) acrylate composition or as required simultaneously, co-polymerized monomer composition with cyano group, vinyl monomer compositions such as preferred (methyl) acrylonitrile composition or styrene, AMS, vinyl acetate.Particularly in the present invention, reactive polymer preferably be less than or equal to 80 weight %, preferably the scope at 5～70 weight % comprises the co-polymerized monomer composition that has cyano group, preferred (methyl) acrylonitrile composition is so that the thermal endurance of reactive polymer and solvent resistance are good.In reactive polymer, co-polymerized monomer components in proportions with cyano group is that 5 weight % are when following, almost there be not effect aspect the raising of thermal endurance and solvent resistance, on the other hand, when surpassing 80 weight %, because the glass transition temperature of resulting reactive polymer surpasses 100 ℃ sometimes, so be unfavorable.Particularly, according to the present invention, reactive polymer preferably is made of the reactive monomer composition of 0.1～20 weight %, (methyl) acrylate composition of 10～95 weight % and (methyl) acrylonitrile of 4.9～60 weight %.
But, in the present invention, above-mentioned reactive polymer is not limited to mentioned component, can get final product with the functional group of isocyanates radical reaction, the polymer of for example reactive hydrogen so long as have, for example also can use have can with the polyolefin polymers of the functional group of isocyanates radical reaction, rubber polymer, polyethers polymer etc.And,, also can will have the acrylic acid modified fluororesin (for example, セ Application ト ラ Le nitre (strain) system セ Off ラ Le コ-ト FG730B can be used as wax and obtains) of hydroxyl in the molecule suitably as reactive polymer according to the present invention.
In addition, according to the present invention, the glass transition temperature of reactive polymer preferably is in 0～100 ℃ scope, especially preferably is in 20～100 ℃ scope.
Above-mentioned reactive polymer can be by for example making needed monomer copolymerization in benzene,toluene,xylene, ethyl acetate, the butyl acetate equal solvent, obtains with the form of polymer solution.On the other hand,, can obtain the aqueous dispersions of reactive polymer, so after making polymer separation, drying thus, make it to be dissolved in the above-mentioned solvent also as polymer solution according to emulsion polymerization.In addition, when being undertaken, except above-mentioned monomer, also can use multifunctional cross-linkable monomers such as divinylbenzene, trimethylolpropane triacrylate in the ratio that is less than or equal to 1 weight % by emulsion method.
As multi-functional isocyanates, except aromatic series such as phenylene diisocyanate, toluene support vulcabond, methyl diphenylene diisocyanate, diphenyl ether vulcabond, HDI, cyclohexane diisocyanate, aromatic-aliphatic, alicyclic, aliphatic diisocyanate, preferably use polyalcohols such as these vulcabond and trimethylolpropane to add the so-called isocyanate addition product that is shaped as.
According to the present invention, such as mentioned above, in the solution of reactive polymer, cooperate scheduled volume, promptly enough make the above-mentioned multi-functional isocyanates of the crosslinked amount of a part of reactive polymer, after making this solution of basis material perforated membrane load, make above-mentioned reactive polymer and above-mentioned multi-functional isocyanate reaction, the functional group that has with reactive polymer (for example, the reactive hydrogen base) reaction, make a part of reactive polymer crosslinked, be made into partial cross-linked bonding agent with cementability, by making this partial cross-linked bonding agent of basis material perforated membrane load, obtain the perforated membrane of the load bonding agent that battery separator of the present invention uses.
According to the present invention, the crosslinked and partial cross-linked bonding agent that constitute of a part that preferably makes above-mentioned reactive polymer has the gel percentage of 5～80% scope.At this, so-called gel percentage is the value as following definition: make reactive polymer composition (A+B) weight portion that the perforated membrane load is made of reactive polymer A weight portion and multi-functional isocyanates B weight portion and make it reaction, after a part that makes reactive polymer is crosslinked, this perforated membrane was flooded 7 days down at 23 ℃ in toluene, dry then, if with after the drying on perforated membrane remaining bonding agent be made as the C weight portion, then the gel percentage is the value of (C/ (A+B)) * 100 (%) definition.
In order to obtain having the percentile partial cross-linked bonding agent of gel of 5～80% scopes, though do not limit, but usually for reactive polymer 100 weight portions, range fit polyfunctional isocyanate and heating with 0.1～10 weight portion make it to solidify, carry out cross-linking reaction and becoming stable aspect the characteristic, can obtain above-mentioned partial cross-linked bonding agent thus up to resulting reactive polymer.The temperature that is heating and curing or time are decided by employed reactive polymer or polyfunctional isocyanate, but can determine these reaction conditions according to experiment.If heating makes it reaction under 50 ℃ temperature in 7 days, cross-linking reaction is finished, resulting partial cross-linked reactive polymer, be that partial cross-linked bonding agent becomes stable aspect characteristic.
Like this, according to the present invention,, therefore, in the present invention, this reaction product is called partial cross-linked bonding agent by making the reaction of polyfunctional isocyanate and reactive polymer, making one partial reaction, the crosslinked reaction product that obtains have cementability.Thereby, by make the perforated membrane load such have a perforated membrane that 5～80% the percentile partial cross-linked bonding agent of gel is made the load bonding agent, as described later, if the electrode pressure is adhered on this perforated membrane, then can easily temporarily bond to electrode on the perforated membrane, like this, can obtain electrode/porous membrane laminated body.
And, after in battery case that this electrode/porous membrane laminated body is packed into, in this battery case, inject when having dissolved the electrolyte of multi-functional isocyanates, keeping under the temporary transient bonding state of electrode/perforated membrane, unreacted reactive polymer is further crosslinked because of the multi-functional isocyanates in the electrolyte in the partial cross-linked bonding agent, thereby can obtain electrode by the adaptation electrode/dividing plate adherend of strong bond to the perforated membrane well.At this, according to the present invention,, can prevent or reduce its stripping in electrolyte because reactive polymer is partial cross-linked to have 5～80% the percentile mode of gel, thereby can be used for the bonding of electrode and perforated membrane effectively, so electrode and perforated membrane are stabilized and are bonding more firmly.According to the present invention, partial cross-linked bonding agent especially preferably has 20～60% gel percentage.
Further, according to load of the present invention in the perforated membrane of partial cross-linked bonding agent, because unreacted reactive polymer can not surpass above-mentioned degree reaction, crosslinked in the partial cross-linked bonding agent, so be stable, even in long-time, preserve, also undergo no deterioration.
In the present invention, in order to make the reactive polymer composition that constitutes by reactive polymer and multi-functional isocyanates load to the basis material perforated membrane.For example, can directly be coated in above-mentioned reactive polymer composition on the basis material perforated membrane and make it dry, in addition, also can be coated on the fissility sheet, transfer to after the drying on the basis material perforated membrane.In addition, in order to improve the screening characteristics of reactive polymer composition to the basis material perforated membrane, also can be coupled in the reactive polymer composition with the ratio that is less than or equal to 50 weight % with organic solvents such as butanone, methylisobutylketone or inorganic micro powder ends such as powdered whiting or silica sand micropowder as mobile modifier.
In addition, according to the present invention, in the time will being coated on the basis material perforated membrane by the reactive polymer composition that reactive polymer and polyfunctional isocyanate constitute, preferably partly, promptly with for example wire, mottled, latticed, striated, tortoise plastron shape decorative pattern shapes etc. partly apply, particularly, by the above-mentioned reactive polymer composition of coating in 5～95% scopes of the surface area of the basis material perforated membrane of application of reactive polymer composition, obtain electrode and perforated membrane (thereby, dividing plate) strong bond between, by using such electrode/dividing plate adherend, can obtain having the battery of good characteristic simultaneously.
According to the present invention, as mentioned above, make the load of basis material perforated membrane have the percentile partial cross-linked bonding agent of 5～80% gels, make the perforated membrane of the load bonding agent that battery separator uses, make electrode along this perforated membrane, preferably pressurize, obtain electrode/porous membrane laminated body while the temperature that is heated to 50～100 ℃.
In the present invention, negative pole and anodal different and different according to battery, but in general can use employing resin binder carrying active substance and conductive agent as required on the conductive base material and the flaky material that constitutes.
According to the present invention, by using such electrode/porous membrane laminated body, do not have mutual slippage between electrode and the perforated membrane, and can make battery efficiently, can obtain that after the battery manufacturing above-mentioned perforated membrane itself plays high performance spacer function and good battery aspect fail safe.
According to the present invention, can make loading section crosslinked bonding agent in two sides in the table of basis material perforated membrane, with electrode, be that negative pole and positive pole are pressed respectively and adhered in this table on the two sides, carry out temporarily bondingly, make electrode/porous membrane laminated body, in addition, the also crosslinked bonding agent of loading section on a surface of basis material perforated membrane only, only on its another surface, press bonding electrode, be any one in negative pole and the positive pole, carry out temporarily bondingly, make electrode/porous membrane laminated body.Certainly, also can make and just have (bearing) utmost point/perforated membrane/duplexer of negative (just) utmost point/porous membrane structure.
Above-mentioned electrode of the present invention/porous membrane laminated body can be suitable for making battery.Promptly, after in battery case that above-mentioned electrode/porous membrane laminated body is packed into, in battery case, inject and dissolved polyfunctional isocyanate's electrolyte, make unreacted reactive polymer reaction in the partial cross-linked bonding agent of itself and above-mentioned electrode/porous membrane laminated body, make it further crosslinked, thus electrode is bonded on the perforated membrane and integrated, then above-mentioned perforated membrane plays the effect of dividing plate, can obtain simultaneously having that electrode bonds on this dividing plate securely and the battery of the electrode/dividing plate adherend that forms.
The ratio of the multi-functional isocyanates in the electrolyte is with respect to reactive polymer 100 weight portions that load to perforated membrane, the normally scope of 0.1～20 weight portion.When the ratio of multi-functional isocyanates is less than 0.1 weight portion with respect to reactive polymer 100 weight portions that load to perforated membrane, the reactive polymer that causes because of multi-functional isocyanates is crosslinked to be inadequate, in resulting electrode/dividing plate adherend, can not obtain between electrode and the dividing plate between strong bond.But with respect to uncrosslinked reactive polymer 100 weight portions during more than 20 weight portions, the bonding agent after crosslinked is too hard, hinders dividing plate and interelectrode adaptation sometimes in the ratio of multi-functional isocyanates.
According to the present invention, to the partial cross-linked bonding agent of the partial cross-linked formation of reactive polymer be loaded on the perforated membrane, make electrode along this surface, under the temperature that does not produce the perforated membrane distortion, heat on one side, pressurize on one side, a part of bonding agent is pressed in the electrode, we can say, electrode is temporarily bonded on the basis material perforated membrane, make electrode/porous membrane laminated body, then, after in battery case that this duplexer is packed into, in this battery case, inject and dissolved polyfunctional isocyanate's electrolyte, make its with above-mentioned partial cross-linked bonding agent in unreacted reactive polymer react, make bonding agent further crosslinked, obtain electrode/perforated membrane adherend.That is, electrode is bonded on the perforated membrane.Thereby in such electrode/perforated membrane adherend, perforated membrane and electrode are firmly bonded.
Dividing plate is played in perforated membrane in the electrode that obtains like this/perforated membrane adherend back in being assembled into battery.At this, in the such electrode of the present invention/perforated membrane adherend, perforated membrane (that is, dividing plate) is less than or equal to 25% usually even at high temperature the area percent thermal shrinkage is also little, preferably is less than or equal to 20%, most preferably is less than or equal to 15%.
Same with above-mentioned electrode/porous membrane laminated body, in the present invention, electrode/dividing plate adherend not only comprises negative pole/dividing plate/anodal adherend structure, also comprises the electrode/dividing plate adherend of any one party in negative pole or the positive pole or just (is bearing) structure of the utmost point/dividing plate/negative (just) utmost point/dividing plate.
Electrolyte be with dissolving electrolyte salt in solvent and the solution that forms.As electrolytic salt, for example can use with alkaline-earth metal such as alkali metal such as hydrogen, lithium, sodium, potassium, calcium, strontium, uncle or quaternary ammonium salt etc. to be cation constituent, be the salt of anion component with organic acids such as inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, fluoboric acid, hydrofluoric acid, hexafluorophosphoric acid, perchloric acid, organic carbonate, organic sulfonic acid, fluorine replacement organic sulfonic acids.But, in these compositions, especially preferably use with the salt of alkali metal ion as cation constituent.
As the solvent of used for electrolyte,, can use any solvent so long as dissolve the solvent of above-mentioned electrolytic salt.As the solvent of non-water class, can use chain ester classes such as ethers such as cyclic ester class, oxolane, dimethoxy-ethane, dimethyl carbonate, diethyl carbonate, ethyl-methyl carbonic ester such as ethylene carbonate, propylene carbonate, butylene carbonate, γ-Ding lactones.These solvents can separately or mix more than 2 kinds and use.
Industrial applicibility
The perforated membrane of the load bonding agent that the application of the invention battery separator is used, can easily obtain not having electrode/perforated membrane (dividing plate) duplexer of slippage, in addition, when the manufacturing of battery, because formation electrode adaptation well, firmly and stably bonds to the electrode/dividing plate adherend on the perforated membrane (dividing plate), so can suppress the generation of substandard product, can make battery with good productivity.And because the perforated membrane of the load bonding agent used of battery separator of the present invention is after the manufacturing of battery, itself at high temperature can not fuse or break, and, play the effect of the little dividing plate of thermal contraction, so can obtain the good battery of fail safe under the high temperature.
Embodiment
Below enumerate embodiment the present invention is described, but the invention is not restricted to these embodiment.Below, following thickness and the voidage of obtaining perforated membrane.
(thickness of perforated membrane)
Obtain based on the mensuration of 1/10000mm (シ Star Network ネ ス ゲ one ジ) and 10000 times of scanning electron microscope photos of perforated membrane section.
(voidage of perforated membrane)
Unit are S (cm by perforated membrane 2) weight W (g), average thickness t (cm) and constitute the density d (g/cm of the resin of perforated membrane 3) calculate with following formula.
Voidage (%)=(1-(W/S/t/d)) * 100
Embodiment 1
(making of perforated membrane A)
To be mixed into pulpous state by the 16 weight account polyethylene resin combinations and the 84 weight portion atoleines of the polyvinyl resin with super-high molecular weight formation of the weight average molecular weight 3,500,000 of the thermoplastic elastomer (TPE) (Sumitomo Chemical (strain) system TPE824) of norbornene open-loop polymer (polynorbornene) powder of 8 weight % (Japanese ゼ オ Application (strain) system (ノ one ソ レ Star Network ス) NB, weight average molecular weight are more than or equal to 2,000,000), 12 weight % and 80 weight %, under 160 ℃ temperature, carry out about 1 hour dissolving, mixing with small-sized kneader.Then, resulting mixing thing is clipped between the metallic plate that is cooled to 0 ℃, while cool off, calendering formation is sheet.Then, carrying out hot pressing under 115 ℃ temperature, is 0.5mm up to the thickness that makes this sheet, so under the identical temperature with 4.5 * 4.5 times of whiles in length and breadth biaxial stretch-formed after, use heptane to carry out desolventizing and handle.In air, under 85 ℃, the perforated membrane that obtains is like this carried out heating in 6 hours, heated 1.5 hours down at 118 ℃ then, carry out the heat treatment of perforated membrane, make the bridging property rubber (above-mentioned polynorbornene) in the perforated membrane crosslinked simultaneously, obtain purpose perforated membrane A.The thickness of this perforated membrane A is that 25 μ m, voidage are 50%, has the pore that average pore size is 0.1 μ m, uses pin described later to go into probe-type thermo-mechanical analysis device and checks that the result shows that heat resisting temperature is 370 ℃.
(going into the heat resisting temperature that probe-type thermo-mechanical analysis device is measured perforated membrane) by pin
Go into the square perforated membrane sample of placing length of side 5mm on the sample stage of probe-type thermo-mechanical analysis device ((セ イ コ one) electronics (strain) system EXSTAR6000) at pin, placing top end diameter on this sample is the probe of 1mm.On this probe, apply the loading of 70gf,, measured the sample thickness variation from the speed heated sample of room temperature with 2 ℃/minute.Sample thickness is become the heat resisting temperature of 1/2 o'clock temperature of the thickness of sample (original depth) when sample applied loading as sample.
(preparation of reactive polymer)
Acrylic acid nitrile 10 weight portions
Methacrylic acid 5 weight portions
Butyl acrylate 30 weight portions
Ethyl acrylate 60 weight portions
Polyalkylene glycol alkyl phenyl ether 3 weight portions
N-dodecane mercaptan 10 weight portions
Potassium peroxydisulfate 0.3 weight portion
Ion exchange water 300 weight portions
Utilize conventional method to make said mixture carry out emulsion polymerisation, obtain the aqueous dispersions of reactive polymer.The weight average molecular weight of this reactive polymer is about 850,000, and glass transition temperature is-13 ℃.10% hydrochloric acid is added in the aqueous dispersions of this reactive polymer, makes the reactive polymer precipitation, after taking out and fully washing, carry out drying under reduced pressure.
The reactive polymer that 100 weight portions are obtained like this is dissolved in toluene/butanone (weight ratio 75/25) mixed solvent, the solution for preparing 7% concentration of above-mentioned reactive polymer, therein the reactive polymer of per 100 weight portions is added the silica sand powder of the average grain diameter 12nm of 5 weight portions, it is disperseed equably, 3 functional isocyanate, 0.3 weight portion that the HDI of further cooperation 3 molar part and the trimethylolpropane addition of 1 molar part obtain, the solution of preparation feedback polymer composition.
(preparation of the perforated membrane of the crosslinked bonding agent of loading section)
Use line bar (ワ イ ヤ one バ one) (line footpath 0.2mm) on peeling paper, to apply the solution of above-mentioned reactive polymer composition, after the drying, above-mentioned reactive polymer composition is transferred to two sides in the table of above-mentioned perforated membrane A with this peeling paper with wire.This perforated membrane is put into the thermostatic chamber 7 days of 50 ℃ of temperature, make a part and the reaction of 3 functional isocyanate of the reactive polymer in the above-mentioned reactive polymer composition, obtain the perforated membrane A of the partial cross-linked bonding agent of load gel percentage 58%.
(making of electrode)
The cobalt acid lithium (LiCoO that mixed average grain diameter 15 μ m by weight 85: 10: 5 2) and powdered graphite and polyvinylidene fluoride resin, it is added in the N-N-methyl-2-2-pyrrolidone N-slurries of preparation solid component concentration 15 weight %.Utilize coating machine after applying these slurries with the thickness of 200 μ m on the aluminium foil surface of thickness 20 μ m, 80 ℃ of dryings 1 hour.Then on the back side of this aluminium foil similarly the thickness with 200 μ m apply above-mentioned slurries, 120 ℃ of dryings after 2 hours,, make the positive plate of thickness 200 μ m by roll-in.
By weight 95: 5 admixed graphite powder and polyvinylidene fluoride resin, it is added in the N-N-methyl-2-2-pyrrolidone N-slurries of preparation solid component concentration 15 weight %.Utilize coating machine after applying these slurries with the thickness of 200 μ m on the copper foil surface of thickness 20 μ m, 80 ℃ dry 1 hour down.Then on the back side of this Copper Foil similarly the thickness with 200 μ m apply above-mentioned slurries, 120 ℃ of dryings after 2 hours,, make the negative plate of thickness 200 μ m by roll-in.
(making of negative pole/dividing plate/anodal duplexer)
Make the surface of above-mentioned positive plate, and make negative plate, then at 80 ℃ of temperature, pressure 5kg/cm along the back side along the perforated membrane A of the above-mentioned partial cross-linked bonding agent of load 2Under carry out heating in 5 minutes, pressurization, obtain the positive and negative electrode sheet and press sticking and temporarily bond to the negative pole/perforated membrane/anodal duplexer that forms on the perforated membrane.
(evaluating characteristics of the assembling of battery and gained battery)
In being full of the glove-box of argon gas, make electrolytic salt phosphorus hexafluoride acid lithium (LiPF 6) be dissolved in ethylene carbonate/ethyl-methyl carbonic ester mixed solvent (volume ratio 1/2), making its concentration is 1.2 moles/L, preparation electrolyte.Further, the toluene di-isocyanate(TDI) of dissolving 3 molar part and the trimethylolpropane of 1 molar part add 3 functional isocyanate, 3 weight portions that are shaped as in the above-mentioned electrolyte of 100 weight portions.
Above-mentioned negative pole/perforated membrane/anodal duplexer is packed in the Coin-shaped battery jar of 2016 sizes of double as positive-negative electrode plate, the electrolyte that will dissolve above-mentioned 3 functional isocyanate inject this Coin-shaped battery the jar in after, battery can is sealed, make semi-finished product.Then, these semi-finished product are put into the thermostatic chamber 7 days of 50 ℃ of temperature, make that unreacted reactive polymer and above-mentioned 3 functional isocyanate carry out cross-linking reaction in the partial cross-linked bonding agent on the perforated membrane that loads on above-mentioned negative pole/perforated membrane/anodal duplexer, make positive and negative electrode bond to perforated membrane, be on the dividing plate, the Coin shape lithium rechargeable battery of (the dividing plate)/anodal adherend that obtains having negative pole/perforated membrane.
For this battery, after carrying out discharging and recharging for 5 times with the speed of 0.2CmA, with the charging of the speed of 0.2CmA, discharge with the speed of 2.0CmA then, be 87% with the discharge load characteristic of the ratio evaluation of the discharge capacity under the discharge capacity under the 2.0CmA speed/0.2CmA speed.
(mensuration and the evaluation of the area percent thermal shrinkage of dividing plate)
Positive pole/the perforated membrane that is die-cut into preliminary dimension/negative pole duplexer is immersed in the electrolyte that has dissolved above-mentioned 3 functional isocyanate, be clipped between the glass plate then, further, in order to suppress the volatilization of electrolyte, encase with the fluororesin sheet, place the weight of 50g thereon, put into the thermostatic chamber 7 days of 50 ℃ of temperature, make reactive polymer and above-mentioned 3 functional isocyanate in the partial cross-linked bonding agent on the perforated membrane that loads on above-mentioned positive pole/perforated membrane/negative pole duplexer carry out cross-linking reaction, thereby positive and negative electrode is bonded on the perforated membrane (being the dividing plate in the battery), obtain positive pole/perforated membrane/negative pole adherend.
Put into 200 ℃ drying machine after 1 hour at the positive pole/perforated membrane that will obtain like this/negative pole adherend from the state between glass plate of being clipped in, take off glass plate from positive pole/perforated membrane/negative pole adherend, peel off dividing plate from positive and negative electrode, read in scanner, with the area of the perforated membrane of initial use relatively, trying to achieve the area percent thermal shrinkage is 10%.
Embodiment 2
(making of perforated membrane B)
To be mixed into pulpous state by the 20 weight account polyethylene resin combinations of the polyvinyl resin with super-high molecular weight formation of the weight average molecular weight 3,000,000 of norbornene open-loop polymer (polynorbornene) powder of 6 weight % (Japanese ゼ オ Application (strain) system (ノ one ソ レ Star Network ス NB), weight average molecular weight are more than or equal to 2,000,000) and 94 weight % and the atoleine of 80 weight portions, and use small-sized kneader under 160 ℃ temperature, to carry out about 1 hour dissolving, mixing.Then, resulting mixing thing is clipped between the metallic plate that is cooled to 0 ℃, Yi Bian Yi Bian sharply cooling, calendering formation are sheet.Then carrying out hot pressing under 117 ℃ temperature, is 0.5mm up to the thickness that makes this sheet, further under the identical temperature with 3.8 * 3.8 times of whiles in length and breadth biaxial stretch-formed after, use heptane to carry out desolventizing and handle.In air, under 85 ℃ the perforated membrane that obtains is like this carried out heating in 6 hours, then 125 ℃ of down heating 2 hours, the heat treatment of carrying out perforated membrane makes the bridging property rubber cross in the perforated membrane simultaneously, obtains purpose perforated membrane B.The thickness of this perforated membrane B is that 23 μ m, voidage are 45%, has the pore that average pore size is 0.07 μ m, uses pin to go into probe-type thermo-mechanical analysis device as described above and checks that the result shows that heat resisting temperature is 430 ℃.
(mensuration of the area percent thermal shrinkage of the evaluation of battery behavior and dividing plate)
Except replace the perforated membrane A among the embodiment 1 with perforated membrane B, obtain the perforated membrane B of the partial cross-linked bonding agent of load gel percentage 58% with method with embodiment 1.Use the perforated membrane B of the crosslinked bonding agent of this loading section, obtain negative pole/dividing plate/anodal duplexer similarly to Example 1, use this duplexer to assemble the Coin shape lithium rechargeable battery similarly to Example 1, this battery is estimated the discharge load characteristic similarly to Example 1, the result is 89%, in addition, the percent thermal shrinkage of dividing plate is 16%.
Embodiment 3
Methyl diphenylene diisocyanate with 2 weight portions replaces the HDI of 3 molar part among the embodiment 1 and the trimethylolpropane of 1 molar part to add 3 weight portions, 3 functional isocyanate that are shaped as, the preparation feedback polymer composition, similarly to Example 1 on the surface of perforated membrane A and the two sides, the back side respectively on its 30% area with point-like coating said composition after, this perforated membrane is put into the thermostatic chamber 7 days of 50 ℃ of temperature, the perforated membrane A of partial cross-linked bonding agent of gel percentage 35% that obtained load.
The perforated membrane A of partial cross-linked bonding agent that used the load obtain like this, obtain negative pole/dividing plate/anodal duplexer similarly to Example 1, use this duplexer to assemble the Coin shape lithium rechargeable battery similarly to Example 1, this battery is estimated the discharge load characteristic similarly to Example 1, the result is 91%, in addition, the percent thermal shrinkage of dividing plate is 18%.
Embodiment 4
Acrylic acid nitrile 40 weight portions
2-hydroxyethylmethacry,ate 2 weight portions
Methyl methacrylate 10 weight portions
2-ethylhexyl acrylate 50 weight portions
Azodiisobutyronitrile 0.3 weight portion
Toluene 300 weight portions
Utilize conventional method to make said mixture carry out emulsion polymerisation, obtain the toluene solution of reactive polymer.The weight average molecular weight of this reactive polymer is about 300,000, and glass transition temperature is 5 ℃.In this reactive polymer solution, cooperate the HDI of 3 molar part and the trimethylolpropane of 1 molar part to add 3 functional isocyanate, 1 weight portion that is shaped as, preparation feedback polymer composition for its solid constituent 100 weight portions.
On 30% surface area of fissility oriented polypropylene resin molding with this reactive polymer composition of mottled coating, after the drying, fit in the same manner on the two sides, the surperficial back side of perforated membrane A with embodiment 1, under 60 ℃ temperature, heat on one side, pressurization is on one side pressed sticking, and put into the thermostatic chamber 7 days of 50 ℃ of temperature, the perforated membrane A of partial cross-linked bonding agent of gel percentage 54% that obtained on two sides, the surperficial back side, having fissility stretched polypropylene films, load.
From this load after the perforated membrane A of partial cross-linked bonding agent peels off above-mentioned fissility stretched polypropylene films, make above-mentioned positive plate along the surface, make above-mentioned negative plate along the back side simultaneously, then at 80 ℃ of temperature, pressure 5kg/cm 2Under carry out 5 minutes the heating, the pressurization, obtaining the positive and negative electrode sheet presses sticking and temporarily bonds on the perforated membrane and the negative pole/dividing plate/anodal duplexer that forms, use the negative pole/dividing plate/anodal duplexer that obtains like this to assemble the Coin shape lithium rechargeable battery similarly to Example 1, estimate the discharge load characteristic similarly to Example 1 for this battery, the result is 89%, in addition, the percent thermal shrinkage of dividing plate is 15%.
Embodiment 5
(making of perforated membrane C)
EPDM (Sumitomo Chemical (strain) system エ ス プ レ Application 512F with 20 weight %, ENB content 4 weight %) and polyethylene resin composition 15 weight portions that constitute of the polyvinyl resin with super-high molecular weight of the weight average molecular weight 1,500,000 of 80 weight % and the atoleine of 85 weight portions be mixed into pulpous state equably, use small-sized kneader under 160 ℃ temperature, to carry out about 1 hour dissolving, mixing., resulting mixing thing be clipped in the metallic plate that be cooled to 0 ℃ between, Yi Bian Yi Bian sharply cooling, calendering formation are sheet thereafter.Carrying out hot pressing then under 115 ℃ temperature, is 0.4mm up to the thickness that makes this sheet, so under 123 ℃ the temperature with 4.0 * 4.0 times of whiles in length and breadth biaxial stretch-formed after, use heptane to carry out desolventizing and handle.In air, under 85 ℃, the perforated membrane that obtains is like this carried out heating in 6 hours, heated 1.5 hours down at 116 ℃ then, carry out the heat treatment of perforated membrane, make the bridging property rubber cross in the perforated membrane simultaneously, obtain purpose perforated membrane C.The thickness of this perforated membrane C is that 24 μ m, voidage are 42%, has the pore that average pore size is 0.08 μ m, as mentioned above, uses pin to go into probe-type thermo-mechanical analysis device and checks that heat resisting temperature is 320 ℃ as a result.
(mensuration of the area percent thermal shrinkage of the evaluation of battery behavior and dividing plate)
Except using perforated membrane C to replace the perforated membrane A among the embodiment 1, the perforated membrane C of partial cross-linked bonding agent of gel percentage 58% that obtained load similarly to Example 1.Use the perforated membrane C of the crosslinked bonding agent of this loading section, obtain negative pole/dividing plate/anodal duplexer similarly to Example 1, use this duplexer to assemble the Coin shape lithium rechargeable battery similarly to Example 1, estimated the discharge load characteristic similarly to Example 1 for this battery, the result is 86%, in addition, the percent thermal shrinkage of dividing plate is 12%.
Embodiment 6
N, N-diethyl acrylic amine 50 weight portions
Butyl acrylate 32 weight portions
Acrylic acid nitrile 15 weight portions
4-hydroxybutyl acrylate 3 weight portions
Azodiisobutyronitrile 0.2 weight portion
Ethyl acetate 150 weight portions
Utilize conventional method to make said mixture carry out polymerisation in solution, obtain the ethyl acetate solution of reactive polymer.The weight average molecular weight of this reactive polymer is about 490,000, and glass transition temperature is 35 ℃.In this reactive polymer solution, cooperate the HDI of 3 molar part and the trimethylolpropane of 1 molar part to add 3 functional isocyanate, 1 weight portion that is shaped as with respect to its solid constituent 100 weight portions, the preparation feedback polymer composition, in addition, the perforated membrane A of partial cross-linked bonding agent of gel percentage 52% that obtained load similarly to Example 1.
The perforated membrane A of partial cross-linked bonding agent that used this load, obtain negative pole/dividing plate/anodal duplexer similarly to Example 1, use this duplexer to assemble the Coin shape lithium rechargeable battery similarly to Example 1, estimate the discharge load characteristic similarly to Example 1 for this battery, the result is 88%, in addition, the percent thermal shrinkage of dividing plate is 9%.
Comparative example 1
Under the condition that does not make the perforated membrane A loading section crosslinked bonding agent identical, directly use this perforated membrane A assembled battery with embodiment 1.That is, make the surface of above-mentioned positive plate, make negative plate along the back side simultaneously, make duplexer along above-mentioned perforated membrane.
Electrode/porous membrane laminated body in using above-mentioned duplexer replacement embodiment 1, assemble the Coin shape lithium rechargeable battery similarly to Example 1, estimate the discharge load characteristic similarly to Example 1 for this battery, the result is 95%, in addition, the percent thermal shrinkage of dividing plate is 72%.
Comparative example 2
(making of perforated membrane D)
Polyethylene resin composition 15 weight portions that will be made of the polyvinyl resin with super-high molecular weight of the weight average molecular weight 1,500,000 of the polyvinyl resin of the weight average molecular weight 200,000 of 60 weight % and 40 weight % and the atoleine of 85 weight portions are mixed into pulpous state, use small-sized kneader to carry out about 1 hour dissolving, mixing under 160 ℃ temperature.Then, resulting mixing thing is clipped between the metallic plate that is cooled to 0 ℃, Yi Bian Yi Bian sharply cooling, calendering formation are sheet.Then, carrying out hot pressing under 115 ℃ temperature, is 0.5mm up to the thickness that makes this sheet, and then, under the identical temperature with 4.0 * 4.0 times of whiles in length and breadth biaxial stretch-formed after, use heptane to carry out desolventizing and handle.In air, under 85 ℃, the perforated membrane that obtains is like this carried out heating in 6 hours, heated 1 hour down at 116 ℃ then, obtain purpose perforated membrane D.The thickness of this perforated membrane D is that 24 μ m, voidage are 39%, has the pore that average pore size is 0.1 μ m, uses pin to go into probe-type thermo-mechanical analysis device as described above and checks that heat resisting temperature is 160 ℃ as a result.
(mensuration of the area percent thermal shrinkage of the evaluation of battery behavior and dividing plate)
Except using perforated membrane D to replace the perforated membrane A among the embodiment 1, the perforated membrane D of partial cross-linked bonding agent of gel percentage 58% that obtained load similarly to Example 1.The perforated membrane D of this partial cross-linked bonding agent of working load, obtain negative pole/dividing plate/anodal duplexer similarly to Example 1, use this duplexer to assemble the Coin shape lithium rechargeable battery similarly to Example 1, estimate the discharge load characteristic similarly to Example 1 for this battery, the result is 90%.In addition, plan to measure the area percent thermal shrinkage of this battery median septum, but partition ruptures can not be measured the area percent thermal shrinkage.

Claims (10)

1. the perforated membrane of the load bonding agent used of a battery separator, it is characterized in that: use pin to go into probe-type thermo-mechanical analysis device, probe with diameter 1mm under the loading of 70g is placed on the perforated membrane, heat this perforated membrane from room temperature for 2 ℃/minute with programming rate on one side, measure its thickness on one side, with this moment this perforated membrane thickness 1/2 o'clock temperature becoming the thickness when placing above-mentioned probe more than or equal to 200 ℃ perforated membrane as the basis material perforated membrane, on this basis material perforated membrane load make have can with reactive polymer and polyfunctional isocyanate's reaction of the functional group of isocyanates radical reaction, thereby make the partial cross-linked and partial cross-linked bonding agent that forms of one.
2. the perforated membrane of the described load bonding agent of claim 1, wherein the basis material perforated membrane is at least the polyolefine resin composition that has the bridging property rubber of two keys in 500,000 vistanex and the strand by weight average molecular weight and constitutes, and is to make above-mentioned bridging property rubber cross and form.
3. the perforated membrane of the described load bonding agent of claim 1, wherein reactive polymer have carboxyl or hydroxyl as can with the functional group of isocyanates radical reaction.
4. the perforated membrane of the described load bonding agent of claim 1, wherein partial cross-linked bonding agent has the gel percentage of 5～80% scopes.
5. the perforated membrane of the described load bonding agent of claim 2, wherein bridging property rubber is ethylene-propylene-ENB terpolymer.
6. the perforated membrane of the described load bonding agent of claim 2, wherein bridging property rubber is polynorbornene.
7. electrode/porous membrane laminated body, it is electrode to be pressed on the perforated membrane that adheres to each described load bonding agent in the claim 1 to 6 form.
8. electrode/perforated membrane adherend, it is reactive polymer and the polyfunctional isocyanate's reaction that makes in the described electrode of claim 7/porous membrane laminated body, make partial cross-linked bonding agent further crosslinked, thereby electrode bonded on the perforated membrane and form.
9. the manufacture method of a battery is characterized in that:
After in the described electrode with claim 7/porous membrane laminated body is packed battery case into, in this battery case, inject the electrolyte and the heating that comprise the polyfunctional isocyanate, make reactive polymer and above-mentioned polyfunctional isocyanate reaction in the partial cross-linked bonding agent that loads on the perforated membrane, thereby make it further crosslinked, electrode is bonded on the perforated membrane, form electrode/perforated membrane adherend, obtain comprising perforated membrane in this electrode/perforated membrane adherend simultaneously as the battery of dividing plate.
10. battery, it is following formation:
After in the described electrode with claim 7/porous membrane laminated body is packed battery case into, in this battery case, inject the electrolyte and the heating that comprise the polyfunctional isocyanate, make reactive polymer and above-mentioned polyfunctional isocyanate reaction in the partial cross-linked bonding agent that loads on the perforated membrane, thereby make it further crosslinked, electrode is bonded on the perforated membrane, like this, in comprising the battery of resulting electrode/perforated membrane adherend as electrode/dividing plate adherend, above-mentioned perforated membrane is at least the polyolefine resin composition that has the bridging property rubber of two keys in 500,000 vistanex and the strand by weight average molecular weight and constitutes, and makes above-mentioned bridging property rubber cross and form.
CNB2004800095580A 2003-04-09 2004-04-01 Adhesive-carrying porous film for cell separator and its application Expired - Fee Related CN100346506C (en)

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