CN1239591A - Separator for battery and alkali secondary battery using same - Google Patents
Separator for battery and alkali secondary battery using same Download PDFInfo
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- CN1239591A CN1239591A CN97180233A CN97180233A CN1239591A CN 1239591 A CN1239591 A CN 1239591A CN 97180233 A CN97180233 A CN 97180233A CN 97180233 A CN97180233 A CN 97180233A CN 1239591 A CN1239591 A CN 1239591A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
A separator for batteries comprising exchangeable fine powder prevented from coming off by fixing the powder by using a binder resin which is placed in fine pores or narrow grooves formed in the surface of organic fibers constituting a porous sheet, having an excellent electrolyte holding property, and exhibiting an ion exchanging ability for a long period. The pores or grooves exist in the surface of olefin fibers. The pores or grooves are formed by etching the fibers with an organic solvent. In the pores or grooves, the binder resin is fixed, partially entering the pores or grooves and projecting outward from the pores or grooves. The ion-exchangeable fine powder is fixed to the ends of the projecting resin. It is preferable to use a styrene-entylene-butylene-styrene (SEBS) thermoplastic copolymer as the resin.
Description
Technical field
The present invention relates to battery separator and use the alkaline secondary cell of this barrier film.
Background technology
For the barrier film that uses in the alkaline secondary cells such as nickel-cadmium, nickel-hydrogen, general alkali resistance and the various performances such as the chemical stability of oxidative resistance etc., electrolyte retentivity, gas permeability that all require to have at high temperature, in order to address this problem, all be mainly to use the formation base material of olefine fibre up to now as barrier film.
Yet though the chemical stability of olefine fibre barrier film is very good, its hydrophobicity is strong, and is poor with the affinity of electrolyte, and the electrolyte retentivity is also poor, and it is dried to cause electrolyte to evaporate into easily when discharging and recharging operation chronically repeatedly.
Therefore, in order to solve the problem that olefine fibre exists, the someone has proposed the non woven fabric thin slice is applied the method that various hydrophilies are handled, comprising:
A, the method for using surfactant to carry out reprocessing as water-soluble wettability imparting agent;
B, the method for utilizing ultraviolet ray or electron ray to make crylic acid resin monomers such as acrylic acid, acrylate or polymer carry out glycerol polymerization;
C, in inert gas, use oxygen or fluorine gas to carry out the method for oxidation processes;
D, use oleum, the concentrated sulfuric acid, chlorosulfonic acid, sulphur dioxide etc. carry out the method for sulfonation processing etc.
In addition, a kind of scheme that someone proposes is, for flash-over characteristic of improving alkaline secondary cell etc., utilize adhesive that a kind of inorganic micro powder body (magnesium silicate) with adsorption of metal ions is fixed on a kind of barrier film skin section of being made by the alkali resistance synthetic fibers, come off from the barrier film top layer and enter the electrolyte so that prevent these powder bodies, thereby and utilize these powder bodies that adsorption of metal ions is prevented that metal ion from shifting (special public clear 52-37574 communique) towards the reversed polarity direction.
A kind of scheme of somebody's proposition is in addition, gives the ionic polymer resin (spy opens flat 4-232158 communique) that one deck is also obtained by interpolation melting mixing metal cation (particularly zinc ion) as matrix by ethene-copolymers of unsaturated carboxylic acids or ethylene-methacrylic acid copolymer on a kind of porous matter thin slice that is made of the olefine kind resin fiber.
In above-mentioned prior art, there is following problems in the barrier film that applies the hydrophily processing.That is to say, with regard to the method for above-mentioned a, c, because the long preservation of battery or carrying out repeatedly of discharging and recharging, make surfactant or oxide (COOH ,-OH) etc. from olefine fibre, come off simply, therefore, electrolyte in barrier film is petered out, and causes that the internal resistance of battery is risen, thereby has reduced its discharge capacity.
For the barrier film of above-mentioned b method,, thereby make the lifetime of battery under high-temperature condition because acrylic resin lacks thermal endurance and oxidative resistance.In addition,, therefore cause the deterioration of olefine fibre owing in graft reaction, use ultraviolet ray or electron ray, thus the danger that produces minute short circuit.And, owing to need the washing procedure of accessory substance (homopolymers) flush away that produces during with graft polymerization, therefore there is the high problem of manufacturing cost.
In addition, barrier film for above-mentioned d method, though its thermal endurance, alkali resistance, oxidative resistance are all good, but it lacks the electrolyte retentivity, in order to improve its electrolyte retentivity, must use strong acid such as oleum to improve its sulphonation rate, therefore cause the deterioration of olefine fibre, thus the danger that produces minute short circuit.In addition, after sulfonation is handled, need a washing procedure that is used for unreacted sulfuric acid flush away, therefore have the high problem of manufacturing cost.
In addition, for utilizing the adhesive barrier film that the inorganic micro powder body is fixing, because used adhesive is an aqueous resin, and alkali resistance fiber is hydrophobic, therefore a little less than the adhesion between adhesive and the alkali resistance fiber, make the inorganic micro powder body come off easily, if and use a large amount of adhesives, then the surface of inorganic micro powder body is covered by adhesive fully, thereby be difficult to bring into play it to Adsorption Properties for Metal Ions, in addition, if use water system dispersion resin (emulsion), then, emulsification profit wherein brings adverse influence to battery performance because being dissolved in the electrolyte.
In recent years, be accompanied by the high performance of the goods (mobile electronic equipments of portable phone and notebook type personal electric computer etc.) that use alkaline secondary cell, performance (long-life, high capacity, miniaturization etc.) to battery is had higher requirement, and above-mentioned prior art can not fully adapt to these requirements, and this is present actual conditions.
Disclosure of an invention
The objective of the invention is in order to solve above-mentioned problems of the prior art, provide a kind of electrolyte retentivity, ion exchange capacity and intensity all higher, alkali resistance and oxidative resistance are also good, self-discharge phenomenon can be suppressed and the long lifetime of battery can be sought, and the battery separator that can make at an easy rate and the alkaline secondary cell that uses this barrier film.
In order to achieve the above object, battery separator of the present invention is characterised in that, on the surface of the organic fibrid that constitutes the porousness thin slice, be formed with fine space or rill, use a kind of adhesive resin that dissolves in the organic solvent to soak into and fill up above-mentioned space or rill, more a kind of ion exchangeable powder body is fixed at least a portion in the surface of above-mentioned organic fibrid and fiber interweaving district.According to this structure, because organic fibrid, adhesive resin, ion exchangeable powder body have good alkali resistance and oxidative resistance all, and these materials each other by the grappling effect securely in conjunction with, therefore avoid the physics of ion exchangeable powder body to come off or chemical breakdown fully, thereby can bring into play electrolyte retentivity and ion-exchange capacity chronically.In addition, compare with hydrophilicity-imparting treatment such as the sulfonation of prior art or acrylic acid-grafted aggregation processing,, only need the adhesion amount of control ion exchange resin according to the present invention, just ion exchange capacity can be improved significantly, and the function that improves the electrolyte retentivity can be brought into play.In addition, when the barrier film with this structure is used for alkaline secondary cell, can improve the adsorption capacity of barrier film to the harmful ion in the electrolyte, can suppress the self discharge of battery simultaneously owing to reciprocating type effect, and be difficult for taking place the phenomenon of electrolyte exhaustion, therefore can seek the long lifetime of battery.
In addition, resemble adhesive resin fixing above-mentioned also can to the fiber that constitutes base material as barrier film each other in conjunction with the very big reinforcing effect of performance, therefore can prevent the fracture accident that when being fit into barrier film in the battery, takes place or owing to carrying out the short circuit phenomenon that charge and discharge cycles causes for a long time.
In above-mentioned battery separator of the present invention, adhesive resin is preferably adhesive resin with the mixed weight ratio of ion exchangeable powder body: the scope of ion exchangeable powder body=1: 0.3～1: 10 is more preferably adhesive resin: the scope of ion exchangeable powder body=1: 0.5～1: 6.
In addition, the ion exchangeable powder body is fixed on the battery separator of the invention described above,, can brings into play the function that keeps alkaline electrolyte simultaneously again so that make it can either adsorb and catch harmful ion in the electrolyte.That is to say, the surface of ion exchangeable powder body is not covered fully by the adhesive resin but its surperficial part is exposed outside, or by a kind of have many micropores and be araneose adhesive resin haply cover, thereby make it can give full play to the ion exchanging function of ion exchangeable powder body.Harmful ion in the so-called in this article electrolyte is meant that those enter chemical ions such as ammonium ion in the electrolyte, chloride ion, nitrate ion and resemble the metal ion that manganese ion, iron ion, aluminium ion etc. can make degradation of cell performance on precipitateing into positive pole the time.
In addition, at least a resin preferably from the polyflon of the acrylic resin of styrene analog thermoplastic polymer with alkali resistance, oxidative resistance, olefines or polyvinyl resin, halogenated polyolefin class, selected of the adhesive resin in the battery separator of the invention described above.As the styrene analog thermoplastic polymer, can use the block copolymer (being called for short SEBS) of styrene-ethylene-butylene-styrene, the block copolymer (being called for short SEPS) of styrene-ethylene-propylene-styrene, the block copolymer (being called for short SIS) of styrene-isoprene-phenylethene, the block copolymer (SBS) of s-B-S etc.
In addition, in above-mentioned adhesive resin, especially preferably wherein part or all is the thermoplastic copolymer of the styrene-ethylene-butylene-styrene class (SEBS) of phenylethylene.
In addition, ion exchangeable powder body in the invention described above battery separator, preferably from the cation exchange resin of phenylethylene or acrylic compounds, the anion exchange resin of phenylethylene, acrylic compounds or phenol, at least a resin of selecting in the chelating resin of phenylethylene or pyridines.In addition, consider at least a group that the ion-exchange group of ion exchangeable powder body is preferably selected from the viewpoint that improves the electrolyte retentivity from sulfonic group, sulphonate-base, carboxylic acid group or carboxylate group.
In addition, ion exchangeable powder body in the invention described above battery separator preferably contains from having alkali-proof and can bring into play at least a compound of selecting in metal oxide, hydroxide and the inorganic salts thereof of ion exchangeable alkaline electrolyte.
In addition, the ion exchangeable powder body in the invention described above battery separator preferably contains at least a compound of selecting from titanium oxide, aluminium oxide, antimony oxide, potassium titanate, zirconia.
In addition, preferably a kind of granular, laminar, whisker shape or flakey that has fine voids in its surface of the shape of the ion exchangeable powder body in the invention described above battery separator.This ion exchangeable powder body can obtain by at least a method of selecting from freezing comminuting method, mechanical crushing method, spray-on process, and wherein preferable methods is freezing comminuting method.In addition, the average grain diameter of ion exchangeable powder body is below 100 μ m (パ ス) preferably, is more preferably below 50 μ m.
In addition, preferably a kind of polymer class fiber of the organic fibrid in the invention described above battery separator with alkali resistance and oxidative resistance.In addition, preferably one of the organic fibrid in the invention described above battery separator one or all be olefine fibre.
In addition, the battery separator of the invention described above alkaline secondary cell barrier film preferably.
And then battery separator of the present invention has the structure that is applicable to that those use the alkaline secondary cell of above-mentioned barrier film.Utilize this structure just can provide a kind of electrolyte retentivity, ion exchange capacity and intensity all very good, alkali resistance and oxidative resistance are also good, self-discharge phenomenon can be suppressed and the long lifetime of battery can be sought, and the battery separator that can make at an easy rate and the alkaline secondary cell that uses this barrier film.
As mentioned above, the present invention at first utilizes the method for organic solvent etch to make surface portion (the top layer part from fiber surface to the fibrous inside) porous of olefine fibre, utilize the grappling effect to make a kind of alkali resistance that has then, oxidative resistance and the adhesive resin that dissolves in the organic solvent are securely fixed on the olefine fibre, utilize this adhesive resin that has firmly fixed that some can be adsorbed and catch harmful ion in the electrolyte at last, the ion exchangeable powder body that has the function that keeps alkaline electrolyte simultaneously is securely fixed on the olefine fibre by the grappling effect.So the ion exchangeable powder body that obtains waits in the operation in the manufacturing process of barrier film or in battery that barrier film is packed into coming off of physics can not taken place, and has good electrolyte retentivity and can bring into play ion exchanging function in for a long time.In addition, as mentioned above, Gu Ding adhesive resin can be brought into play a kind of reinforcing effect, make the fiber adhesion each other that constitutes base material as barrier film improve and improve the intensity of barrier film itself greatly, therefore can prevent the fracture accident of generation when being fit into barrier film in the battery or owing to carrying out the short circuit phenomenon that charge and discharge cycles causes for a long time.
Simple declaration to accompanying drawing
Fig. 1 is the model enlarged drawing of an embodiment of expression battery separator of the present invention.
Fig. 2 is the model enlarged drawing of expression another embodiment of battery separator of the present invention.
Fig. 3 is the graph of a relation of the mixed weight comparison ion exchange capacity of the adhesive resin of one embodiment of the invention and ion exchangeable powder body.
Fig. 4 is the graph of a relation of the mixed weight comparison electrolyte conservation rate of the bonding sharp resin of one embodiment of the invention and ion exchangeable powder body.
Fig. 5 is a plot, and it shows the comparable situation of the electrolyte conservation rate of barrier film when pressurization of embodiments of the invention and comparative example and prior art example.
Fig. 6 is a plot, and it shows the comparable situation of the ion exchange capacity of embodiments of the invention and comparative example and prior art example.
Fig. 7 is a curve chart, and it shows the comparable situation of the hermetic type nickel-hydrogen cell of the barrier film that uses the embodiment of the invention and prior art example being carried out the utilance of high rate discharge.
Fig. 8 is a plot, and it shows preserves 2 comparable situation of capability retention when all to the hermetic type nickel-hydrogen cell that uses the embodiment of the invention and the barrier film of the prior art example back of charging down at 45 ℃.
Fig. 9 is a curve chart, and it shows in the hermetic type nickel-hydrogen cell of the barrier film that uses the embodiment of the invention and prior art example, the comparable situation that battery capacity changes with cycle-index.
The preferred plan that is used to carry out an invention
Utilize accompanying drawing to describe below.Fig. 1 is the model enlarged drawing of a kind of embodiment of expression battery separator of the present invention.In Fig. 1, the 1st, as the olefine fibre of matrix.Surface element at above-mentioned olefine fibre 1 exists fine space 2 or rill.Above-mentioned fine space 2 or rill can form by the method for the above-mentioned olefine fibre of etch with an organic solvent.Adhesive resin 3 immerses in above-mentioned fine voids 2 or the rill with a part and another part is fixed on the above-mentioned olefin(e) fibre to the outstanding structure in outside, and ion exchangeable powder body 4 then is fixed in the front end area of adhesive resin 3 protuberances.In addition, the part of above-mentioned ion exchangeable powder body 4 has exposed division 5.
Fig. 2 is the model enlarged drawing of expression another embodiment of the present invention, wherein, exist many at surface element owing to the fine voids 2 or the rill that are formed by the organic solvent etch as the olefine fibre 1 of matrix, adhesive resin 3 is fixed with the form that its part immerses in above-mentioned fine voids 2 or the rill, and with the porous portion 6 that has many micropores on its surface the ion exchangeable powder body is being fixed simultaneously.
The present invention at first forms countless fine spaces or rill on the surface of the organic fibrid that constitutes the porousness thin slice, use a kind of adhesive resin that has alkali resistance and oxidative resistance and dissolve in the organic solvent that above-mentioned space or rill are soaked into, filled up then, utilize these to soak into again and the adhesive resin that filled up above-mentioned space or rill is fixed on a kind of ion exchangeable powder body at least a portion surface in above-mentioned organic fibrid surface and fiber interweaving district and make the major part of this ion exchangeable powder body expose its surperficial part.
Above-mentioned adhesive resin compares generally in 1: 0.3～1: 10 scope with the mixed weight of ion exchangeable powder body, preferably in 1: 0.5～1: 6 scope, when this mixed weight compares less than 1: 0.3, the surface of ion exchangeable powder body is covered by the adhesive resin fully, therefore can not obtain sufficient electrolyte maintenance dose and ion exchange capacity, in addition, when above-mentioned mixing ratio during greater than 1: 10, this adhesive resin will cause that the physical property of ion exchangeable powder body comes off to the confining force deficiency of ion exchangeable powder body in the time of therefore in the manufacturing process of barrier film and in battery that barrier film is packed into.
In order to confirm above-mentioned viewpoint, solution (the organic solvent: mixed xylenes) make test film on the non woven fabric in a kind of polypropylene fibre system that uses a class to form than in 1: 0.2～1: 12 scope, changing by mixed weight by bonding sharp resin (SEBS) and ion exchangeable powder body (styrene sulfonic acid type storng-acid cation exchange resin powder body), use this test film according to the following determination of test method mixed weight ratio and the relation of ion exchange capacity then, obtained result shown in Figure 3.Also measured the relation of mixed weight ratio in addition, obtained result shown in Figure 4 with the electrolyte conservation rate.From these results as can be seen, when the mixed weight of adhesive resin and ion exchangeable powder body than less than 1: 0.3 the time, ion exchange capacity and electrolyte conservation rate are insufficient, and above 1: 10 o'clock, will cause coming off of ion exchangeable powder body, and can confirm that at this moment ion exchange capacity and electrolyte conservation rate have all reduced.
As the adhesive resin that dissolves in the organic solvent, can use any in the polyflon of the acrylic resin of those styrene analog thermoplastic copolymers, olefines or polyvinyl resin, halogenated polyolefin class or more than one with good alkali resistance, oxidative resistance, especially consider from the adhesiveness aspect of TPO fiber and ion exchangeable powder body, preferably use styrene-ethylene-butylene-styrene (SEBS) analog copolymer or all as one one of adhesive resin.
As the ion exchangeable powder body, what be suitable for is that those ion exchange capacities when moisture are that 0.5～4.5eq/ rises and with phenylethylene or the acrylic resin cation exchange resin as parent, with phenylethylene, acrylic compounds or phenol resin anion exchange resin, with phenylethylene or pyridines chelating resin as parent as parent; Or ion exchange capacity is metal oxide, hydroxide or its inorganic salts of zirconium class, titanium class, aluminium class or the antimony class of 0.4～10.0meq/g, and wherein particularly suitable is titanium oxide, potassium titanate, antimony oxide, aluminium oxide or zirconia.
Ion exchangeable resin as organic class, what be suitable for is to carry out strongly acidic cation-exchange or its slaine that the three-dimensional cross-linked polystyrene resin that forms obtains by sulfonation by divinylbenzene, perhaps carry out weak-type cation exchange resin or its slaine that the three-dimensional cross-linked polyacrylate resin that forms obtains by hydrolysis, the perhaps mixture that obtains by their appropriate combination by divinylbenzene.
So-called above-mentioned ion exchangeable powder body is meant that those are shaped as granular (it is granular or microgranular to comprise spherical, little porousness), laminar, whisker shape or lepidiod ion exchangeable powder body, and they can use or mix use separately.Wherein especially preferably use those to have the powder body of fine porous (space) shape in its surface, at this moment, these powder bodies are owing to the anchoring effect that has with resin is fixed, the increase of simultaneous surface area and can bring into play its ion-exchange capacity in alkaline electrolyte fully.
In addition, the average grain diameter of above-mentioned ion exchangeable powder body is generally below 100 μ m, preferably below 50 μ m, because the surface area of resin is very big, therefore the ion exchange capacity that can bring into play resin fully and had, thus its electrolyte retentivity can be improved and therefore film resistance (internal resistance) can be reduced.
, if above-mentioned slaine is the state of potassium type or sodium type salt, then can easily obtain powder body by mechanical crushing.
In addition, manufacture method as the ion exchange resin powder body, can be by being 35～75% with a kind of moisture content, particle size distribution is that the ion exchange resin of the spherical or broken shape of 0.3～1.2mm carries out dried so that moisture evaporation wherein falls, and uses liquid nitrogen that its freezing pulverizing is made then.
As commercially available ion exchange resin, can use " the ス ミ キ レ-ト (registered trade mark) " of Sumitomo Chemical system, " ダ イ ャ イ is Application (registered trade mark) ", " デ ユ is the ラ イ ト (registered trade mark) " of mouth-system ア Application De Ha-ス system, " the ダ ウ エ Star Network ス (registered trade mark) " of ダ ウ ケ ミ カ Le system etc. of Mitsubishi Chemical's system.
In addition, as porous inorganic powder body with ion exchangeable, those various metal oxides, hydroxide or its slaine be can use, titanium oxide or potassium titanate, antimony oxide, aluminium oxide, zirconia etc. especially preferably used with alkali-proof zirconium class, antimony class or aluminium class.
Of course, in these solvent based adhesive resins and ion exchangeable powder body, the combination of especially preferably using styrene-ethylene-butylene-styrene analog thermoplastic copolymer and strongly acidic cation-exchange or its slaine is as the alkaline secondary cell barrier film.
As being applicable to organic fibrid of the present invention, it must be polymer fiber with alkali resistance, oxidative resistance, preferably wherein part or all used olefine fibre, and as olefine fibre, except by polypropylene and polyethylene or by splitting the membranous type fiber that polymethylpentene and polyethylene constitute, can also use polyethylene, polypropylene, polymethylpentene fiber or a class of olefines to be core with polypropylene, with the polyethylene is the core-sheath polyolefine fiber of skin, or the polyethylene or the polypropylene fibre of porous matter type.
Enumerate below as the alkaline battery with above-mentioned formation with one of the manufacture method of barrier film example, at first prepare a kind ofly can make the olefine fibre swelling and make its surface element form the aromatic hydrocarbon solvent of many spaces or rill, adhesive resin is dissolved in the above-mentioned solvent and with the ion exchangeable powder body is scattered in wherein to form a kind of slurry, with this slurry dipping, scatter or be coated on a kind of non woven fabric thin slice of making by olefine fibre, use heated-air drying then so that solvent evaporation, thereby make battery separator.
; in above-mentioned method; by the method for the adherence method of slurry being changed into dipping, being scattered or apply; can make the ion exchangeable powder body be evenly dispersed in the inside of non woven fabric thin slice haply; perhaps from surface element to inner or conversely; form one deck and disperse the high-density region that forms and one deck to disperse the density regions that forms, thereby obtain a kind of density gradient type structure by the ion exchangeable powder body of greater particle size by ion exchangeable powder body than fine grain.Under situation with this density gradient type structure, when being fit into barrier film in the battery, with its high density side towards negative pole, and with its low-density side towards positive pole, can further improve its gas-premeable like this.
As the organic solvent that is applicable to above-mentioned manufacture method, can from dimethylbenzene, toluene, hexahydrotoluene, tetrahydronaphthalene, decahydronaphthalenes, suitably select any one or more.
Under the aromatic hydrocarbon solvent situation of using the fast benzene of those evaporation rates or cyclohexane and so on, in case heating-up temperature is too high, will make before the surface element formation space or rill of dissolution at fiber by solvent, solvent just evaporates, therefore the poor adhesion that causes olefine fibre and adhesive resin, also cause coming off of ion exchangeable powder body in addition easily, therefore bad.
Under according to situation of the present invention, at first use a kind of solvent that when heating, can produce dissolution to form countless fine spaces or rill at the olefine fibre surface portion, a kind of adhesive resin is infiltrated through in above-mentioned space or the rill and firmly fix herein, then utilize this adhesive resin with anchoring effect the ion exchangeable powder body to be firmly fixed at least a portion surface in the fiber surface of above-mentioned porousness thin slice or fiber interweaving district again and most ion exchangeable powder body is exposed outside with its surperficial part.
Herein, so-called most ion exchangeable powder body exposes outside with its surperficial part and is meant, the state that all surfaces of the ion exchangeable powder body of not all dispersion is all covered fully by the adhesive resin, but the powder body that a powder body that is capped fully and a part are capped is mixed in together, and the powder body that a part is capped accounts for state more than half.
In addition, the state that a so-called part is capped is meant the state that has exposed division on the part on each ion exchangeable powder body surface, but preferably the ratio more than 1/3 of ion exchangeable powder body surface area is a kind of araneose state with many little porous portion.
In addition, mixed weight by regulating adhesive resin and ion exchangeable powder body than and adhesion amount and merge use cation exchange powder body and the anion exchange powder body as above-mentioned ion exchangeable powder body, just can freely control electrolyte retentivity and ion-exchange performance etc. according to desired battery performance.
Below utilize embodiment to be described more specifically the present invention.Embodiment 1
(trade name DF-72, fiber number 2d are made in big and weaving to the membranous type polyolefine fiber that splits that use is made by polyethylene and polypropylene, split the fiber number 0.2d behind the film), by common copy slurry legal system flakiness after, its spray water processing and hot calender are processed, having made a kind of weight per unit area is 30g/m
2, thickness is the non woven fabric thin slice of 100 μ m.
Then above-mentioned non woven fabric thin slice is placed the slurry (solvent: mixed xylenes that makes by following matching requirements, solid component concentration 10%) dipping in, the heated-air drying of then carrying out 80 ℃ * 5 minutes is handled so that solvent evaporates wherein, and then in order to adjust the thickness of thin slice, use hot roll (125 ℃ of temperature) to roll processing, made a kind of adhesion amount 6g/m
2, weight per unit area 36g/m
2, the barrier film a of thickness 100 μ m.
Matching requirements 1 mixed weight is than SEBS resin (Shell system, trade name Kraton 100G-1652) styrene sulfonic acid type strongly acidic cation exchange tree 300 fat powder bodies (Rome and Hass system is discussed the following name of an article DuoliteC-20 of 100 μ m) mechanical crushing embodiment 2
Use the non woven fabric thin slice of embodiment 1, be placed in the slurry (solvent is identical with embodiment 1 with solid component concentration) that makes by following matching requirements 2 and flood, make a kind of adhesion amount 6g/m according to similarly to Example 1 method
2, weight per unit area 36g/m
2, the barrier film b of thickness 100 μ m.
Use the non woven fabric thin slice of embodiment 1, be placed in the slurry (solvent is identical with embodiment 1 with solid component concentration) that makes by following matching requirements 3 and flood, make a kind of adhesion amount 6g/m according to similarly to Example 1 method
2, weight per unit area 36g/m
2, the barrier film c of thickness 100 μ m.
The structure image of the various barrier films of the foregoing description 1,2,3 is as such shown in Fig. 1 of model expanded view, on the surface of olefine fibre 1, has countless space 2, the adhesive resin 3 of solvent system is impregnated into and has filled up above-mentioned space 2 and is firmly fixed at herein, and at least a portion surface in this solvent to be adhesive resin 3 be firmly fixed at ion exchangeable powder body 4 fiber surface and fiber interweaving district and make this ion exchangeable powder body on its most surfaces, have exposed division 5.Embodiment 4
Using a kind of core is (the big and weaving of poly core-sheath polyolefine fiber as polypropylene, skin zone, trade name NBF, fiber number 0.9d/1.5d, mixed proportion 1: 1), after combing method routinely is made into the intertexture thin slice, it is carried out hot calender processing, make a kind of weight per unit area 50g/m
2, thickness 170 μ m the non woven fabric thin slice.
Use the slurry (solvent is identical with embodiment 1 with solid component concentration) that makes by following matching requirements 4 to make above-mentioned slurry be impregnated into the inside of non woven fabric thin slice then, above-mentioned non woven fabric thin slice is coated with processing, made a kind of adhesion amount 6g/m
2, weight per unit area 56g/m
2, the battery separator d of thickness 170 μ m.
Use non woven fabric thin slice similarly to Example 4, make the slurry (solvent is identical with embodiment 1 with solid component concentration) of following matching requirements 5 be impregnated into above-mentioned thin slice inside, made a kind of adhesion amount 6g/m according to method similarly to Example 4
2, weight per unit area 56g/m
2, the battery separator e of thickness 170 μ m.
Use non woven fabric thin slice similarly to Example 4, make the slurry (solvent is identical with embodiment 1 with solid component concentration) of following matching requirements 6 be impregnated into above-mentioned thin slice inside, made a kind of adhesion amount 6g/m according to method similarly to Example 4
2, weight per unit area 56g/m
2, the battery separator f of thickness 170 μ m.
Use non woven fabric thin slice similarly to Example 4, make the slurry (solvent is identical with embodiment 1 with solid component concentration) of following matching requirements 7 be impregnated into above-mentioned thin slice inside, made a kind of adhesion amount 6g/m according to method similarly to Example 4
2, weight per unit area 56g/m
2, the battery separator g of thickness 170 μ m.
Matching requirements 7 mixed weights are than the chemical system of SEBS resin (Shell system, trade name Kraton 100G-1652) potassium tetratitanate whisker shape (Da mound, 300 trade name TISMO) below the mechanical crushing 50 μ m
The structure image of the various barrier films of the foregoing description 4,5,6,7 is as such shown in Fig. 2 of model expanded view, on surface, have many fine voids or rills that form owing to the organic solvent etch as the olefine fibre 1 of matrix, adhesive resin 3 is impregnated in these fine spaces or the rill and is fixed in herein, and resin 3 is firmly fixed at ion exchangeable powder body 4 on its surface.In addition, on above-mentioned adhesive resin 3, have the little porous portion 6 that forms many micropores, ion exchangeable powder body 4 present a kind of can with the direct state of contact of outside liquid.Comparative example 1
Use the slurry (solvent: water, solid component concentration 10%) of following matching requirements 8, make a kind of adhesion amount 6g/m according to method similarly to Example 1
2, weight per unit area 36g/m
2, the barrier film h of thickness 100 μ m.
Matching requirements 8 mixed weights are than PP emulsion (Mitsui petrochemistry system, ケ ミ パ-l00 Le WP100, active ingredient 40%) styrene sulfonic acid type strongly acidic cation exchange tree 300 fat powder bodies (Rome and Hass system is discussed the following name of an article DuoliteC-20 of 100 μ m) mechanical crushing comparative example 2
Use a kind ofly, make a kind of adhesion amount 6g/m by SEBS resin and ion exchange resin powder body non woven fabric thin slice by weight the slurry Processing Example of making at 100: 20 1
2, weight per unit area 56g/m
2, the barrier film i of thickness 170 μ m.Comparative example 3
Use a kind ofly, make a kind of adhesion amount 6g/m by SEBS resin and ion exchange resin powder body non woven fabric thin slice by weight the slurry Processing Example of making at 100: 1,200 4
2, weight per unit area 36g/m
2, the barrier film j of thickness 100 μ m.Prior art example 1
According to known method, the weight per unit area 30g/m that uses the oleum and the concentrated sulfuric acid respectively a kind of method according to similarly to Example 1 to be made
2, the weight per unit area 50g/m that the non woven fabric thin slice of thickness 100 μ m and a kind of method according to similarly to Example 4 make
2, the non woven fabric thin slice of thickness 170 μ m carries out sulfonation to be handled, and has made barrier film k and l respectively.Prior art example 2
According to known method, use acrylic acid respectively to according to a kind of weight per unit area 30g/m that makes with the same method of embodiment 1, embodiment 4
2, thickness 100 μ m and a kind of weight per unit area 50g/m
2, the non woven fabric thin slice of thickness 170 μ m carries out glycerol polymerization to be handled, and has made barrier film m and n respectively.
Then, totally 14 kinds of barrier film a, b, c, d, e, f, g, h, i, j, k, l, m, n that use makes in the foregoing description 1,2,3,4,5,6,7 and comparative example 1,2,3 and prior art example 1,2, alkali resistance, oxidative resistance, electrolyte conservation rate, ion exchange capacity and intensity according to following these barrier films of determination of test method have obtained the result shown in the table 1.
Table 1
| Strength ratio (%) | Alkali resistance (%) | Oxidative resistance (%) | Electrolyte conservation rate (%) | Ion exchange capacity (meq/m 2) | |
| Embodiment a | ???130 | ????-0.15 | ???-0.25 | ??????45 | ??????7.2 |
| Embodiment b | ???150 | ????-0.22 | ???-0.27 | ??????33 | ??????5.2 |
| Embodiment c | ???130 | ????-0.13 | ???-0.21 | ??????43 | ??????6.9 |
| Embodiment d | ???150 | ????-0.12 | ???-0.21 | ??????38 | ?????11.2 |
| Embodiment e | ???130 | ????-0.22 | ???-0.35 | ??????32 | ?????20.5 |
| Embodiment f | ???150 | ????-0.21 | ???-0.25 | ??????40 | ??????8.9 |
| Embodiment g | ???150 | ????-0.11 | ???-0.23 | ??????35 | ?????10.7 |
| Comparative example h | ???105 | ????-1.5 | ???-5.84 | ??????38 | ??????6.8 |
| Comparative example i | ???210 | ????-0.10 | ???-0.20 | ??????19 | ??????0.9 |
| Comparative example j | ???110 | ????-0.21 | ???-0.26 | ??????82 | ?????22.3 |
| Prior art example k | ????80 | ????-0.35 | ???-0.94 | ??????24 | ??????0.24 |
| Prior art example l | ????85 | ????-0.31 | ???-0.95 | ??????15 | ??????0.8 |
| Prior art example m | ????90 | ????-0.21 | ???-1.05 | ??????22 | ??????0.18 |
| Prior art example n | ????95 | ????-0.44 | ???-1.75 | ??????17 | ??????0.25 |
Test method to relevant physics value in embodiment, comparative example and the prior art example is as follows.
Strength test: using a cupping machine, is that 10cm clamps the two ends of test film (wide 2cm) according to the distance between two chucks, stretches then, measures the intensity of this test film when fracture, calculates its strength ratio according to following formula.
Test film intensity * 100 before test film intensity/processing after strength ratio (%)=processing
Alkali resistance: make test film reach the water balance state, measure its weight (W), be impregnated in a kind of proportion then and be in 1.30 the potassium hydroxide solution, at 100 ℃ of dippings 1 hour down.Then with its washing and drying, the weight (W when measuring it and reaching the water balance state
1), obtain its alkali resistance according to following formula.
Alkali resistance (%)=(W-W
1)/W * 100
Oxidative resistance: make test film reach the water balance state, measure its weight (W), be impregnated in then in a kind of mixed solution that in the liquor potassic permanganate 250cc of 1 weight %, adds 30% potassium hydroxide solution 500cc and form, flooded 1 hour down at 50 ℃.Then with its washing and drying, the weight (W when measuring it and reaching the water balance state
1), obtain its oxidative resistance according to following formula.
Oxidative resistance (%)=(W-W
1)/W * 100 (%)
The electrolyte conservation rate: make test film (5cm is square) reach the water balance state, measure its weight (W), using proportion then is that 1.30 potassium hydroxide solution is by 0.025g/cm
2Consumption replace air in the test film so that potassium hydroxide solution remains in the test film.Then, (diameter 20cm) this test film clamping from upper and lower two sides with two filter paper, and the weight that applies 5kg from the top pressurizeed 10 minutes, measured the weight (W of this test film then
1), obtain its electrolyte conservation rate according to following formula.
Electrolyte conservation rate (%)=(W-W
1)/W * 100
Ion exchange capacity: make test film reach the water balance state, measure its weight (W).Place the hydrochloric acid 200cc of 5N to flood 3 hours this test film, fully wash with its taking-up and with distilled water then, drying is 1 hour under 100 ℃.Then, this test film is placed the potassium hydroxide solution 50cc of 0.05N,, carefully draw the 10cc supernatant,, use hydrochloric acid (the titer f of 0.05N to wherein adding the bromocresol green indicator at 60 ℃ of dippings 5 hours down
C1) carry out titration.As Xcc, obtain ion exchange capacity with the consumption of 0.05 N hydrochloric acid at this moment by following formula.
Ion exchange capacity (meq/m
2)=(10f
K-f
Cl* X)/4W
Then, use the 14 kinds of barrier film a that rise, b, c, d, e, f, g, h, i, j, k, l, m, n, with the cream formula Ni utmost point as positive pole, with the cream formula MH utmost point as negative pole, and use alkaline electrolyte, thereby make capacitance is the closed nickel-hydrogen battery A of the inferior C size (サ Block C サ イ ズ) of 2.1～2.5A (discharging and recharging in 0.1 hour), B, C, D, E, F, G, H, I, J, K, L, M, N, utilance when measuring the high rate discharge of these batteries then, capability retention after the self discharge and charge and discharge circulation life carry out performance evaluation to various barrier films in view of the above.Measurement result is shown in Table 2.
Table 2
| Utilance during high rate discharge (%) (2.0C/0.1C) | Capability retention after the self discharge (%) (45 ℃ * 2 week) | Capacity sustainment rate (%) after 500 circulations | |
| Embodiment A | ?????????91.5 | ????????52.3 | ??????100 |
| Embodiment B | ?????????90.3 | ????????52.5 | ??????100 |
| Embodiment C | ?????????91.2 | ????????51.5 | ??????100 |
| Embodiment D | ?????????91.0 | ????????52.7 | ??????100 |
| Embodiment E | ?????????82.7 | ????????48.1 | ??????100 |
| Embodiment F | ?????????90.0 | ????????50.8 | ??????100 |
| Embodiment G | ?????????90.8 | ????????51.8 | ??????100 |
| Comparative Example H | ?????????89.0 | ????????32.5 | ???????80 |
| Comparative Example I | ?????????89.5 | ????????40.2 | ???????80 |
| Comparative Example J | ??????????- | ??????????- | ???????- |
| Prior art example K | ?????????87.0 | ????????39.0 | ???????82 |
| Prior art example L | ?????????86.3 | ????????39.5 | ???????82 |
| Prior art example M | ?????????86.5 | ????????30.4 | ???????75 |
| Prior art example N | ?????????87.8 | ????????32.8 | ???????82 |
Test method to various physics values in embodiment, comparative example and the prior art example is as follows.
The initial stage activation condition: 30 ℃ of temperature, 0.1C leads (290mA) * 12 hour by charging, stops 0.5 hour, and charging 0.1C leads the system of (final voltage 1.0V) and carries out 10 circulations.
High rate discharge test: 30 ℃ of temperature, charging 0.2C leads (290mA) * 6 hour, stopped 0.5 hour, the 0.1C that discharges then leads (final voltage 0.8V), measures the discharge capacity of this moment, again according to identical condition charging, press 2.0C then and lead (final voltage 0.8V) discharge, measure the discharge capacity of this moment, obtain the ratio of the latter's discharge capacity at last, the utilance (%) with this ratio during as high rate discharge to the former discharge capacity.
Self discharge test: 30 ℃ of temperature, the charging 0.1C lead * 12 hours, stopped 0.5 hour, the 0.1C that discharges then leads (final voltage 1.0V), measures the discharge capacity of this moment, again according to identical condition charging, then it was placed for two weeks down at 45 ℃, measure the remaining capacity (0.1C leads discharge, final voltage 1.0V) of this moment, obtain the ratio of this remaining capacity and above-mentioned discharge capacity, with the capability retention (%) of this ratio after as self discharge.
Cycle life characteristics: under 30 ℃ of temperature, according to charging 0.2C lead * 5 hours, 0.5 hour off time, the system that discharge 0.2C leads (final voltage 1.0V) is carried out 500 circulations, measures and obtain its capacity sustainment rate then.
In addition, in Comparative Example J, the ion exchange resin powder body comes off, in the battery of can not packing into.
The comparable situation at the electrolyte conservation rate in when pressurization that above-mentioned table 1 is listed is made the plot of Fig. 5.In addition, with the plot of relatively making Fig. 6 of the ion exchange capacity listed in this table.The comparable situation of utilance is made the curve chart of Fig. 7 during in addition, with the high rate discharge of above-mentioned table 2.The plot of relatively making Fig. 8 with the capability retention after the self discharge of this table.And then the comparable situation that the battery capacity of this table is changed with cycle-index is made the curve chart of Fig. 9.
From above-mentioned table 1～2 and Fig. 5～9 as can be seen, compare with hermetic type nickel-hydrogen cell K～N with the barrier film k～n of prior art example, barrier film a～the g of the embodiment of the invention and hermetic type nickel-hydrogen cell A～G improve aspect electrolyte conservation rate, ion exchange capacity and intensity significantly, also confirm in addition, in the test of battery performance, the raising of leap is arranged aspect the capacity sustainment rate after the capability retention after the self discharge test and 500 circulations particularly.
In the above-described embodiments, as olefine fibre, use is split the membranous type fiber and is made into thin slice with copying the slurry method by what polyethylene and polypropylene constituted, also can use the core-sheath fiber in addition and be made into thin slice, but also can use other the organic fibrids beyond the above-mentioned fiber and be made into thin slice with conventional combing method.
The possibility of industrial utilization
As mentioned above, according to the present invention, at first form countless fine voids or rill on the surface of olefine fibre, soak into adhesive resin again and be bonded in these spaces or the rill, then the ion exchangeable powder body is securely fixed at least a portion surface in olefine fibre surface and fiber interweaving district by the grappling effect, therefore, its electrolyte retentivity, ion exchange capacity and intensity are all very good, and its alkali resistance and oxidative resistance are also very good, thereby can seek the control of self discharge and make the battery long lifetime.
In addition, adhesive resin is fixed on the surface of olefine fibre with the grappling effect, therefore the mutual cohesive force between the fiber had strengthening action, even if use the fiber of thin dawn value also can not make the strength decreased of fiber, can the fracture accident in the time of in the battery of packing into, can not cause fiber deteriorated owing to repeatedly discharging and recharging yet, therefore can not produce minute short circuit, thereby can seek the filming of battery separator, and can be adapted to the high capacity of battery.
And, do not resemble the acrylic acid-grafted polymerization of prior art or sulfonation and process and need a washing to unreacted reactant remove operation like that, so can make at an easy rate. In addition, owing to do not use ultraviolet ray, electron ray or strong acid, can not make therefore that to consist of the olefine fibre of fiber base material as barrier film deteriorated, thereby the danger of minute short circuit can not occur.
In addition, by mixed weight ratio or the adhesion amount of change adhesive resin with the ion exchangeable powder body, can adjust simply electrolyte retentivity or ion-exchange performance etc.
Use the alkaline secondary cell of this barrier film to have good flash-over characteristic, also can have high capacity dimension holdup even carry out repeatedly charge and discharge cycles.
Claims (22)
1. alkaline secondary cell barrier film, it is characterized in that, on the surface of the organic fibrid that constitutes the porousness thin slice, be formed with fine space or rill, use a kind of adhesive resin that dissolves in the organic solvent to soak into and fill up above-mentioned space or rill, more a kind of ion exchangeable powder body is fixed at least a portion in the surface of above-mentioned organic fibrid and fiber interweaving district.
2. battery separator as claimed in claim 1, wherein, the mixed weight of adhesive resin and ion exchangeable powder body is than being binder resin: the scope of ion exchangeable powder body=1: 0.3～1: 10.
3. battery separator as claimed in claim 2, wherein, the mixed weight of adhesive resin and ion exchangeable powder body is than being binder resin: the scope of ion exchangeable powder body=1: 0.5～1: 6.
4. battery separator as claimed in claim 1, wherein, the ion exchangeable powder body has absorption and catches the function of harmful ion in the electrolyte and the function of maintenance alkaline electrolyte.
5. battery separator as claimed in claim 1, wherein, adhesive resin is at least a resin of selecting from the polyflon of the acrylic resin of styrene analog thermoplastic polymer with alkali resistance, oxidative resistance, olefines or polyvinyl resin, halogenated polyolefin class.
6. battery separator as claimed in claim 1, wherein, part or all of adhesive resin is styrene-ethylene-butylene-styrene class (SEBS) thermoplastic polymer of phenylethylene.
7. battery separator as claimed in claim 5, wherein, part or all of adhesive resin is styrene-ethylene-butylene-styrene class (SEBS) thermoplastic polymer of phenylethylene.
8. battery separator as claimed in claim 1, wherein, the ion exchangeable powder body contains from the cation exchange resin of phenylethylene or acrylic compounds, the anion exchange resin of phenylethylene, acrylic compounds or phenol, at least a resin of selecting in the chelating resin of phenylethylene or pyridines.
9. battery separator as claimed in claim 8, wherein, the ion exchange substrate of ion exchangeable powder body is at least a group of selecting in sulfonic group, sulphonate-base, carboxylic acid group and the carboxylate group.
10. battery separator as claimed in claim 1, wherein, the ion exchangeable powder body contains from having alkali-proof and can bring into play at least a compound of selecting in metal oxide, hydroxide and the inorganic salts thereof of ion exchangeable alkaline electrolyte.
11. battery separator as claimed in claim 4, wherein, the ion exchangeable powder body contains from having alkali-proof and can bring into play at least a compound of selecting in metal oxide, hydroxide and the inorganic salts thereof of ion exchangeable alkaline electrolyte.
12. battery separator as claimed in claim 11, wherein, the ion exchangeable powder body contains at least a compound of selecting from titanium oxide, aluminium oxide, antimony oxide, potassium titanate, zirconia.
13. battery separator as claimed in claim 1, wherein, the ion exchangeable powder body is a kind of granular, laminar, whisker shape or flakey that has fine voids from the teeth outwards.
14. battery separator as claimed in claim 5, wherein, the ion exchangeable powder body is a kind of granular, laminar, whisker shape or flakey that has fine voids from the teeth outwards.
15. battery separator as claimed in claim 1, wherein, the average grain diameter of ion exchangeable powder body is below 100 μ m.
16. battery separator as claimed in claim 5, wherein, the average grain diameter of ion exchangeable powder body is below 100 μ m.
17. as claim 15 or 16 described battery separators, wherein, the average grain diameter of ion exchangeable powder body is below 50 μ m.
18. battery separator as claimed in claim 1, organic fibrid wherein are a kind of polymer class fibers with alkali resistance and oxidative resistance.
19. battery separator as claimed in claim 1, wherein, part or all of organic fibrid is olefine fibre.
20. battery separator as claimed in claim 18, wherein, part or all of organic fibrid is olefine fibre.
21. battery separator as claimed in claim 1, this battery separator are the alkaline secondary cell barrier films.
22. alkaline secondary cell that uses the described barrier film of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97180233A CN1239591A (en) | 1997-05-12 | 1997-05-12 | Separator for battery and alkali secondary battery using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97180233A CN1239591A (en) | 1997-05-12 | 1997-05-12 | Separator for battery and alkali secondary battery using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1239591A true CN1239591A (en) | 1999-12-22 |
Family
ID=5177704
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97180233A Pending CN1239591A (en) | 1997-05-12 | 1997-05-12 | Separator for battery and alkali secondary battery using same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1239591A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100459228C (en) * | 2003-08-26 | 2009-02-04 | 日东电工株式会社 | Reactive polymer-supporting porous film for battery seperator and use thereof |
| CN100492718C (en) * | 2004-06-17 | 2009-05-27 | 可乐丽股份有限公司 | Battery separator and alkaline battery |
| CN100590760C (en) * | 2002-03-28 | 2010-02-17 | 日本贵弥功株式会社 | Solid electrolytic capacitor and process for producing the same |
| CN101523639B (en) * | 2006-09-28 | 2011-11-23 | 日本韦琳株式会社 | Alkaline battery separator, process for production thereof and alkaline batteries |
| CN104115306A (en) * | 2012-01-19 | 2014-10-22 | Sihl股份有限公司 | Separator comprising a porous layer and method for producing said separator |
| CN104684732A (en) * | 2012-10-08 | 2015-06-03 | 特里奥凡德国有限公司及两合公司 | Microporous separator film having homogeneous porosity and greater resistance to puncturing |
| CN108023051A (en) * | 2018-01-04 | 2018-05-11 | 东莞市魔方新能源科技有限公司 | A kind of isolation film and the lithium ion battery containing the isolation film |
| CN108155324A (en) * | 2017-12-19 | 2018-06-12 | 河南惠强新能源材料科技股份有限公司 | A kind of lithium ion battery difunctional application type diaphragm and preparation method thereof |
| CN108767177A (en) * | 2012-08-07 | 2018-11-06 | 赛尔格有限责任公司 | Improved diaphragm and correlation technique for lithium ion battery |
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| CN100590760C (en) * | 2002-03-28 | 2010-02-17 | 日本贵弥功株式会社 | Solid electrolytic capacitor and process for producing the same |
| CN100459228C (en) * | 2003-08-26 | 2009-02-04 | 日东电工株式会社 | Reactive polymer-supporting porous film for battery seperator and use thereof |
| CN100492718C (en) * | 2004-06-17 | 2009-05-27 | 可乐丽股份有限公司 | Battery separator and alkaline battery |
| CN101523639B (en) * | 2006-09-28 | 2011-11-23 | 日本韦琳株式会社 | Alkaline battery separator, process for production thereof and alkaline batteries |
| CN104115306A (en) * | 2012-01-19 | 2014-10-22 | Sihl股份有限公司 | Separator comprising a porous layer and method for producing said separator |
| US9997755B2 (en) | 2012-01-19 | 2018-06-12 | Sihl Gmbh | Separator comprising a porous layer and method for producing said separator |
| CN104115306B (en) * | 2012-01-19 | 2018-06-26 | Sihl股份有限公司 | Separator comprising porous layer and the method for making the separator |
| CN108767177A (en) * | 2012-08-07 | 2018-11-06 | 赛尔格有限责任公司 | Improved diaphragm and correlation technique for lithium ion battery |
| CN104684732A (en) * | 2012-10-08 | 2015-06-03 | 特里奥凡德国有限公司及两合公司 | Microporous separator film having homogeneous porosity and greater resistance to puncturing |
| CN108155324A (en) * | 2017-12-19 | 2018-06-12 | 河南惠强新能源材料科技股份有限公司 | A kind of lithium ion battery difunctional application type diaphragm and preparation method thereof |
| CN108023051A (en) * | 2018-01-04 | 2018-05-11 | 东莞市魔方新能源科技有限公司 | A kind of isolation film and the lithium ion battery containing the isolation film |
| CN108023051B (en) * | 2018-01-04 | 2023-09-12 | 东莞市魔方新能源科技有限公司 | Isolation film and lithium ion battery containing same |
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