CN1294416A - Battery diaphragm and battery using same - Google Patents
Battery diaphragm and battery using same Download PDFInfo
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- CN1294416A CN1294416A CN00108570A CN00108570A CN1294416A CN 1294416 A CN1294416 A CN 1294416A CN 00108570 A CN00108570 A CN 00108570A CN 00108570 A CN00108570 A CN 00108570A CN 1294416 A CN1294416 A CN 1294416A
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- Y02E60/10—Energy storage using batteries
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Abstract
A battery separator comprises: a divided compound fiber (A), a polyolefine compound fiber (B), as the necessary components, and, optionally, a non-woven fabric of a third synthetic fiber (C). Based on 100 weight % of the total amount of the constituent fibers, each of the divided compound fiber (A) or the polyolefine compound fiber (B) shall not exceed 60 weight %. Furthermore, the non-woven fabric has been subjected to a hydrophilic treatment. The divided compound fiber (A) comprises a methyl pentene polymer (formed of poly (4-methylpentene-1) or 4-methylpentene-1 and other olefine polymer) as a first component and a polyolefine polymer different from the first component or its copolymer as a second component. The second component is interleaved and adjacent to each other in fiber cross-section. Furthermore, at least one component in the second component is divided into more than one. The polyolefine compound fiber (B) comprises a high melting point component and a low melting point component.
Description
The present invention relates to alkaline storage battery used battery diaphragm and manufacture methods thereof such as a kind of suitable nickel-cadmium cell, nickel-zinc cell and Ni-MH battery.
In recent years, preferably use by the fibrous non-weaving cloth of polyalkenes such as polypropylene, particularly proposed the battery diaphragm of the non-weaving cloth hydrophilic treated that will form by the TPO superfine fibre as battery diaphragm.For example, the applicant opens in flat 5-186911 communique and the flat 5-186964 communique of Te Kai the spy, proposed in, contained and introduce the above fiber assembly of sulfonic sulfonation polyalkenes fiber 60wt% by the Splittable conjugate fiber that the methylpentene base polymer/the polyolefin polymers combination is formed.
And open in the flat 7-147154 communique the spy, provided and will carry out the battery diaphragm of hydrophilic treated such as vinyl monomer glycerol polymerization, sulfonation processing by the water thorn complexing non-weaving cloth that the above TPO Splittable conjugate fiber of 50wt% is formed.And open in the flat 8-273654 communique the spy, provided and will form by the above TPO superfine fibre of 50wt%, make the water thorn complexing non-weaving cloth of part welding between the superfine fibre carry out the battery diaphragm of hydrophilic treated.
But there is following problem in above-mentioned battery diaphragm.For example, use as battery diaphragm, then have the tendency of the non-weaving cloth intensity step-down after sulfonation is handled as the fiber assembly of the spy being opened flat 5-186911 communique and the flat 5-186964 communique of Te Kai, and the cost rising, not talkative very desirable.And open the battery diaphragm of flat 7-147154 communique the spy, with the Splittable conjugate fiber formed by polyethylene/polypropylene as main body, owing to make its heat fusing bonding by the composite molten bondable fibers that polypropylene/the low density polyethylene (LDPE) combination is formed, so non-weaving cloth intensity is low, hydrophilic treated etc. efficiently, technology is poor.The spy who studies for head it off opens the battery diaphragm of flat 8-273654 communique, make between a kind of composition low melting point superfine fibre of Splittable conjugate fiber melting adhered after, because it is cut apart and complexing, although so non-weaving cloth improved strength, but owing to make the mutual welding of superfine fibre composition self, be difficult to guarantee the space, guarantor's fluidity is insufficient.
The present invention is in view of these actual conditions, its purpose is to obtain having excellent guarantor's fluidity and sufficient non-weaving cloth intensity, under the situation that battery life is reduced, the battery diaphragm that helps battery capacity to improve, and have the battery that can improve excellent battery behaviors such as self-discharge.
For achieving the above object, battery diaphragm of the present invention be characterised in that it be a kind of by the methylpentene base polymer of forming with poly-(4-methylpentene-1) or 4-methylpentene-1 and the copolymer of other alkene as first composition, with the polyolefin polymers different or its copolymer with first composition as second composition, two kinds of compositions are alternately in abutting connection with configuration on the fiber section, at least a composition in two kinds of compositions is split into the Splittable conjugate fiber (A) that forms more than two, two kinds of necessary compositions of fibers conduct with the TPO composite fibre (B) that becomes to be grouped into by high-melting-point composition and low melting point, the non-weaving cloth that contains the third synthetic fibers (C) as required, when being 100wt% with the total amount that constitutes fiber, the use level of previous segmentation type composite fibre (A) or TPO composite fibre (B) is no more than 60wt% respectively, and aforementioned non-weaving cloth is by hydrophilic treated.By adopting this formation, can obtain having excellent guarantor's fluidity and sufficient non-weaving cloth intensity, and the battery diaphragm of battery behavior excellence.
The use level of previous segmentation type composite fibre (A) is more preferably more than 5wt%, in the scope below the 55wt%, in the scope below the above 50wt% of 15wt%.
And the use level of aforementioned TPO composite fibre (B) is more preferably in the scope below the above 55wt% of 5wt%, in the scope below the above 50wt% of 20wt%.
The use level of aforementioned the third synthetic fibers (C) is preferably in the scope below 40wt%.
Aforementioned non-weaving cloth preferably constitutes the polymer not fusion in fact of two kinds of compositions of the Splittable conjugate fiber in the non-weaving cloth, and by the low melting point composition of TPO composite fibre, the fiber that constitutes non-weaving cloth is bonding by heat fusing.
And if the fibre length of the fiber of formation non-weaving cloth can obtain fine and close non-weaving cloth in 3～25mm scope, help protecting fluidity.
The composite non-weaving cloth that aforementioned non-weaving cloth preferably forms by the different fibrofelt of lamination fibre length is so that non-weaving cloth intensity improves.
Preferred version as battery diaphragm of the present invention, the preferred compound foil of other thin slice of lamination on a kind of at least a portion layer of aforesaid non-weaving cloth, aforementioned compound foil is by hydrophilic treated, and this helps the raising of non-weaving cloth intensity, helps batching property and anti-short-circuit.
As the preferred another kind of scheme of battery diaphragm of the present invention, preferred other thin slice of lamination at least a portion layer of the non-weaving cloth of aforesaid hydrophilic treated.
Previous segmentation type composite fibre preferably with the methylpentene base polymer as first composition, with polypropylene based polymers as second composition.And the preferred sheath composition of aforementioned TPO composite fibre is a high density polyethylene (HDPE), and the core composition is polyacrylic core-sheath-type composite fibre.
Further, the preferred sulfonation of hydrophilic treated is handled, if sulfonation adopts oleum processing, chlorosulfonic acid processing or anhydrous slufuric acid to handle any in handling, helps improving the self-discharge of battery.And sulfonation degree is preferably at 0.4～2wt%.
Pack into aforementioned in the battery of any battery diaphragm, all can improve self-discharge, be specially adapted to electric automobile (PEV) and hybrid vehicle (HEV).
Specify content of the present invention below.
The Splittable conjugate fiber (A) that the present invention is used, be that the methylpentene base polymer formed with poly-(4-methylpentene-1) or 4-methylpentene-1 and the copolymer of other alkene is as first composition, with the polyolefin polymers different or its copolymer with first composition as second composition, have two kinds of alternately adjacency configurations of compositions on the fiber section, at least a composition in two kinds of compositions can be split into more than two, its component units is continuous in the longitudinal direction, and all the part of component units must have the section configuration on exposed fiber surface.Particularly, first composition and second composition can preferably use as Fig. 1～arrangement shown in Figure 3.
As the first composition methylpentene base polymer of previous segmentation type composite fibre (A), can enumerate the copolymer of poly-(4-methylpentene-1) or 4-methylpentene-1 and other alkene.As other alkene of copolymerization, can enumerate for example ethene, propylene, 1-butylene, 1-amylene, 1-hexene and 3-methyl-1-butene etc.
Second composition as Splittable conjugate fiber (A), can use polyethylene, polypropylene and poly-polyolefin polymers or its copolymers different such as (butene-1s) with first composition, especially preferably using fusing point (D2m) is more than 130 ℃, more preferably the polyolefin polymers more than 150 ℃ or its copolymer.By aforementioned first composition and the second one-tenth combination Splittable conjugate fiber excellent heat resistance that is grouped into,, can fully adapt to for the intense reaction in the battery.Particularly the methylpentene base polymer is as first composition, and polypropylene based polymers is as the tool effect of the combination of second composition.
The compound ratio of cutting apart preferred 5～20, the two kinds of compositions of number of two kinds of compositions is from the difficulty or ease consideration of spinning technique in the previous segmentation type composite fibre (A), and preferred first composition: second composition is about 30: 70～70: 30.And the fiber number of Splittable conjugate fiber (A) can be cut apart number and the suitable decision of compound ratio by adjustment, and the fiber number that makes each component units after cutting apart is 0.1～0.5dtex.This is because if the fiber number of each component units after cutting apart less than 0.1dtex, when handling with oleum and chlorosulfonic acid, causes sharply aging and the intensity of non-weaving cloth is reduced, thereby undesirable.And if greater than 0.5dtex, diminish with the fiber number difference of composite fibre described later or synthetic fibers, can not guarantee fine and close space.
Previous segmentation type composite fibre (A) shared ratio in battery diaphragm of the present invention is being no more than in the scope of 60wt% preferred 5～55wt%, more preferably 15～50wt%.This is because if the content of Splittable conjugate fiber (A) is very few, the ratio of methylpentene base polymer is very few, if not under stronger hydrophilic conditions, just can not introduce sufficient hydrophilic group, cause non-weaving cloth intensity to reduce, cost raises, and if surpass 60wt%, the tendency that also exists the non-weaving cloth intensity after the hydrophilic treated to reduce, and cost raises.
Secondly, the TPO composite fibre (B) that is become to be grouped into by high-melting-point composition and low melting point that the present invention is used can adopt polyolefin polymers or its copolymers such as polyethylene, polypropylene, poly-(butene-1), poly-(4-methyl butene-1) and ethylene-vinyl alcohol copolymer.If establishing the fusing point of high-melting-point composition is B1m, the fusing point of low melting point composition is B2m, and the low melting point composition preferably satisfies following relation.
(1)B1m＞B2m
(2)120℃＜B2m＜D2m
As the TPO composite fibre (B) that satisfies above-mentioned relation, can enumerate for example high density polyethylene (HDPE)/polypropylene, ethylene-propylene copolymer/polypropylene etc., if adopt them, the fibre strength excellence, the splitting of two composition interlaminar resins is also few, can obtain sufficient heat seal strength, therefore and preferably.
The fibre morphology of composite fibre is not a particular determination, can enumerate the single fiber of concentric circles or eccentric core-sheath-type composite fibre, Splittable conjugate fiber or two or more mixing of aforementioned material, and section configuration also can be circular or special-shaped any.
Among the present invention, the preferred especially concentric circles core-sheath-type composite fibre of forming by high density polyethylene (HDPE)/polypropylene, because its processing temperature field when non-weaving cloth heat treatment is wide, the non-weaving cloth intensity of gained is big, resistance to chemical reagents, the aging excellence of resistance to oxidation.
Further, aforementioned TPO composite fibre (B) preferably contains 5～55wt%, more preferably 20～50wt% in being no more than the scope of 60wt%.This is because the content of TPO composite fibre is very few, can not obtain sufficient non-weaving cloth intensity, is difficult to guarantee the space if surpass 60wt%, and guarantor's fluidity is insufficient.
Further, in battery diaphragm of the present invention, also can mix the third synthetic fibers (C) as required, mix in the scope below 40wt% this moment.More preferably at 20～40wt%.If this is that the effect of hydrophilic treated diminishes, and can not obtain necessary performance because the content of the third synthetic fibers surpasses 40wt%.For example, as in order to ensure between fiber, forming the space, can use than big by the fiber number of each component units after formed cutting apart of cutting apart of Splittable conjugate fiber, the synthetic fibers identical or little with the fiber number of TPO composite fibre, and if hydrophily is further improved, also can use hydrophilic reagent etc. is pre-mixed synthetic fibers in resin.So, if the 3rd synthetic fibers can use general synthetic fibers such as polypropylene, polyester, nylon from selecting the fiber of not fusion in fact under the melt temperature of polyalkenes composite fibre.Particularly fiber number is 0.5～5dtex, and fibre strength is the polypropylene fibre of 6～15cN/dtex, because resistance to chemical reagents is high more preferably.
The aforementioned form that contains the fibrofelt that constitutes fiber, the long fibre felt that wet type felt that can adopt the dry type felt that obtains by comb and parallel cotton fibers prior to spinning method and air lay method etc., obtains by damp process or direct methods such as meltblown and spun-bond process obtain.The fibre length of especially aforementioned formation fiber is the wet type felt that 3～25mm forms, and is preferred owing to the felt that can obtain homogeneous.More preferably fibre length is at 5～15mm.This be because if fibre length less than 3mm, when High-Pressure Water described later is handled, fiber disperses, interfibrous staggered complexing is insufficient, technology is undesirable, if surpass 25mm, the situation of particularly copying the non-weaving cloth of paper manufactured by wet type, fiber dispersion variation in the paper pulp can not obtain uniform non-weaving cloth.
These fibrofelts can pass through methods such as hot-pressing processing, hot blast processed and High-Pressure Water processing to be handled.At this moment preferably do not have under the situation of fusion in fact at two kinds of compositions that constitute Splittable conjugate fiber at least, bonding by the low melting point composition heat fusing of TPO composite fibre.At this, so-called fusion in fact is not to be softening flat by hot pressing etc., and is not bonding as yet between the fiber, and is meant the complete fusion of a part of fiber.If just the low melting point composition heat fusing of TPO composite fibre is bonding between the formation fiber, superfine fibre and other synthetic fibers that Splittable conjugate fiber is cut apart gained continue to guarantee the space, because the high-melting-point composition of composite fibre is kept fibre strength and make it melting adhered, so, the intensity of non-weaving cloth is disperseed little, can guarantee fine and close space.
Further, as the form of other non-weaving cloth, the change composite rate that also can in above-mentioned formation fiberoptic scope, suit lamination, the non-weaving cloth of lamination between perhaps that fibre length is the different fibrofelts.For example, if the latter on the fibrofelt of the formation fiber of aforementioned fibers length 3～25mm being copied the formation of paper method by wet type, fibre length can be surpassed the fibrofelt of the short fiber formation of 25mm, or the long fibre carpet veneer amasss at least one face.If make the different fibrofelt lamination of fibre length, the long staple fiber batt of fiber helps compactness, and the long long fibre felt of fiber helps non-weaving cloth intensity to improve, and so the productivity excellence when inserting battery is preferred.These fibrofelts can be that comb and parallel cotton fibers prior to spinning etc. does not make the bonded nonwoven cloth of its combination or handles any forms such as non-weaving cloth that make its staggered complexing by acupuncture or High-Pressure Water by bonding agent or self are bonding etc. in conjunction with felt, the part that will constitute fiber.Method as lamination, can be after the lamination, to make staggered complexing between the fiber between with unconjugated felt, also can be to use above-mentioned combination or staggered complexing method non-weaving clothization in advance to a kind of fibrofelt of major general, after the lamination, make staggered complexing between the fiber again.
Further, as other the form of non-weaving cloth, also can be at least a portion layer of aforementioned non-weaving cloth other thin slice of lamination.At this, can be at least a portion layer of aforementioned non-weaving cloth other thin slice of lamination, carry out hydrophilic treated after having made compound foil in advance, also can be in advance after the hydrophilic treated with aforementioned non-weaving cloth, other thin slice of lamination on part layer.At this, so-called other thin slice be meant by fibre length be the fibroplastic wet type non-weaving cloth of 3～25mm, the fibroplastic part that will constitute fiber that surpasses 25mm by fibre length by bonding agent or self bonding etc. make its combination handle the non-weaving cloth that makes its staggered complexing in conjunction with non-weaving cloth, by acupuncture or High-Pressure Water, or porous film etc.If using fibre length in aforementioned other thin slice is the fibroplastic wet type non-weaving cloth of 3～25mm, although pay down, also can obtain the few non-weaving cloth of through hole generation ratio at low constant volume weight order, can reduce the short circuit ratio of battery.And if the use fibre length surpasses fiber or the porous film of 25mm, also can further improve non-weaving cloth intensity.
The material of aforementioned other thin slice there is no particular restriction, can be polyolefin resin, polyamide-based resin or polyester resin etc. any.And the lamination method is if other thin slice of lamination also there is no particular restriction at least a portion layer, both can be on the single face of non-weaving cloth of the present invention or two sides other thin slice of lamination, also can between aforementioned non-weaving cloth, insert other thin slice.Further, more than also can be two-layer with above-mentioned laminate lamination.And the associated methods of each interlayer of above-mentioned laminate also there is no particular restriction, for example, make non-weaving cloth of the present invention in advance by the High-Pressure Water processing, make after itself and other thin slice lamination, combined with heat treatment by hot blast or hot-rolling etc. also can, make to constitute fibrofelt of the present invention and other thin slice in advance after the lamination, handle making its combination also passable by High-Pressure Water.
The constant volume weight order of aforementioned non-weaving cloth or compound foil is paid and can be regulated by fibre weight, preferably sets at 30～100g/m
2This is because as less than 30g/m
2Non-weaving cloth intensity step-down is short-circuited between positive pole and negative pole easily, as surpassing 100g/m
2Reductions such as gas permeability.
Further, aforementioned non-weaving cloth or compound foil are preferably by hydrophilic treated.As hydrophilic treated, can enumerate the graft copolymerization processing, fluorine gas processing, sulfonation processing, Corona discharge Treatment, plasma treatment of vinyl monomer etc., therefore and preferred especially the self-discharge that helps improving battery is handled in sulfonation.Handle as sulfonation, can enumerate concentrated sulfuric acid processing, oleum processing, chlorosulfonic acid processing and anhydrous slufuric acid processing etc.During sulfonation was handled, oleum was handled, chlorosulfonic acid is handled or anhydrous slufuric acid processing reaction height, handled than being easier to sulfonation, and is therefore preferred.And sulfonation degree is preferably at 0.4～2wt%, and 0.7～1.5wt% more preferably.This be because if sulfonation degree less than 0.4wt%, the self-discharge property improvement of battery is insufficient, if surpass 2wt%, not only causes processing cost to increase, and causes that non-weaving cloth intensity reduces.Hydrophilic treated is considered and should be carried out after non-weaving cloth forms from the productivity aspect, and the situation of non-weaving cloth laminate, also can contain the non-weaving cloth hydrophilic treated of Splittable conjugate fiber to the major general.
Below just an example of the manufacture method of battery diaphragm of the present invention describe.As the manufacture method of the base material non-weaving cloth that becomes battery diaphragm of the present invention, preferred wet type is copied the paper method, and wet type is copied paper and got final product with usual way.At first, mix other synthetic fibers, its concentration by 0.01～0.6wt% is dispersed in the water, be modulated into paper pulp with Splittable conjugate fiber 15～60wt%, TPO composite fibre 20～60wt%, in being no more than the scope of 40wt%.At this moment also can add the dispensed in small quantity agent.Paper pulp can adopt short net formula, cylinder or both composite type paper machines etc. to copy paper.Then,, make slight combination between fiber in advance if make the fusion of TPO composite fibre, the processing good operability of non-weaving cloth, therefore and preferably.In a single day the fusion of TPO composite fibre can be carried out with drying when the dried in machine hand's journey simultaneously, and has made after the wet type non-weaving cloth, heat treated also can.
Further, the fusion by the TPO composite fibre makes slight combination between fiber, and form is become after the stable status, carries out High-Pressure Water and handles, and Splittable conjugate fiber is cut apart made staggered complexing between fiber when forming superfine fibre.High-Pressure Water is handled the nozzle that is provided with the interval of 0.5～1.5mm from the hole of aperture 0.05～0.5mmr, with the column current of hydraulic pressure 5～20Mpa more than spraying once on the positive and negative of non-weaving cloth respectively.The non-non-weaving cloth of staggered complexing of gained with 120～D2m ℃, preferred 130～145 ℃ of dryings the time, the low melting point composition by the TPO composite fibre makes that to constitute between the fiber heat fusing bonding.
After this, non-weaving cloth is immersed in oleum reactive tank, chlorosulfonic acid reactive tank or the anhydrous slufuric acid reactive tank, introduces sulfo group.The sulfonation treatment conditions can suit to set, so that sulfonation degree reaches 0.4～2wt%, for example, if handle with anhydrous slufuric acid, can handle under sulfur trioxide gas volumetric concentration 10～80%, 10～90 ℃ of reaction temperatures, 10～600 seconds reaction time condition.At this moment,, also can make after the non-weaving cloth activate, carry out sulfonation again and handle by this ultraviolet ray or radioactive ray in order to promote sulfonation.
Further, on non-weaving cloth, carry out after the hydrophilic treated, can the hydrophilic surfactant active evenly be adhered to, also can cooperate other hydrophilic treated method by infusion process, spray-on process, roller contact method.After this, carry out hot calender and handle, be adjusted to fixed thickness, can obtain battery diaphragm of the present invention.
[embodiment]
Enumerate embodiment below content of the present invention is described.Wherein, tensile strength, guarantor's liquid rate, short circuit ratio, capacity retention rate, cycle life and sulfonation degree are measured by the following method.
(1) endwise tensile strength
According to JIS L 1096, for the wide 5cm of longitudinal direction clamping of non-weaving cloth, the sample of length 15cm,, use the tension type cupping machine of constant speed with 10cm clamping at interval, stretch with the 30cm/min draw speed, the load value during with fracture is as tensile strength.
(2) protect the liquid rate
The weight (W) of the water balance state of sample is measured to 1mg.Then sample is immersed in the KOH solution of proportion 1.30, makes its absorption of K OH solution after 1 hour, from solution, take out, place after 10 minutes, measure the weight (W1) of sample, by formula guarantor liquid rate (%)=(the liquid rate of protecting is calculated in (W1-W)/W) * 100.
(3) the airtight Ni-MH battery of cylindrical shape
Negative pole is that to add water in hydrogen-storage alloy, carbonyl nickel, carboxymethyl cellulose (CMC) and polytetrafluoroethylene (PTFE) mixing, be modulated into slip, with the dip coating in the punch metal of nickel plating of this slip, afterwards, in 80 ℃ of dryings, extrusion forming makes the hydrogen-storage alloy negative pole.The known sintering nickel polar of anodal use.Each barrier film of clamping inserts electric groove pot between above-mentioned negative pole and positive pole, injects electrolyte, is made into the airtight Ni-MH battery of cylindrical shape.
(4) capacity retention rate
With the airtight Ni-MH battery of cylindrical shape of aforementioned making, lead charging 12 hours with 0.1C, suspend 0.5 hour, lead discharge with 0.1C, set final voltage 1.0V, circulating repeatedly discharges and recharges for 10 times, does the initial activity of battery.
So, will be after doing the initial activity of battery, for lead down charging 12 hours with 0.1C, suspend 0.5 hour, lead discharge with 0.1C, set final voltage 1.0V, circulating repeatedly discharges and recharges discharge capacity afterwards for 5 times, after same condition (0.1C leads) charging, the capacity retention rate after the remaining capacity (0.1C leads discharge, final voltage 1.0V) when placing 14 days down for 45 ℃ is defined as self-discharge with its ratio.Discharge and recharge under 25 ℃ and carry out.
(5) short circuit ratio
To when 100 airtight Ni-MH batteries of cylindrical shape of assembling, cause that the ratio of short circuit is defined as short circuit ratio.
(6) cycle life
With the airtight Ni-MH battery of cylindrical shape of having done initial activity, lead charging 10 hours with 0.1C, suspend 0.5 hour, lead discharge (final voltage 1.0V) with 0.1C, the utilance of obtaining the relative theory capacity becomes 90% cycle-index when following.Discharge and recharge under 25 ℃ and carry out.
(7) sulfonation degree
Take the sample of 5cm * 5cm by sample, dipping is 30 minutes in 13% the KOH aqueous solution.With washing from the beginning 30 minutes, further washed 30 minutes afterwards with pure water, then 60 ℃ with sample drying 1 hour, the modulation sample.So, use the fluorescent X-ray determinator, measure the element sulphur concentration in the non-weaving cloth, 100 multiples after will removing with whole concentration of element are defined as sulfonation degree.
(8) fiber is prepared
Prepare following fiber as raw material.In following fiber, be fiber 1, fiber 2 and fiber 8 corresponding to the fiber of Splittable conjugate fiber (A).And be fiber 3～5 corresponding to the fiber of TPO composite fibre (B).And be fiber 6～7 corresponding to the fiber of the third synthetic fibers (C).
[fiber 1] first composition is the methylpentene analog copolymer (Mitsui Chemicals (strain) system) of 240 ℃ of fusing points (D1m), second composition is the polypropylene (Japanese Port リ ケ system (strain) system) of 163 ℃ of fusing points (D2m), compound ratio is 50: 50, has fiber section as shown in Figure 1, fiber number 2.3dtex, the Splittable conjugate fiber of fibre length 6mm.
[fiber 2] first composition is the methylpentene analog copolymer (Mitsui Chemicals (strain) system) of 240 ℃ of fusing points (D1m), second composition is the polypropylene (Japanese Port リ ケ system (strain) system) of 163 ℃ of fusing points (D2m), compound ratio is 50: 50, has fiber section as shown in Figure 1, fiber number 2.3dtex, the Splittable conjugate fiber of fibre length 45mm.
[fiber 3] sheath composition is the high density polyethylene (HDPE) (Japanese Port リ ケ system (strain) system) of 132 ℃ of fusing points (B2m), the core composition is the polypropylene (Japanese Port リ ケ system (strain) system) of 163 ℃ of fusing points (B1m), compound ratio is 50: 50, fiber number 1.7dtex, the concentric circles core-sheath-type composite fibre of fibre length 10mm.
[fiber 4] sheath composition is the low density polyethylene (LDPE) (Japanese Port リ ケ system (strain) system) of 105 ℃ of fusing points (B2m), the core composition is the polypropylene (Japanese Port リ ケ system (strain) system) of 163 ℃ of fusing points (B1m), compound ratio is 50: 50, fiber number 1.7dtex, the concentric circles core-sheath-type composite fibre of fibre length 10mm.
[fiber 5] sheath composition is the high density polyethylene (HDPE) (Japanese Port リ ケ system (strain) system) of 132 ℃ of fusing points (B2m), the core composition is the polypropylene (Japanese Port リ ケ system (strain) system) of 163 ℃ of fusing points (B1m), compound ratio is 50: 50, fiber number 1.7dtex, the concentric circles core-sheath-type composite fibre of fibre length 51mm.
[fiber 6] formed by the polypropylene (Japanese Port リ ケ system (strain) system) of 163 ℃ of fusing points, fiber number 0.8dtex, the polypropylene fibre of fibre length 10mm.
[fiber 7] formed by the polypropylene (Japanese Port リ ケ system (strain) system) of 163 ℃ of fusing points, fiber number 0.8dtex, the polypropylene fibre of fibre length 51mm.
[fiber 8] first composition is ethylene-vinyl alcohol copolymer (ethylene contents 38mol%), and second composition is a polypropylene, and compound ratio is 50: 50, has fiber section as shown in Figure 2, fiber number 3.3dtex, the Splittable conjugate fiber of fibre length 6mm.
[embodiment 1]
With the non-weaving cloth of gained impregnation process 1 hour in the processing of 40 ℃ of liquid temperature that 50wt% chlorosulfonic acid and the 50wt% concentrated sulfuric acid mix is bathed, dipping after 10 minutes in dilute sulfuric acid afterwards floods in KOH solution and neutralized in 1 hour.Washing and drying carries out hot calendering machine and handles afterwards, obtains constant volume weight order and pays 65g/m
2, the battery diaphragm of thickness 0.15mm.
[embodiment 2]
Except treatment fluid with the 100wt% chlorosulfonic acid, use the method identical with embodiment 1, obtain constant volume weight order and pay 65g/m
2, the battery diaphragm of thickness 0.15mm.
[embodiment 3]
Except the mixed liquor of treatment fluid with 20wt% oleum and the 80wt% concentrated sulfuric acid, use the method identical with embodiment 1, obtain constant volume weight order and pay 65g/m
2, the battery diaphragm of thickness 0.15mm.
[embodiment 4]
The non-weaving cloth of gained is immersed in the acrylic acid aqueous solution, and irradiation ultraviolet radiation makes acrylic monomers graft copolymerization afterwards.Clean this non-weaving cloth and remove after the unreacted acrylic acid, drying is carried out hot calendering machine and is handled, and obtains constant volume weight order and pays 65g/m
2, the battery diaphragm of thickness 0.15mm.
[embodiment 5]
Then, in the wet type paper machine, at the entrance side of drum drier aforementioned non-weaving cloth is set, modulation is by the paper pulp that constitutes fibrous 0.5wt% of embodiment 1, on one side wet type copy paper to make constant volume weight be 50g/m
2, on one side the dry type non-weaving cloth that sets in advance of lamination.Syringe drying machine with 135 ℃ is heat-treated, and obtains making the two-layer bonding composite non-weaving cloth of heat fusing cementability fibers melt.
With the non-weaving cloth of gained impregnation process 1 hour in the processing of 40 ℃ of liquid temperature that 50wt% chlorosulfonic acid and the 50wt% concentrated sulfuric acid mix is bathed, dipping after 10 minutes in dilute sulfuric acid afterwards floods in KOH solution and neutralized in 1 hour.Washing and drying carries out hot calendering machine and handles afterwards, obtains constant volume weight order and pays 65g/m
2, the battery diaphragm of thickness 0.15mm.
[embodiment 6]
Replace the fibers 3 except raw material uses fiber 4, use the method identical, obtain constant volume weight order and pay 65g/m with embodiment 1
2, the battery diaphragm of thickness 0.15mm.
[embodiment 7]
Except the mixing ratio with fiber becomes 10wt% fiber 1,50wt% fiber 3 and 40wt% fiber 6, use the method identical with embodiment 1, obtain constant volume weight order and pay 65g/m
2, the battery diaphragm of thickness 0.15mm.
[embodiment 8]
After the non-weaving cloth of embodiment 1 handled 30 seconds in sulfur trioxide gas,, clean, under 60 ℃, make its drying then with ion exchange water with the NaOH neutralization.Carry out hot calendering machine and handle, obtain constant volume weight order and pay 65g/m
2, the battery diaphragm of thickness 0.15mm.
[comparative example 1]
Replace the fibers 1 except raw material uses fiber 8, use the method identical, obtain constant volume weight 65g/m with embodiment 1
2, the battery diaphragm of thickness 0.15mm.
Below, provide the rerum natura such as the table 1 of embodiment 1～8 and comparative example 1.[table 1]
Embodiment 4 is not because there is sulfo group, cycle life is short slightly, embodiment 7 is few because of the combined amount of the Splittable conjugate fiber of being made up of methylpentene analog copolymer and polyolefin polymers, not only the introducing amount of hydrophilic group is few, and the compactness of barrier film is poor, capacity retention rate and cycle life are also low slightly, and for embodiment 1～3,5,6,8, even after hydrophilic treated, still keep full intensity, and it is nearly 80% that the capacity retention rate when the insertion battery also keeps, and helps the improvement of self-discharge.On the other hand, comparative example 1 is owing to undue excessive hydrophilicity-imparting treatment such as sulfonation processing, and fiber damages more than necessary degree, and tensile strength sharply reduces longitudinally, occurs breakage during assembling, and short circuit ratio raises, and productivity significantly reduces.
Battery diaphragm of the present invention is the Splittable conjugate fiber of forming with by methylpentene base polymer and polyolefin polymers, and the TPO composite fibre that is become to be grouped into by high-melting-point composition and low melting point is a main body, by carrying out hydrophilic treated, has the stable on heating while, also has excellent guarantor's fluidity and sufficient non-weaving cloth intensity, under the situation that battery life is reduced, can improve battery capacity.Handle if hydrophilic treated is sulfonation, help the improvement of self-discharge especially.
Further, the battery of the aforementioned battery diaphragm of the present invention of packing into, self-discharge is enhanced, and is specially adapted to electric automobile (PEV) and hybrid vehicle (HEV).
[accompanying drawing simple declaration]
The example of the fibre profile figure of the Splittable conjugate fiber that uses among [Fig. 1] expression the present invention.
The example of the fibre profile figure of the Splittable conjugate fiber that uses among [Fig. 2] expression the present invention.
The example of the fibre profile figure of the Splittable conjugate fiber that uses among [Fig. 3] expression the present invention.
Claims (17)
1. battery diaphragm, it is characterized in that it by the methylpentene base polymer of forming with poly-(4-methylpentene-1) or 4-methylpentene-1 and the copolymer of other alkene as first composition, with the polyolefin polymers different or its copolymer with first composition as second composition, two kinds of compositions are alternately in abutting connection with configuration on the fiber section, at least a composition in two kinds of compositions is split into the Splittable conjugate fiber (A) that forms more than two, with these two kinds of necessary compositions of fibers conduct of the TPO composite fibre (B) that becomes to be grouped into by high-melting-point composition and low melting point, the non-weaving cloth that contains the third synthetic fibers (C) as required, when being 100wt% with the total amount that constitutes fiber, the use level of previous segmentation type composite fibre (A) or TPO composite fibre (B) is no more than 60wt% respectively, and above-mentioned non-weaving cloth is by hydrophilic treated.
2. by the described battery diaphragm of claim 1, wherein, the use level of previous segmentation type composite fibre (A) is more than 5wt%, in the scope below the 55wt%.
3. by the described battery diaphragm of claim 2, wherein, the use level of previous segmentation type composite fibre (A) is more than 15wt%, in the scope below the 50wt%.
4. by the described battery diaphragm of claim 1, wherein, the use level of aforementioned TPO composite fibre (B) is more than 5wt%, in the scope below the 55wt%.
5. by the described battery diaphragm of claim 4, wherein, the use level of aforementioned TPO composite fibre (B) is more than 20wt%, in the scope below the 50wt%.
6. press the described battery diaphragm of claim 1, wherein, in the scope of use level below 40wt% of aforementioned the third synthetic fibers (C).
7. by the described battery diaphragm of claim 1, wherein, constitute the polymer not fusion in fact of two kinds of compositions of the Splittable conjugate fiber in the non-weaving cloth, by the low melting point composition of TPO composite fibre, the fiber that constitutes non-weaving cloth is bonding by heat fusing.
8. by the described battery diaphragm of claim 1, wherein, the fibre length of the fiber of formation non-weaving cloth is in 3～25mm scope.
9. by the described battery diaphragm of claim 1, wherein, non-weaving cloth is the composite non-weaving cloth that lamination forms between the different fibrofelt of fibre length.
10. battery diaphragm it is characterized in that the compound foil that this battery diaphragm forms for other thin slice of lamination on by at least a portion layer of the described non-weaving cloth of claim 1, and aforementioned compound foil is by hydrophilic treated.
11. a battery diaphragm is characterized in that this battery diaphragm other thin slice of lamination on by at least a portion layer of the non-weaving cloth of the described hydrophilic treated of claim 1 forms.
12. by the described battery diaphragm of claim 1, wherein, Splittable conjugate fiber with the methylpentene base polymer as first composition, with polypropylene based polymers as second composition.
13. by the described battery diaphragm of claim 1, wherein, the TPO composite fibre is that the sheath composition is a high density polyethylene (HDPE), the core composition is polyacrylic core-sheath-type composite fibre.
14. by the described battery diaphragm of claim 1, wherein, hydrophilic treated is that sulfonation is handled.
15. by the described battery diaphragm of claim 14, wherein, it is from any of oleum is handled, chlorosulfonic acid is handled and anhydrous slufuric acid is selected handling at least a processing that sulfonation is handled.
16. by the described battery diaphragm of claim 14, wherein, sulfonation degree is 0.4～2wt%.
17. pack into by the battery of the described battery diaphragm of claim 1 for one kind.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31208499A JP3678081B2 (en) | 1998-11-16 | 1999-11-02 | Battery separator and battery using the same |
| JP312084/1999 | 1999-11-02 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1294416A true CN1294416A (en) | 2001-05-09 |
| CN1160812C CN1160812C (en) | 2004-08-04 |
Family
ID=18025053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001085700A Expired - Fee Related CN1160812C (en) | 1999-11-02 | 2000-05-15 | Battery diaphragm and battery using same |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN1160812C (en) |
| HK (1) | HK1035961A1 (en) |
| TW (1) | TW466795B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100364147C (en) * | 2002-05-22 | 2008-01-23 | 三菱制纸株式会社 | Non-woven fabric for separator of alkali cell and method for production thereof |
| CN101043091B (en) * | 2006-03-24 | 2011-03-16 | 三洋电机株式会社 | Nickel hydrogen storage battery |
| CN102725882A (en) * | 2010-02-05 | 2012-10-10 | 三菱制纸株式会社 | Separator for battery |
| CN102903878A (en) * | 2011-07-28 | 2013-01-30 | 三菱制纸株式会社 | Septum used in battery |
| CN102903877A (en) * | 2011-07-28 | 2013-01-30 | 三菱制纸株式会社 | Battery baffle |
| CN101777635B (en) * | 2009-12-30 | 2013-09-18 | 莱州联友金浩新型材料有限公司 | Sulfonated battery diaphragm |
| CN109898322A (en) * | 2019-03-15 | 2019-06-18 | 天津工业大学 | A kind of sulfonation non-woven cloth and preparation method |
| CN114752164A (en) * | 2022-03-18 | 2022-07-15 | 国家电投集团氢能科技发展有限公司 | Ethylene-vinyl alcohol copolymer compound and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI729548B (en) * | 2019-10-31 | 2021-06-01 | 希世比能源科技股份有限公司 | Battery device |
-
2000
- 2000-04-21 TW TW089107538A patent/TW466795B/en not_active IP Right Cessation
- 2000-05-15 CN CNB001085700A patent/CN1160812C/en not_active Expired - Fee Related
-
2001
- 2001-09-12 HK HK01106355A patent/HK1035961A1/en not_active IP Right Cessation
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100364147C (en) * | 2002-05-22 | 2008-01-23 | 三菱制纸株式会社 | Non-woven fabric for separator of alkali cell and method for production thereof |
| CN101043091B (en) * | 2006-03-24 | 2011-03-16 | 三洋电机株式会社 | Nickel hydrogen storage battery |
| CN101777635B (en) * | 2009-12-30 | 2013-09-18 | 莱州联友金浩新型材料有限公司 | Sulfonated battery diaphragm |
| CN102725882A (en) * | 2010-02-05 | 2012-10-10 | 三菱制纸株式会社 | Separator for battery |
| CN102725882B (en) * | 2010-02-05 | 2015-04-22 | 三菱制纸株式会社 | Separator for battery |
| CN102903878A (en) * | 2011-07-28 | 2013-01-30 | 三菱制纸株式会社 | Septum used in battery |
| CN102903877A (en) * | 2011-07-28 | 2013-01-30 | 三菱制纸株式会社 | Battery baffle |
| CN102903878B (en) * | 2011-07-28 | 2015-09-30 | 三菱制纸株式会社 | Battery separator |
| CN102903877B (en) * | 2011-07-28 | 2016-01-20 | 三菱制纸株式会社 | Battery separator |
| CN109898322A (en) * | 2019-03-15 | 2019-06-18 | 天津工业大学 | A kind of sulfonation non-woven cloth and preparation method |
| CN114752164A (en) * | 2022-03-18 | 2022-07-15 | 国家电投集团氢能科技发展有限公司 | Ethylene-vinyl alcohol copolymer compound and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| HK1035961A1 (en) | 2001-12-14 |
| CN1160812C (en) | 2004-08-04 |
| TW466795B (en) | 2001-12-01 |
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