CN103208593A - Battery packaging materials, molding method of battery packaging materials, and lithium secondary battery - Google Patents
Battery packaging materials, molding method of battery packaging materials, and lithium secondary battery Download PDFInfo
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- CN103208593A CN103208593A CN2013100049390A CN201310004939A CN103208593A CN 103208593 A CN103208593 A CN 103208593A CN 2013100049390 A CN2013100049390 A CN 2013100049390A CN 201310004939 A CN201310004939 A CN 201310004939A CN 103208593 A CN103208593 A CN 103208593A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides battery packaging materials, a molding method of battery packaging materials, and a lithium secondary battery. According to the invention, a peripheral part enclosing a recessed part does not lean back during molding of the recessed part. The battery packaging materials provided by the invention is characterized by stacking an outer layer 51 containing heat-resistant resin film, a metal foil layer 52, and an inner layer 53 containing thermoplastic resin film added with a slip agent, wherein the surface of the outer layer 53 is attached with the slip agent.
Description
Technical field
The present invention relates to battery and use forming method and the lithium secondary battery of housing material with housing material, battery.
Background technology
Along with carried change, the miniaturization of electronic equipments such as video camera, notebook computer, mobile portable phone, the requirement of battery miniaturization and of drive source as them is also improved, popularized lithium secondary battery of high performance.Recently, for the vehicle power that makes lithium secondary battery be suitable as electric automobile or hybrid vehicle uses, studied the maximization of lithium secondary battery.
But because the limited mounting space of vehicle power on the vehicle, and the shape of mounting space neither be fixed, so same with the situation of electronic equipment etc., not only require vehicle mounted lithium secondary battery miniaturization (slimming) or lightweight, and require the degree of freedom of shape.As the outer casing container of this lithium secondary battery, for example, known the outer casing container that following patent documentation 1 is such.The outer casing container of patent documentation 1 uses the housing material of the sheet that is laminated by resin bed skin processed, aluminium foil and resin bed internal layer processed and forms, and the resin bed of the internal layer of formation housing material has been endowed heat sealability.By in the outer casing container that is formed by this housing material, inserting monocell (cell), internal layer is sealed each other, can access the lithium secondary battery of the degree of freedom excellence of seal and shape.
Above-mentioned outer casing container is for example made in the following manner.The sheet housing material that preparation is laminated by skin, aluminium foil and internal layer carries out drawing and forming processing to this housing material, forms recess at the housing material central portion.Then housing material and another housing material after the drawing and forming processing are sealed, make outer casing container.The recess that is arranged on the housing material becomes positive pole, negative pole and the electrolytical space that accommodates lithium secondary battery, in addition, with the peripheral part that recess fences up, becomes be used to making housing material integrated heat-sealing portion each other.In addition, the drawing and forming of housing material processing is, prepares to have the 1st mould of protuberance and has the 2nd mould with the protuberance corresponding concave part, disposes housing material between the 1st, the 2nd mould, by these moulds housing material carried out drawing and forming.In addition, as the processing and forming of housing material, except pull and stretch processing, can use bulge forming (bulge forming) processing.
The prior art document
Patent documentation 1: No. 4431822 communique of Japan Patent
Summary of the invention
The problem that invention will solve
But carry out drawing and forming processing or bulge forming adds man-hour at housing material, exist peripheral part that recess is fenced up to the problem of layback.Peripheral part is to layback, takes place that heat-sealing is bad, anodal in just may the subsequent handling after the moulding of recess, the insertion of negative pole etc. is bad.
The present invention In view of the foregoing, its purpose is, the periphery that when being provided at the moulding of recess recess is fenced up to the battery of layback with housing material, battery forming method and the lithium secondary battery with housing material.
Solve the means of problem
. a kind of battery housing material, it is characterized in that, be laminated by the skin that contains heat-resistant resin film, metal foil layer and the internal layer that contains thermoplastic resin film, added slipping agent in the described thermoplastic resin film, and in described outer field surface attachment described slipping agent has been arranged.
. as [1] described battery housing material, the scope of the content of the described slipping agent in the described thermoplastic resin film below the above 3000ppm of 500ppm.
. as [1] or [2] described battery housing material, contain the particle more than a kind or 2 kinds that is selected from acrylic resin, silicone resin, fluororesin, the silicon dioxide in the described thermoplastic resin film.
. as each described battery housing material of [1]～[3], described thermoplastic resin film is formed by polyolefin.
. as each described battery housing material of [1]～[4], the thickness of described internal layer is the scope of 50～100 μ m.
. as each described battery housing material of [1] ~ [5], described skin and described internal layer, be situated between with described metal foil layer and fitted by adhesive linkage.
. as each described battery housing material of [1] ~ [6], at least one in the face of the described internal layer side of described metal foil layer and the face of described outer layer side is provided with the chemical conversion processing layer.
. as each described battery housing material of [1] ~ [7], the face of described internal layer side is provided with the recess that forms by drawing and forming, and is provided with the heat-sealing portion that described recess is fenced up.
. a kind of lithium secondary battery, possess [1] ~ the described battery of each of [8] is with housing material, positive pole, negative pole and electrolyte.
. a kind of battery forming method of housing material, it is characterized in that, will be by the skin that contains heat-resistant resin film, metal foil layer and contain battery that the internal layer of thermoplastic resin film is laminated with housing material with helical coil around, state with described internal layer and described outer close attachment carries out slaking, implement drawing and forming then, the heat-sealing portion that thereby recess is set and described recess is fenced up wherein, has added slipping agent in the described thermoplastic resin film.
. as the forming method of [10] described battery with housing material, at the face of described internal layer side described recess is set.
The invention effect
The present invention can be provided at drawing and forming and add the periphery that man-hour recess is fenced up can not used housing material to the battery of layback with housing material, battery forming method and lithium secondary battery.
Description of drawings
The cross section ideograph of Fig. 1 lithium secondary battery that to be battery with embodiments of the present invention form with housing material.
Fig. 2 is the amplification cross section ideograph that the battery of embodiments of the present invention is used housing material.
Fig. 3 is the ideograph of using the forming method of housing material for the battery of explanation embodiments of the present invention.
Fig. 4 is the ideograph of using the forming method of housing material for the battery of explanation embodiments of the present invention.
Fig. 5 is the ideograph of using the forming method of housing material for the battery of explanation embodiments of the present invention.
Fig. 6 shows that battery that the forming method moulding by embodiments of the present invention obtains is with the cross section ideograph of housing material.
Fig. 7 shows that battery that the forming method moulding by in the past obtains is with the cross section ideograph of housing material.
Embodiment
Below to as the battery of embodiment of the present invention with housing material with have battery and illustrated with the lithium secondary battery of housing material.
As shown in Figure 1, the lithium secondary battery 1 of present embodiment has anodal 2, negative pole 3, electrolyte and battery case container 5 that anodal 2, negative pole 3 and electrolyte are wired up and constituting at least.Battery case container 5 constitutes with housing material 5a, 5b coincident configuration pouch by the battery with sheet.And positive pole 2, negative pole 3 and electrolyte are inserted into the inside of battery case container 5.In addition, in example shown in Figure 1, configuration dividing plate 6 between positive pole 2 and negative pole 3.Also can between positive pole 2 and negative pole 3, replace this dividing plate 6 by the configuration solid electrolyte film.
Battery case container 5 for example is, battery housing material 5a, the 5b of 2 sheets overlapped in internal layer mode respect to one another, the peripheral part 5c of battery housing material 5a, 5b is sealed and is shaped to a bag shape.Peripheral part 5c becomes heat-sealing portion.Battery with housing material 5a, 5b by the skin that contains heat-resistant resin film, metal foil layer with to contain the internal layer of the thermoplastic resin film that has added slipping agent stacked and constitute.In addition, formed for accommodating positive pole 2, negative pole 3 and electrolytical recess 5d at a battery housing material 5a by drawing and forming.In example shown in Figure 1, on another battery housing material 5b, recess is not set, but can recess be set at another battery housing material 5b yet.
Positive pole 2 and negative pole 3 can use by metal forming or wire netting collector body 2a processed, 3a and be layered in the electrode composite material 2b on collector body 2a, the 3a, the electrode that 3b constitutes respectively.Contain positive active material among anodal 2 the electrode composite material 2b, in the electrode composite material 3b of negative pole 3, contain negative electrode active material.
And then anodal 2 and each collector body 2a, 3a of negative pole 3 engaged as label lead-in wire (tab lead) 2c, the 3c that takes out terminal.Label lead-in wire 2c, 3c, the radicle of its length direction is bonded on collector body 2a, the 3a of battery exterior body inside, and the leading section of length direction runs through the peripheral part 5c (heat-sealing portion) of battery case container 5 and outside outstanding at battery 1.Near the 5c of heat-sealing portion of label lead-in wire 2c, 3c, label lead-in wire 2c, 3c are clipped by 2 layers of battery housing material 5a, 5b of sheet, are the state that seals the internal layer of battery housing material 5a, 5b on the surface of label lead-in wire 2c, 3c.
When making lithium secondary battery shown in Figure 1, preparation has the battery case container 5 of the bag shape of peristome, insert positive pole 2, negative pole 3 and electrolyte and dividing plate 6 to battery case container 5, and then inject electrolyte as required, then will peristome being shut, seal from the mode that the outstanding label of peristome lead-in wire 2c, 3c clamp, thereby obtain the lithium secondary battery 1 that peristome has been sealed.
Next, the battery to present embodiment is elaborated with housing material.The battery of present embodiment is laminated by skin 51, metal foil layer 52 and internal layer 53 with housing material 5a, 5b as shown in Figure 2.In addition, as shown in Figure 2, can also outer 51 and metal foil layer 52 between, clip adhesive linkage 54,55 between internal layer 53 and the metal foil layer 52.
(outer 51)
Constituting battery contains the heat-resistant resin film more than at least 1 layer or 2 layers with the skin 51 of housing material 5a, 5b and constitutes.Skin when being made of the heat-resistant resin film more than 2 layers, it is stacked by adhesive linkage to be situated between between the preferred heat-resistant resin film.
Constitute outer 51 heat-resistant resin film, mold be used to accommodating anodal 2 and during the situation of the recess 5d of negative pole 3 with housing material 5a at battery, performance guarantees that battery is with the effect of the mouldability of housing material 5a, so preferably use the stretched film of polyamide (nylon) resin or mylar.In addition, constitute the fusing point of outer 51 heat-resistant resin film, preferably than the fusing point height of the thermoplastic resin film that constitutes internal layer 53.Can when making lithium secondary battery 1, carry out the heat-sealing of peristome effectively thus.
Outer 51 thickness is preferably 10～50 μ m degree, more preferably 15～30 μ m degree.Be 10 μ m when above at thickness, when carrying out battery with the moulding of housing material 5a, the hypometria of stretched film can not occur, constriction (Necking) can not take place in metal foil layer 52, can not cause that moulding is bad.In addition, as long as thickness is below the 50 μ m, just can give full play to the effect of mouldability.
In addition, on outer 51 and face 51a faces metal foil layer 52 side opposition sides, adhered to the slipping agent that contains in the thermoplastic film of internal layer during with the moulding of housing material 5a at battery.This slipping agent is transferred from the internal layer side, can remove after the processing and forming of battery housing material 5a finishes, and in addition, also can place, and can also and then allow its Lock-out.The adhesion amount of the slipping agent in the time of in the transfer printing just is preferably 0.10 μ g/cm
2～0.40 μ g/cm
2Scope, 0.20 μ g/cm more preferably
2～0.35 μ g/cm
2Scope.Adhesion amount can improve the mouldability that battery is used housing material 5a when this scope.In addition, adhere to the affirmation means of slipping agent and the assay method of adhesion amount on the skin, for example can list, after battery is used housing material 5a moulding, with for example solvent stripping of alcohol or chloroform etc. of slipping agent that is attached on outer 51, with the quantitative method that waits of liquid chromatogram.
(metal foil layer 52)
Constitute battery with the metal foil layer 52 of housing material 5a, 5b, bring into play the effect of the block of guaranteeing battery housing material 5a, 5b.As this metal foil layer 52, use aluminium foil, stainless steel foil, Copper Foil etc., consider mouldability, light weight, preferably use aluminium foil.Preferably use the O material (soft material) of fine aluminium system or aluminium-iron-based alloy as the material of aluminium foil.
The thickness of metal foil layer 52 is in order to ensure processability, guarantee block, prevent that oxygen and moisture from entering in the battery that 20～80 μ m are necessary.Thickness is 20 μ m when above, and metal foil layer 52 can be not disrumpent feelings during with the moulding of housing material 5a at battery, and pin hole (pin hole) can not take place, and can prevent the intrusion of oxygen and moisture.In addition, if thickness is below the 80 μ m, disrumpent feelingsly in the time of just moulding can being made improve effect and pin hole prevents that effect is maintained, in addition, can not make the total thickness of battery housing material 5a, 5b become blocked up, prevent that weight from increasing, and improves the volume energy density of battery 1.
In addition, metal foil layer 52 in order to improve it with outer 51 and the cementability of internal layer 53, improves corrosion resistance, can also handle its chemical conversion of implementing the base treatment, chromate processing etc. of silane coupler, titanium coupling agent etc.
(internal layer 53)
Next, constitute battery with the internal layer 53 of housing material 5a, 5b, contain the thermoplastic resin film that has added slipping agent and constitute.The thermoplastic resin film that uses in the internal layer 53, be to have heat sealability, play the effect that the resistance to chemical reagents of the electrolyte that makes the strong lithium secondary battery of tolerance corrosivity etc. improves, and can guarantee that the thermoplastic resin film of the positive pole 2 of metal foil layer 52 and lithium secondary battery 1 or the insulating properties between the negative pole 3 is better.For example preferably use the unstretching film of not drawing polyolefin film, vinyl-acrylate copolymer or the ionomer resin etc. of polypropylene, maleic acid modified polypropene etc. as this thermoplastic resin film.
In addition, constitute the thermoplastic resin film of internal layer 53, though can be constituted by single thermoplastic resin, also can be stacked and constitute by a plurality of thermoplastic resins.
The thickness of internal layer 53 is preferably the scope of 0.1～200 μ m, more preferably the scope of 50～100 μ m.More than thickness is 0.1 μ m, be preferably 50 μ m when above, heat seal strength becomes fully, the corrosion resistance of electrolyte resistance etc. improves in addition, the insulating properties between metal foil layer and the negative or positive electrode improves.In addition, thickness be 200 μ m following, be preferably 100 μ m when following, do not having obstacle aspect heat sealability and the resistance to chemical reagents, in addition, can improve the volume energy density of lithium secondary battery.
And then the fusing point that constitutes the thermoplastic resin film of internal layer 53 is preferably 130 ℃～170 ℃ scope, more preferably 160～165 ℃ scope.Fusing point is when this scope, and the thermal endurance of internal layer 53 improves, and can improve the insulating properties of internal layer 53, and does not reduce the thickness of internal layer 53 when heat-sealing.
(slipping agent)
To add the slipping agent of ormal weight in the thermoplastic resin film of formation internal layer 53.The slipping agent here is for preventing when the drawing and forming mould and battery with close attachment between the housing material, and improves both slidings, and the purpose of the mouldability when improving drawing and forming is added.In addition, be transferred to the surface of skin 51 in the curing step of slipping agent before battery is with the processing and forming of housing material 5a.As slipping agent, preference as, the fatty acid acyl amine of the fatty acid series of the hydrocarbon system of atoleine etc., stearic acid etc., stearmide etc., metallic soap, native paraffin, siloxanes etc., special preferred fatty acid amide-type.As the concrete example of fatty acid acyl amine, can list erucyl amide, oleamide, lauric amide, palmitamide, stearic amide, ethylene two erucyl amides, ethylene two oleamides etc.
The adding method that adds slipping agent in the thermoplastic resin film does not limit, can use following method: directly add to the necessary amount of slipping agent in the resin, give membranization with film-making machine, perhaps, the resin and the mixed with resin of wanting membranization of the additive of high concentration will be contained in advance, membranization then perhaps is dissolved in slipping agent solubilize in the suitable solvent, is applied to then on the thermoplastic resin film surface.It should be noted that slipping agent does not add skin 51 to and adds in the internal layer 53, this is preferred aspect the intensity that can keep skin 51.
The addition of slipping agent is not particularly limited, preferably in the scope of 500～5000ppm.The addition of slipping agent can prevent that battery improves sliding with close attachment between housing material 5a and the mould when processing and forming when 500ppm is above, improve the mouldability that battery is used housing material 5a.In addition, can guarantee to be transferred to the transfer printing amount of the slipping agent on outer 51.And then, if the addition of slipping agent is below the 5000ppm, then can not reduce the mechanical strength of internal layer 53, in addition, improve heat sealability.The addition of slipping agent is the scope of 500ppm～3000ppm more preferably, and then is preferably the scope of 800ppm～3000ppm, most preferably is the scope of 1000ppm～2000ppm.
(particle)
In addition, preferably contain the particle more than a kind or 2 kinds that is selected from acrylic resin, silicone resin, fluororesin, the silicon dioxide in the thermoplastic resin film.By contain these particles in thermoplastic resin film, battery improves the mouldability that battery is used housing material 5a with the sliding between housing material 5a and the mould in the time of can improving processing and forming.In order to improve battery with the mouldability of housing material 5a, for example, preferably make the scope of content below 1 quality % more than the 0.05 quality % of these particles in the thermoplastic resin film, more preferably the scope below 0.5 quality % more than the 0.1 quality %.In addition, preferred average grain diameter is the following scopes of the above 10 μ m of 0.5 μ m, the more preferably scope of 5 μ m more than 1 μ m.
Contain slipping agent by making in the thermoplastic resin film that constitutes internal layer 53, can make the coefficient of kinetic friction with surperficial 53a metal foil layer 52 side opposition sides internal layer 53 is below 0.3.Can when processing and forming, improve battery like this with the sliding between housing material 5a and the mould, improve the mouldability that battery is used housing material 5a.The assay method of the coefficient of kinetic friction for example can be measured according to the method for JIS K7125 (plastics-film and sheet test method of friction coefficient).
(adhesive linkage)
In order will to be bonded together between skin 51 and the metal foil layer 52, will to be bonded together between internal layer 53 and the metal foil layer 52, outer 51 and metal foil layer 52 between, configuration adhesive linkage 54,55 between internal layer 53 and the metal foil layer 52.
Particularly, the adhesive linkage 54 of outer layer side and the adhesive linkage 55 of internal layer side, the preferred adhesive linkage that is formed by different materials that uses.Combination as adhesive linkage 54,55 material, be preferably: when outer 51 are made of PET or nylon, bonding agent as outer layer side uses urethane adhesive, when internal layer 53 was made of polypropylene, using acrylic acid series bonding agent or sour modified olefin as the bonding agent of internal layer side was bonding agent.
By as the adhesive linkage 54 of outer layer side and the adhesive linkage 55 of internal layer side, use the adhesive linkage that is formed by different materials, can give adhesive strength and electrolyte resistance performance between each material.
In addition, also can make internal layer 53 and metal foil layer 52 be situated between laminated by adhesive linkage 55.In addition, it is bonding also can to use the thermal bonding resin of resistance to chemical reagents, electrolyte resistance excellence to be undertaken by hot laminating, in this situation, can access better close attachment between internal layer 53 and metal foil layer 52.In this situation, will be by modifications such as maleic anhydrides between metal foil layer 52 and internal layer 53 the thermal bonding resin of maleic anhydride modified polypropylene etc. carry out extrusion molding, hot laminating.In this hot laminating, compare with the modification thermal bonding resin that uses individual layer, use and polyolefin, for example polypropylene and the modified polypropylene resin of the thermoplastic resin film identical systems of internal layer between the coextrusion resin, the method that metal foil layer and modified polypropene, internal layer and polypropylene thermal is laminated has advantage at cost.
The battery of present embodiment is coated with the laminated bonding agent of using of dry type with housing material 5a, 5b on the surface of skin 51 or metal foil layer 52, makes dry type laminated with the solvent evaporates that contains in the bonding agent.
And, by make outer 51 and metal foil layer 52 to carry out dry type laminated, make the dry type laminate film.
Next, at the metal foil layer 52 of dry type laminate film or the laminated bonding agent of using of surface another dry type of coating of internal layer 53, make this dry type laminated with the solvent evaporates that contains in the bonding agent.It is laminated to make dry type laminate film and internal layer 53 carry out dry type then.Battery housing material 5a, the 5b of present embodiment have so just been produced.
Below, the battery of the present embodiment forming method with housing material 5a is illustrated.
At first, will with the helical form continuous reeling, form coiling body 5e with as shown in Figure 3 by each layer 51～55 by the laminated and stacked sheet battery housing material 5a that obtains of dry type.In coiling body 5e, form battery with the skin 51 of housing material 5a, 5b and be wound on internal layer 53 state of close attachment each other of the volume outer circumferential side of this skin 51.It should be noted that, when coiling, both can be inboard the coiling with the internal layer, also can be inboard with the skin.Then this coiling body 5e is placed in 40 ℃～70 ℃ temperature range and carried out slaking in 40 hours～200 hours.
Through this slaking, the slipping agent that adds in the thermoplastic resin film of internal layer 53 oozes out, and is transferred to outer 51 surface, and is attached to outer 51 surface.
Next, with the coiling body 5e debatching after the slaking end, make the battery housing material 5a of sheet, this battery is carried out drawing and forming processing with housing material 5a.
Specifically, as shown in Figure 4 and Figure 5, prepare to have the 1st mould 61 of protuberance 61a and have the 2nd mould 62 with the chimeric peristome 62a of protuberance 61a, setting battery housing material 5a between the 1st, the 2nd mould 61,62.Battery housing material 5a disposes in the mode of internal layer 53 towards the 1st mould 61 sides.Then as shown in Figure 5, the 1st mould 61 is raise, battery is carried out drawing and forming with housing material 5a.
At this moment, in the internal layer 53 of battery with housing material 5a, be added with slipping agent, in addition, adhered in curing step from the next slipping agent of internal layer 53 transfer printings outer 51, so outer 51 improve with respect to the sliding of the 2nd mould 62 and internal layer 53 sliding with respect to the 1st mould 61, skin 51 during drawing and forming and the extensible extent of internal layer 53 are basic identical, extension residual stress and the extension residual stress in the internal layer 53 in the face in the feasible skin 51 is basic identical thus, thereby has suppressed the generation of battery with the peripheral part 5c layback of housing material 5a.
So just as shown in Figure 6, obtained being provided with at the face of internal layer side the battery housing material 5a of recess 5d.
The battery of present embodiment housing material 5a, owing to have the internal layer 53 that contains the thermoplastic resin film that has added slipping agent, and the surface attachment outer 51 has slipping agent, so drawing and forming add man- hour mould 61,62 and outer 51 and internal layer 53 between sliding improve, particularly can improve battery with the mouldability of housing material 5a, swing back and can peripheral part 5c not take place when forming recess 5d and its peripheral part 5c.
In addition, the battery of present embodiment housing material 5a, because the scope of content below the above 5000ppm of 500ppm of the slipping agent in the thermoplastic resin film, so can improve the mouldability that battery is used housing material 5a.
And then, the battery of present embodiment housing material 5a, owing in thermoplastic resin film, contain the particle more than a kind or 2 kinds that is selected from acrylic resin, silicone resin, fluororesin, the silicon dioxide, can further improve the mouldability that battery is used housing material 5a.
And then in addition, the battery of present embodiment housing material 5a is owing to thermoplastic resin film is formed by polyolefin, so can improve the heat sealability when making outer layer container 5 when keeping mouldability.
In addition, the battery of present embodiment housing material 5a is because the thickness of internal layer 53 is the scope of 50～100 μ m, so can further improve the heat sealability when making outer casing container 5 when keeping mouldability.
And then, the battery of present embodiment housing material 5a, owing to outer 51 and internal layer 53 and metal foil layer 52 between clip adhesive linkage 54,55 and fit, so the peeling off of each layer can prevent to seal the time.
And then in addition, the battery of present embodiment housing material 5a is because at least one in the face of the face of the internal layer side of metal foil layer 52 or outer layer side is provided with the chemical conversion processing layer, so can prevent peeling off of each layer.
And then, in addition, the battery of present embodiment housing material 5a is owing to be provided with the recess 5d that forms by drawing and forming at the face 53a of internal layer side, and around recess 5d, be provided with the 5c of heat-sealing portion, so can be configured for taking in positive pole 2, negative pole 3 and electrolytical outer casing container 5.
Next, the battery of the present embodiment forming method of housing material 5a, since with battery with housing material 5a with helical coil around, form the state of internal layer 53 and outer 51 close attachment, after this state slaking, implement drawing and forming, so can be by the slipping agent and the slipping agent that originally adds in the internal layer 53 that are transferred to by slaking on outer 51, improve the relative mould 61 of housing material 5a, 62 sliding, improve battery thus with the mouldability of housing material 5a, suppress the generation of the peripheral part 5c layback of recess 5d.
In addition, the battery of present embodiment owing at the face 53a of internal layer side recess 5d is set, so can improve battery with the mouldability of housing material 5a, further is suppressed at the generation of the peripheral part 5c layback of recess 5d with the forming method of housing material 5a.
Embodiment
(embodiment 1)
The stretched polyamide film of thickness 25 μ m of acrylic resin pearl of the average grain diameter 2 μ m of 0.1 quality % has been added in preparation, be adhesive linkage at speed: 80m/ minute, roll temperature be situated between two-package curing type polyurethane by 3 μ m of the aluminium foil (JIS standard A 8079H-O) of this outer membrane and thickness 40 μ m: it is laminated to carry out dry type under 80 ℃ the condition, produces outer layer metal paper tinsel tunic.
Next, prepare to have added un-stretched polypropylene film (the ethene containing ratio is the atactic copolymerized polypropene film of 4 quality %) as the thickness 40 μ m of the acrylic resin pearl 0.3 quality % of the erucyl amide 1500ppm of slipping agent and average grain diameter 2 μ m as internal layer, make the two-package curing type acrylic acid series adhesive linkage that clips 1.5 μ m between this internal layer and the outer layer metal paper tinsel tunic at speed: 80m/ minute, roll temperature: it is laminated to carry out dry type under 80 ℃ the condition, produces the battery housing material of the embodiment 1 of length 4000m, width 700mm, thickness 113 μ m thus.
Next, as shown in Figure 3, with the battery of embodiment 1 with housing material with internal layer as inboard, become coiling body with the helical form continuous reeling.Then this coiling body is placed at 40 ℃ and carried out slaking in 120 hours.
Next, the coiling body debatching with after the slaking end cuts out the length of regulation as the battery housing material of sheet, and this battery is carried out drawing and forming processing with housing material.
Specifically, as shown in Figure 4 and Figure 5, the 2nd mould of preparing to have the 1st mould of protuberance and having peristome, setting battery housing material between each mould disposes with housing material battery in the mode of internal layer towards the 1st die side.Then as shown in Figure 5, the 1st mould is raise, battery is carried out drawing and forming with housing material.The degree of depth of pull and stretch processing is made as 5mm, in addition, makes the size of overlooking of recess be the size of 5.3cm * 3.3cm, and then with pruning around the recess, forms the size of whole 9.5cm * 6.5cm.The width of peripheral part is made as 30mm.So just obtained the battery housing material after the processing and forming of embodiment 1.
(embodiment 2～7)
Except slipping agent and the particle that adds in the internal layer are changed as following table 1, will set for the curing time table 1 like that beyond, make the battery housing material after the processing and forming of embodiment 2～7 similarly to Example 1.
(comparative example 1)
Prepare the stretched polyamide film of thickness 25 μ m, be adhesive linkage with speed: 80m/ minute, roll temperature be situated between two-package curing type polyurethane by 3 μ m of the aluminium foil (JIS standard A 8079H-O) of this outer membrane and thickness 40 μ m: it is laminated that 80 ℃ condition is carried out dry type, thereby produce outer layer metal paper tinsel tunic.
Next prepare the un-stretched polypropylene film (the ethene containing ratio is the atactic copolymerized polypropene film of 4 quality %) of thickness 40 μ m as internal layer, make the two-package curing type acrylic acid series adhesive linkage that clips 1.5 μ m between this internal layer and the outer layer metal paper tinsel tunic at speed: 80m/ minute, roll temperature: it is laminated to carry out dry type under 80 ℃ the condition, thereby produces the battery housing material of the comparative example 1 of length 4000m, width 700mm, thickness 113 μ m.
Next, the battery of comparative example 1 is cut out the length of regulation as the battery housing material of sheet with housing material, this battery is carried out drawing and forming processing similarly to Example 1 with housing material.
So just obtained the battery housing material after the processing and forming of comparative example 1.The battery of gained with housing material as shown in Figure 7, peripheral part towards the concave depth direction greatly to layback.
The housing material of the embodiment of gained and comparative example is measured the layback amount of peripheral part.The assay method of layback amount is with housing material recess to be made progress on the battery after the moulding and place in the plane, measure the height the peripheral part end from planar portions to the short-movie side, be averaged.The result is as shown in table 1.As shown in table 1, to compare with comparative example as can be known, the housing material layback amount of embodiment reduces significantly.As shown in table 2 in addition, to compare with comparative example as can be known, the coefficient of kinetic friction of the housing material of embodiment reduces significantly.It should be noted that the assay method of the coefficient of kinetic friction is according to JIS K7125 (plastics-film and sheet test method of friction coefficient).
In addition, the adhesion amount that adheres to slipping agent at skin has been shown in the table 2.Adhesion amount is by the battery after the moulding being immersed in the chloroform with housing material, extracting the slipping agent that is attached on the skin, with the slipping agent in the quantitative extract of liquid chromatogram, thereby measure.Can infer: owing to skin when slaking has adhered to slipping agent, so reduced the coefficient of kinetic friction of housing material, prevented the generation of swinging back in the processing and forming among the embodiment.
Table 1
Table 2
Claims (11)
1. battery housing material, it is characterized in that, be laminated by the skin that contains heat-resistant resin film, metal foil layer and the internal layer that contains thermoplastic resin film, added slipping agent in the described thermoplastic resin film, and in described outer field surface attachment described slipping agent has been arranged.
2. battery housing material as claimed in claim 1, the scope of the content of the described slipping agent in the described thermoplastic resin film below the above 3000ppm of 500ppm.
3. battery housing material as claimed in claim 1 or 2 contains the particle more than a kind or 2 kinds that is selected from acrylic resin, silicone resin, fluororesin, the silicon dioxide in the described thermoplastic resin film.
4. battery housing material as claimed in claim 1 or 2, described thermoplastic resin film is formed by polyolefin.
5. battery housing material as claimed in claim 1 or 2, the thickness of described internal layer is the scope of 50～100 μ m.
6. battery housing material as claimed in claim 1 or 2, is situated between with described metal foil layer and is fitted by adhesive linkage described skin and described internal layer.
7. battery housing material as claimed in claim 1 or 2, at least one in the face of the described internal layer side of described metal foil layer and the face of described outer layer side is provided with the chemical conversion processing layer.
8. battery housing material as claimed in claim 1 or 2, the face of described internal layer side is provided with the recess that forms by drawing and forming, and is provided with the heat-sealing portion that described recess is fenced up.
9. a lithium secondary battery possesses claim 1 or 2 described batteries housing materials, positive pole, negative pole and electrolyte.
10. a battery is with the forming method of housing material, it is characterized in that, will be by the skin that contains heat-resistant resin film, metal foil layer and contain battery that the internal layer of thermoplastic resin film is laminated with housing material with helical coil around, state with described internal layer and described outer close attachment carries out slaking, implement drawing and forming then, the heat-sealing portion that thereby recess is set and described recess is fenced up wherein, has added slipping agent in the described thermoplastic resin film.
11. battery as claimed in claim 10 is with the forming method of housing material, at the face of described internal layer side described recess is set.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| JP2012007444A JP5959205B2 (en) | 2012-01-17 | 2012-01-17 | Battery exterior material, battery exterior material molding method and lithium secondary battery |
| JP007444/2012 | 2012-01-17 |
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| Publication Number | Publication Date |
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| CN103208593A true CN103208593A (en) | 2013-07-17 |
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| CN201310004939.0A Active CN103208593B (en) | 2012-01-17 | 2013-01-07 | Battery housing material, the forming method of battery housing material and lithium secondary battery |
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| CN2013200056629U Expired - Lifetime CN203288659U (en) | 2012-01-17 | 2013-01-07 | Outer packaging material for battery and lithium secondary battery |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN103208593B (en) | 2016-12-28 |
| JP2013149397A (en) | 2013-08-01 |
| CN203288659U (en) | 2013-11-13 |
| JP5959205B2 (en) | 2016-08-02 |
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