CN203267345U - Packaging material for forming and lithium secondary battery - Google Patents
Packaging material for forming and lithium secondary battery Download PDFInfo
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- CN203267345U CN203267345U CN2013200443778U CN201320044377U CN203267345U CN 203267345 U CN203267345 U CN 203267345U CN 2013200443778 U CN2013200443778 U CN 2013200443778U CN 201320044377 U CN201320044377 U CN 201320044377U CN 203267345 U CN203267345 U CN 203267345U
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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
Abstract
The utility model provides a packaging material for forming. The packaging material has the advantage that the generation of pinholes can be inhibited when press forming including a procedure for forming a corner portion with a very small bending radius is carried out. According to the packaging material for forming, provided by the utility model, the surface and inside of the packaging material have resin layers, an Al-Fe series aluminum-alloy foil with the thickness of 30-120 microns is used, the average crystal grain diameter of crystal grains contained in the Al-Fe series aluminum-alloy foil is 5-20 microns, a plurality of crystal grains, which have the maximum length greater than 0.6 times the thickness of the Al-Fe series aluminum-alloy foil and lower than 0.8 times the thickness of the Al-Fe series aluminum-alloy foil in the foil rolling direction section of the Al-Fe series aluminum-alloy foil in the thickness direction of the Al-Fe series aluminum-alloy foil, exist, and the spacing between every two crystal grains is greater than 1 mm.
Description
Technical field
The utility model relate to for be shaped to make battery with the shaping of the package body of exterior body etc. with packaging material with possess the lithium secondary battery of the battery use exterior body that its shaping is formed.
Background technology
In recent years, lithium secondary battery is just utilized widely as vehicle power of drive source, electric automobile or the hybrid electric vehicle of the electronic equipments such as portable phone, notebook personal computer etc.
Battery exterior body (battery container) as lithium secondary battery, use is with stamped metal processing and containerization becomes cylindric or rectangular-shaped metal-made tank, perhaps, the compressing recess that forms of laminated body that will be consisted of by the heat adhesiveness resin bed of outermost heat-resistant resin layer, metal forming, innermost layer, the laminated body of taking in embossing (emboss) type that battery main body forms in above-mentioned recess.
In the metal-made tank, because container outer wall is firm, so the free degree of shape is restricted, and also there is the limit in the thin-walled property of tank.
On the other hand, in the laminated body (being designated hereinafter simply as laminated body) of embossing type, by composition and the thickness of selecting stacked material, the thin-walled property of laminated body is easier to.Therefore, can obtain flexibility and the strength of materials and percentage elongation by the material of selecting suitable laminated body excellent, and the free degree of shape (shaping) is high, more small-sized battery exterior body.As the metal forming of such laminated body, the alloy foil of known strength and extensibility excellence.
The performance of lithium secondary battery is mainly estimated with volume energy density and weight energy density.Therefore, in requiring the slim and light-weighted portable information terminal device of lithium secondary battery, adopt the high rectangular-shaped battery exterior body of the free degree of shape more.
Recently, the lift-launch of smart mobile phone etc. the portable information terminal device of touch panel sharply increase, require the further slim and lightweight of lithium secondary battery.Be accompanied by slim and lightweight, in order to obtain battery capacity to greatest extent in the space in limited arranging, require angle (corner) part to be very sharp-pointed rectangular-shaped battery exterior body.
In order to make more sharp-pointed rectangular-shaped battery exterior body, when laminated body material compressing, the part that the wall thickness of material among cuboid is reduced maximum angle is bent into the shape near the right angle.Therefore, require to have in the lump intensity and can tolerate the alloy foil of the flexibility of the bending when compressing.
For obtaining to have improved the aluminium alloy of formability, various technology and manufacture method have been proposed.
In patent documentation 1, aluminium alloy plate and the method for warm compaction of the warm working (warm forming) of using as parts such as the transporting equipments such as automobile, boats and ships, vehicle, machinery, electrical apparatus product, works, optical devices disclosed.
In patent documentation 1, be composition, the average crystal grain particle diameter of (Al-Mg-Si system) alloy by controlling 6000, can obtain having the aluminium alloy plate of good warm working, the average crystal grain particle diameter is set as the scope of 10～50 μ m.
In addition, patent documentation 1 is to be conceived to 6000 line aluminium alloys (Al-Mg-Si systems, extruded material) scheme of the material property of monomer (composition, crystal grain) and method of warm compaction, the size of microcrystal of aluminium alloy is recited as 10～50 μ m, but be not the scheme that relates to the formability of the laminated body as resin bed/metal forming/resin bed, the kind of aluminium alloy is also different from Al-Fe.
In addition, in patent documentation 2, secondary cell housing aluminium alloy plate and manufacture method thereof are disclosed.By with Cu content: 0.2～1.0 % by weight, Mn content: 0.5～2.0 % by weight, its surplus is set as below 150 μ m by the average crystal grain particle diameter of the aluminium alloy that forms that Al and impurity consist of, the aluminium alloy plate that can obtain intensity, has excellent formability.
Patent documentation 2 is schemes of the material property that is conceived to 3000 line aluminium alloys (Al-Mn system) monomer (form, crystal grain) and manufacture method thereof, and purposes is the secondary cell housing, but it is to relate to metal can with the scheme of the formability of material.Thereby different from aluminium alloy (Al-Fe system) kind of (resin bed/metal forming/resin bed) laminated body that is used for the embossing type, the average crystal grain particle diameter also becomes the size of microcrystal scope of the following broader region of 150 μ m.
In addition, in patent documentation 3, the container forming laminated body that food, dessert purposes are used is disclosed.The container forming laminated body of patent documentation 3 is characterized in that, is that two sides below 20 μ m, the Al-Fe line aluminium alloy is provided with synthetic resin layer at the average crystal grain particle diameter.
This container forming laminated body, the inboard that is the Al-Fe line aluminium alloy paper tinsel of 25～40 μ m at thickness is laminated with the CPP film that thickness is 150～500 μ m, being laminated with thickness in the outside is the OPP(oriented polypropylene of 5～50 μ m) film or without the tensile nylon film.Laminated body as described above consists of, the bore that can carry out containers for food use etc. is shaped as circle, the shaping of angle R, drift shoulder (punch shoulder) container that R is large, but the shaping of the angle type container of more sharp-pointed shapes as the type lithium secondary battery housing of angle, angle R1～10, drift shoulder R0.5～5 etc. is more difficult.
In addition, in patent documentation 4, the one side at aluminium foil that discloses packing cake, cigarette etc. is situated between by binding agent the integrated packaging material of quires layer.The packaging material of patent documentation 4, be the one side that the average crystal grain particle diameter is the Al-Fe line aluminium alloy paper tinsel of 5～20 μ m be situated between by the binding agent of polyvinyl acetate, ethylene-vinyl acetate EVA etc. and the quires layer integrated the aluminium laminated body.
These packaging material relate to pack the aluminium-paper packing material of cake, cigarette etc., imagine by bending, fold the packing content thing.Therefore, be not that to be shaped press grain forming by deep-draw be angle type shape, fill the lithium secondary battery element, form the packaging material of the battery packages of angle type.In addition, the kind of binding agent also use from the applying of aluminium foil and resin molding, that biliquid curing type urethanes is dry lamination is different with binding agent.
The prior art document
Patent documentation 1: TOHKEMY 2008-266684 communique
Patent documentation 2: TOHKEMY 2000-129384 communique
Patent documentation 3: Japanese kokai publication sho 60-161142 communique
Patent documentation 4: TOHKEMY 2004-27353 communique
The utility model content
A kind of Al-Fe as alloy foil is associated goldleaf, is to have excellent intensity, the soft paper tinsel of ductility, is used as the constituent material of laminated body all the time.
But, with in the manufacturing of exterior body, minimum if the bending radius of angle part becomes at rectangular-shaped battery, easily produce the problem of pin hole (pinhole) when having Al-Fe line aluminium alloy paper tinsel compressing in the angle part.
The utility model is In view of the foregoing completed, and its purpose is to provide a kind of shaping packaging material, and it also can suppress the generation of pin hole when the formation operation that comprises the angle part that bending radius is minimum compressing.
[1] a kind of shaping packaging material, possessing resin bed, used thickness in table is the shaping packaging material of the Al-Fe line aluminium alloy paper tinsel of 30 μ m～120 μ m, in above-mentioned Al-Fe line aluminium alloy paper tinsel, the average crystal grain particle diameter of contained crystal grain is 5 μ m～20 μ m, and exist a plurality of paper tinsels that have above-mentioned Al-Fe line aluminium alloy paper tinsel in the paper tinsel rolling direction cross section of above-mentioned Al-Fe line aluminium alloy paper tinsel on the thickness direction of above-mentioned Al-Fe line aluminium alloy paper tinsel thick more than 0.6 times and lower than the crystal grain of the maximum length of 0.8 times, these are more than a plurality of crystal grain mutual distance 1mm.
Moreover, in above-mentioned Al-Fe line aluminium alloy paper tinsel the average crystal grain particle diameter of contained crystal grain and have the paper tinsel of above-mentioned Al-Fe line aluminium alloy paper tinsel thick more than 0.6 times and lower than the distance of the crystal grain mutual distance of the maximum length of 0.8 times, be the value that adopts assay method described later to try to achieve.
[2] shaping packaging material described according to [1], at least one of the resin bed in above-mentioned table is heat stable resin, used the stretched film that is made of polyamide or polyester film as above-mentioned heat stable resin.
[3] shaping packaging material described according to [1] or [2], at least one of the resin bed in above-mentioned table is stretched film, above-mentioned stretched film is dry lamination binding agent and above-mentioned Al-Fe line aluminium alloy paper tinsel bonding by biliquid curing type urethanes.
[4] the described shaping packaging material of any one of basis [1]～[3], be at least one surface to above-mentioned Al-Fe line aluminium alloy paper tinsel, implemented that chemical conversion that the chromium phosphate hydrochlorate processes is processed or with acrylic resin (comprising acrylic acid (acryl) is water-soluble resin) or the acrylic acid series water-soluble resin material with the crosslinked base treatment of slaine.
[5] the described shaping packaging material of any one of basis [1]～[4], the one of the resin bed in above-mentioned table is heat stable resin, another one is adhesion resin, perhaps both are heat stable resin, and, one side at least to above-mentioned Al-Fe line aluminium alloy paper tinsel has been implemented the chemical conversion processing, has tack coat between the above-mentioned Al-Fe line aluminium alloy paper tinsel of processing through chemical conversion and above-mentioned resin bed.
[6] shaping packaging material described according to [5], above-mentioned tack coat are the dry lamination adhesive layer of modified polypropene system or modified polypropene and the polyacrylic coextrusion resin bed that makes the mode of above-mentioned chemical conversion treated side side bonding modified polypropene.
[7] a kind of lithium secondary battery possesses the battery exterior body that the described shaping of any one of [1]～[6] is shaped and forms with packaging material.
According to shaping packaging material of the present utility model, the generation of the pin hole in can preventing Al-Fe line aluminium alloy paper tinsel when the formation operation that comprises the angle part that bending radius is minimum compressing.Therefore, by using shaping packaging material of the present utility model, can be with sharp-pointed shape, carry out the high battery of intensity with the shaping of the package body of exterior body etc., can obtain the battery of heat sealability, chemical-resistant, sealing excellence with the package body of exterior body etc.
Description of drawings
Fig. 1 means the shaping of the present utility model sectional view of one example of packaging material.
Fig. 2 means the shaping of the present utility model stereogram of one example of packaging material.
Fig. 3 means shaping of the present utility model another stereogram of one example of packaging material.
Description of reference numerals
1 ... Al-Fe line aluminium alloy paper tinsel; 2,3 ... resin bed; 4 ... coarse grain; 10 ... be shaped and use packaging material; 24 ... outside Al-Fe line aluminium alloy paper tinsel volume; 26 ... the section sample
The specific embodiment
(embodiment)
Below, for the shaping packaging material as embodiment of the present utility model, Yi Bian illustrate on one side with reference to accompanying drawing.
Fig. 1 uses the sectional view of packaging material 10 rolling direction D1 with the shaping of an example of packaging material as shaping of the present utility model.
Be shaped and possess the shaping laminating foil of resin bed 2,3, Al-Fe line aluminium alloy paper tinsel 1 with packaging material 10 in table.
Al-Fe line aluminium alloy paper tinsel 1 is made of the Al-Fe line aluminium alloy.
As this alloy, for example can enumerate Fe content: 0.7～1.3 % by weight, Si content: 0.05～0.3 % by weight, Cu content: 0.05 % by weight is following, Zn content: below 0.10 % by weight, its surplus is the alloy of Al and other inevitable impurity.In addition, above-mentioned alloy also can contain the Mg of the following content of 0.05 % by weight.
In Al-Fe line aluminium alloy paper tinsel, by Fe content is set as 0.7～1.3 % by weight, compare with the aluminium foil that does not contain Fe, can improve ductility, prevent the generation of the pin hole that caused by bending etc.Because in the situation that Fe content is lower than 0.7 % by weight, confirm also to confirm the effect of improving less than formability less than preventing the pin hole produce an effect in Al-Fe line aluminium alloy paper tinsel.In addition, because in the situation that Fe content surpasses 1.3 % by weight, the flexibility of Al-Fe line aluminium alloy paper tinsel 1 suffers damage, and is not preferred for the manufacturing of laminated body.
In addition, Fe has the effect that makes crystal grain fine, but the effect of adding during lower than 0.7 % by weight is insufficient, surpass 1.3 % by weight produce thick intermetallic compound if add, and formability variation not only, corrosion resistance is variation also.
Si and Fe have the effect that makes size of microcrystal fine jointly, but the effect of adding during lower than 0.05 % by weight is insufficient, surpass 0.3 % by weight, the corrosion resistance variation of paper tinsel if add.
The thick Z of paper tinsel on the thickness direction D2 of Al-Fe line aluminium alloy paper tinsel 1 is 30 μ m～120 μ m, more preferably 30 μ m～100 μ m, more preferably 30 μ m～40 μ m.The reason that is set as so thick Z of paper tinsel is in order to ensure machinability and the barrier that prevents the intrusion of moisture.
If the thickness of Al-Fe line aluminium alloy paper tinsel 1 lower than 30 μ m, when compressing (deep drawing shaping), easily causes the fracture of Al-Fe line aluminium alloy paper tinsel 1, though also easily produce when not rupturing in addition pin hole etc. therefore the moisture danger of invading uprise.On the other hand, if the thickness of Al-Fe line aluminium alloy paper tinsel 1 surpasses 120 μ m, the further effect of improving of the fracture when can't see for shaping prevents that the pin hole produce an effect from also there is no improvement.In addition, only thicken the packaging material gross thickness, the weight energy density of the battery that adopting is shaped uses packaging material 10 and volume energy density are reduced.
Thickness with respect to Al-Fe line aluminium alloy paper tinsel 1 is 30 μ m～120 μ m, and in Al-Fe line aluminium alloy paper tinsel 1, the average crystal grain particle diameter of contained crystal grain is 5 μ m～20 μ m.
The further raising that the average crystal grain particle diameter is confirmed less than formability lower than the Al-Fe line aluminium alloy paper tinsel 1 of 5 μ m.In addition, easily to contain maximum length L2 shown in Figure 1 be crystal grain (then explanation coarse grain 4) more than 0.8 times if the average crystal grain particle diameter greater than 20 μ m, becomes, and formability reduces.
There are a plurality of coarse grains 4 in Al-Fe line aluminium alloy paper tinsel 1.
In this manual, so-called coarse grain refers on thickness direction D2, has more than 0.6 times and lower than the crystal grain of the maximum length L2 of 0.8 times of the thick Z of paper tinsel of Al-Fe line aluminium alloy paper tinsel 1.
In the situation of 0.6 times of maximum length L2 on the thickness direction D2 of coarse grain 4 lower than the thick Z of paper tinsel, formability is made a very bad impression.In addition, if the maximum length L2 on the thickness direction D2 of coarse grain 4 is more than 0.8 times of the thick Z of paper tinsel, more easily produce pin hole near this coarse grain 4.
In addition, as shown in Figure 1, the center C of coarse grain 4 sow discord distance X apart from being important more than 1mm.If 4 of coarse grains to sow discord distance shorter than 1mm, when the shaping that is shaped with packaging material 10, easily produce pin hole in Al-Fe line aluminium alloy paper tinsel 1.
Resin bed 2,3, preferred one is heat stable resin, and another one is adhesion resin, and perhaps, both are heat stable resin.
Namely, as resin bed 2,3 and the formation of the packaging material of Al-Fe line aluminium alloy paper tinsel 1, can enumerate such as heat stable resin I/Al-Fe line aluminium alloy paper tinsel/heat stable resin II/adhesion resin, heat stable resin I/heat stable resin II/Al-Fe line aluminium alloy paper tinsel/heat stable resin III/adhesion resin, heat stable resin/Al-Fe line aluminium alloy paper tinsel/adhesion resin, heat stable resin I/heat stable resin II/Al-Fe line aluminium alloy paper tinsel/adhesion resin etc.
Be shaped with in packaging material 10, need to preventing the caused fracture of constriction (necking) of the Al-Fe line aluminium alloy paper tinsel 1 when compressing, carrying out the shaping of sharp-pointed shape.Therefore, as the heat stable resin of intensity and percentage elongation excellence, preferred stretched film is at single face or the two sides contact laminating of Al-Fe line aluminium alloy paper tinsel 1.In addition, being shaped seals after shaping with packaging material 10, therefore can use well to have stable on heating stretched film.
As stretched film, can use polyamide (nylon) or polyester film.Especially, preferably be rich in heat resistance, intensity and percentage elongation are high, the stretched film that directionality is few.
Like this, by with PA membrane or polyester film single face or the two sides contact laminating at Al-Fe line aluminium alloy paper tinsel 1, perhaps make polyester film and PA membrane stacked, single face or two sides contact laminating at Al-Fe line aluminium alloy paper tinsel 1, the constriction of the Al-Fe line aluminium alloy paper tinsel 1 in the time of can effectively suppressing to be shaped obtains the battery exterior body of dark and sharp-pointed shape.
In the situation that resin bed 2,3 one or both use above-mentioned stretched film, preferably the thickness with stretched film is made as 9～50 μ m.If the thickness of stretched film is lower than 9 μ m, when carrying out sharp-pointed shaping, the percentage elongation of stretched film is not enough, in Al-Fe line aluminium alloy paper tinsel 1, constriction occurs, and the caused cob webbing of fracture of Al-Fe line aluminium alloy paper tinsel 1 easily occurs.On the other hand, if the thickness of stretched film surpasses 50 μ m, although the intensity of shape maintains improves, but the effect that prevents the formability of the fracture of Al-Fe line aluminium alloy paper tinsel 1, sharp-pointed shape does not improve, only thickening shaping with in packaging material 10, weight energy density and volume energy density are reduced.
On Al-Fe line aluminium alloy paper tinsel 1 during contact laminating, preferably using biliquid curing type urethanes is the dry lamination binding agent with stretched film.Its reason is owing to can utilizing cold forming (deep drawing is shaped or the protruding shaping of drum) to realize fully sharp-pointed shaping after aging (ageing).
In addition, in the situation that resin bed 2,3 one use adhesion resin, preferably use the unstretching film of polyethylene, polypropylene, polypropylene EVA, maleic acid modified polypropene, ethylene-acrylate EVA or ionomer resin etc. as adhesion resin.Unstretching film as described above can improve the chemical-resistant for the electrolyte of invading the lithium secondary battery produces hydrofluoric acid because of moisture etc., has good heat sealability, can keep the sealing of housing, container, therefore preferably.Polypropylene, polypropylene EVA (with a small amount of ethene and/or the EVA of other polymerizable monomer), maleic acid modified polypropene, its fusing point is more than poly equal reaching, sealing intensity at high temperature is high, therefore the possibility that causes the unfavorable conditions such as run-down, expansion, fracture in the High temperature storage test (safety testing) of battery is little, thereby excellent.
Unstretching film can be directly stacked on Al-Fe line aluminium alloy paper tinsel 1, perhaps also can be stacked on PA membrane or polyester film.But, at the stacked unstretching film of inner face that is shaped with the single face of packaging material 10, owing to having heat sealability, guarantee the high chemical-resistant to the content of electrolyte etc., therefore preferred.
During the unstretching film of laminated polyethylene, polypropylene, polypropylene EVA, maleic acid modified polypropene, ethylene-acrylate EVA, ionomer resin, no matter to be Al-Fe line aluminium alloy paper tinsel 1 or stretched film all can use biliquid curing type urethanes to base material is the dry lamination binding agent.
But, as lithium secondary battery, filling and pack and contain electrolyte, because the moisture intrusion produces in the situation of the such content of hydrofluoric acid, general urethanes is the dry lamination binding agent, the swelling due to electrolyte, effect of acid of this adhesive layer, the problem that exists caking property to descend.Therefore, the preferred use for organic solvent, acid has the biliquid curing type dry lamination binding agent that sufficient close-burning sour modified polypropene is.
In the situation that resin bed 2,3 one use above-mentioned unstretching film, preferably the thickness with unstretching film is made as 9～100 μ m.If unstretching film is lower than 9 μ m, thickness after forming is thin, easily produces pin hole, and the anxiety for the corrosion resistance decline of electrolyte etc. is arranged.On the other hand, even use the unstretching film of the thickness that surpasses 100 μ m, chemical-resistant and heat sealability further do not improve yet, and volume energy density is reduced.
Moreover, for the purpose of raising with the wetability of binding resin, and/or prevent for the dissolving due to the Al-Fe line aluminium alloy paper tinsel 1 of invading the hydrofluoric acid that the electrolytical decomposition that causes produces to the moisture of electrolyte, improve corrosion proof purpose, the chemical conversion of preferably Al-Fe line aluminium alloy paper tinsel 1 being implemented chromium phosphate hydrochlorate processing etc. is processed, and/or with acrylic resin, the acrylic acid series water-soluble resin base treatment with the crosslinked painting type of slaine.
In addition, when the one side at least of Al-Fe line aluminium alloy paper tinsel 1 having been implemented in the situation of chemical conversion processing, on this chemical conversion treated side, the tack coat that can consist of across the dry lamination binding agent by modified polypropene system, the tack coat that is perhaps consisted of by modified polypropene and polyacrylic coextrusion resin bed, stacked heat adhesiveness resin bed.Thus, in the situation that deep drawing is configured as sharp-pointed shape, the pin hole in the angle part of formed products is difficult to produce, and can obtain the good packaging material of formability.
Base material is in the situation of Al-Fe line aluminium alloy paper tinsel 1, can adopt coetrusion, sandwich laminating that unstretching film is carried out lamination.In this situation, under the mode that makes Al-Fe line aluminium alloy paper tinsel 1 side bonding modified polypropene, use modified polypropene and polyacrylic coextrusion resin bed as tack coat.
Kind according to electrolyte, when using the heat lamination packaging material that these obtain by coetrusion, sandwich laminating, do not need coating, the drying process of binding agent, therefore have bonding defect few, the reduction of the cohesive force that electrolyte brings is also few, can obtain the situation of good sealing.
Then, the shaping that relates to for the utility model is lifted concrete example and is described with the manufacture method of packaging material.
When packaging material are used in the shaping that manufacturing the utility model relates to, implement successively the manufacturing process of Al-Fe line aluminium alloy paper tinsel and the bonding operation of resin bed.
(manufacturing process of Al-Fe line aluminium alloy paper tinsel)
In the present embodiment, by melt, casting, base (slab), building up by welding, (homogenize homogenizes; Processing homogenizes), hot rolling, cold rolling, intermediate annealing, cold rolling, paper tinsel is rolling, each operation of final annealing, produces Al-Fe line aluminium alloy paper tinsel 1.
In melting process and casting process, for example, melted alloy consists of Fe content: 0.7～1.3 % by weight, Si content: 0.05～0.3 % by weight, Cu content: 0.05 % by weight is following, Zn content: below 0.10 % by weight, the material that its surplus is made of Al and other inevitable impurity (for example, JIS standard A 8079H-O), make ingot casting.
Then, in preforming, ingot casting is processed into the slab shape.The thickness of the material when being processed into the slab shape for example is made as 500～600mm.
Then, in the building up by welding operation, 4～6 faces that are processed into the alloy material of slab shape are cut equably, remove impurity.In this operation, carry out the cutting of alloy material with for example 6～12mm/ single face.
Then, in the operation that homogenizes, carry out the processing that homogenizes of the alloy material after the building up by welding operation.The treatment temperature that homogenizes preferably is made as 400～600 ℃.In addition, processing time that homogenizes preferably is made as 2～10 hours.
Then, in hot-rolled process, the rolling alloy material that homogenizes after processing at high temperature.The hot-rolled temperature of the alloy material in this operation preferably is made as 280～300 ℃.In addition, the thickness of the alloy material after hot rolling is made as the 5mm left and right.
Then, in cold rolling process, the alloy material of hot rolling is carried out cold rolling, stretch than unfertile land.
The thickness of the cold rolling temperature of the alloy material in this operation, rolling rate, the alloy material after rolling preferably is made as respectively 110～240 ℃, 40～90%(4 passage), 0.6mm.
Then, in the intermediate annealing operation, remove the strain of the alloy material inside after cold rolling by heat treatment, make organization softening, improve ductility.Treatment temperature in this operation is preferably 380～400 ℃, is particularly preferably 390 ℃.In addition, the processing time preferably is made as 1.5～2.5 hours.
The average crystal grain particle diameter of Al-Fe line aluminium alloy paper tinsel is greatly affected according to the rolling rate in the paper tinsel rolling process and intermediate annealing condition.
For the average crystal grain particle diameter with crystal grain contained in Al-Fe line aluminium alloy paper tinsel is made as 5 μ m～20 μ m, and be not formed on the crystal grain that has the maximum length of 0.8 times thick over paper tinsel in the paper tinsel rolling direction cross section of Al-Fe line aluminium alloy paper tinsel, and form a plurality of have paper tinsel thick more than 0.6 times and lower than the crystal grain of the maximum length of 0.8 times, preferably: the treatment temperature during with intermediate annealing is set as 380～400 ℃, processing time and is set as 1.5～2.5 hours, and the rolling rate that the paper tinsel of Al-Fe line aluminium alloy paper tinsel is rolling is made as 30～50% scope.
Then, in cold rolling process, the alloy material after the annealing of centre is rolled.In addition, the rolling rate in this operation and cold rolling after the thickness of alloy material preferably be made as 0.3mm, 50%(1 passage).
Then, in the paper tinsel rolling process, that alloy material is further rolling with a plurality of passages, stretch than unfertile land.The thickness of the alloy material after the rolling rate in this operation and paper tinsel are rolling preferably is made as 40 μ m, (3～4 passage) below 50%.By processing under this condition, can prevent from being formed in the paper tinsel rolling direction cross section of Al-Fe line aluminium alloy paper tinsel and have 0.6 times little or the crystal grain of maximum length 0.8 times or more that paper tinsel thick thicker than paper tinsel.
Then, in the final annealing operation, the alloy material that rolls out than unfertile land is implemented annealing in process.Treatment temperature in this operation and processing time preferably are made as respectively 240～300 ℃, 24～96 hours.
By processing under above condition, can make a kind of Al-Fe line aluminium alloy paper tinsel 1, its average crystal grain particle diameter is 5 μ m～20 μ m, and exist a plurality of have on the thick direction of paper tinsel in paper tinsel rolling direction cross section paper tinsel thick more than 0.6 times and lower than the crystal grain of the maximum length of 0.8 times, these are more than a plurality of crystal grain mutual distance 1mm.
(the bonding operation of resin bed)
At first, prepare to contain the resin bed 2,3 of heat-resistant resin film.In the situation that resin bed 2 contains the heat-resistant resin film more than 2, preferred heat-resistant resin film more than 2 is stacked across tack coat each other.
Then, be situated between resin bed 2 and the Al-Fe line aluminium alloy paper tinsel 1 that obtains so stacked by binding agent.More particularly, for example, on the surface of resin bed 2 or the surface-coated dry lamination binding agent of Al-Fe line aluminium alloy paper tinsel 1, after making dry lamination with solvent evaporates contained in binding agent, that resin bed 2 and Al-Fe line aluminium alloy paper tinsel 1 is stacked.
, adopt the method for dry lamination etc., resin bed 3 and Al-Fe line aluminium alloy paper tinsel 1 fitted thereafter, make contain resin bed 2,3 and the shaping of Al-Fe line aluminium alloy paper tinsel 1 with packaging material 10.
(embodiment 1)
Manufacture method based on the Al-Fe line aluminium alloy paper tinsel 1 that illustrates in above-mentioned embodiment produces Al-Fe line aluminium alloy paper tinsel as follows.
In the present embodiment, at first be Si content with alloy composition: 0.05 % by weight, Fe content: 1.10 % by weight, Cu content: 0.01 % by weight, Mg content: 0.01 % by weight, Zn content: 6 faces of the ingot casting (thickness is 500mm) of the Al-Fe line aluminium alloy of 0.01 % by weight (JIS standard A 8079H-O) carry out the building up by welding of 6～12mm left and right, carry out the processing that homogenizes of 5 hours under 500 ℃.Then, carry out hot rolling until thickness of slab is 5mm at the rolling paper tinsel temperature of 280～300 ℃.
Cold rolling rolling rate is 40～90%, is that the scope of 110～240 ℃ is implemented repeatedly in rolling paper tinsel temperature, forms the thickness of slab of 0.6mm during cold rolling the end.In the moment of the thickness of slab of this 0.6mm, the intermediate annealing operation that enters 2 hours under 390 ℃ is 50% in rolling rate after intermediate annealing, and it is cold rolling that rolling paper tinsel temperature is that the scope of 100～230 ℃ is carried out, and forms the thickness of slab of 0.3mm.
Then, adopt the overlapping 2 pieces of coincidence rollings that are rolled of milled sheet, under rolling rate is condition below 50%, carry out 3 paper tinsels rolling, the paper tinsel that forms 40 μ m is thick, carries out the final annealing of 40 hours at last under 270 ℃, produces the soft paper tinsel of Al-Fe line aluminium alloy.
With the composition of the Al-Fe line aluminium alloy in the present embodiment with create conditions and be shown in table 1.
Use the above-mentioned Al-Fe line aluminium alloy paper tinsel that produces, heat-resistant resin layer (stretched film), heat adhesiveness resin bed (unstretching film), chemical conversion processing layer and the tack coat shown in following, making is shaped uses packaging material.
The shaping of the present embodiment is as shown in table 2 with the formation of packaging material, forms the laminated body by the order formation of ON25/AD1/AC/AL40/AC/AD2/CPP40.
Moreover the AL40 in table 2 and AL30 represent the Al-Fe line aluminium alloy paper tinsel in each embodiment and comparative example.
(embodiment 2)
Be made as the composition of the Al-Fe line aluminium alloy shown in table 1 and create conditions, and adopting the formation of the packaging material shown in table 2, obtaining similarly to Example 1 in addition the shaping packaging material of embodiment 2.
(embodiment 3)
Be made as the composition of the Al-Fe line aluminium alloy shown in table 1, and middle temperature in the intermediate annealing operation is made as 380 ℃ creating conditions, and adopt the formation of the packaging material shown in table 2, obtain similarly to Example 1 in addition the shaping packaging material of embodiment 3.
(embodiment 4)
Be made as the composition of the Al-Fe line aluminium alloy shown in table 1, and middlely rolling rate is made as to carry out 4 coincidences below 50% rolling creating conditions, the paper tinsel that is made as 30 μ m is thick, and adopt the formation of the packaging material shown in table 2, obtain similarly to Example 1 in addition the shaping packaging material of embodiment 4.
(comparative example 1)
Be made as the composition of the Al-Fe line aluminium alloy shown in table 1, and middle temperature in the intermediate annealing operation is made as 405 ℃ creating conditions, make rolling rate greater than 50% and to carry out 3 coincidences below 60% rolling, the paper tinsel that is made as 40 μ m is thick, and adopt the formation of the packaging material shown in table 2, obtain similarly to Example 1 in addition the shaping packaging material of comparative example 1.
(comparative example 2)
Be made as the composition of the Al-Fe line aluminium alloy shown in table 1 and create conditions, and adopting the formation of the packaging material shown in table 2, similarly obtaining in addition the shaping packaging material of comparative example 2 with comparative example 1.
(comparative example 3)
Be made as the composition of the Al-Fe line aluminium alloy shown in table 1, and middle temperature in the intermediate annealing operation is made as 410 ℃ creating conditions, and adopt the formation of the packaging material shown in table 2, similarly obtain in addition the shaping packaging material of comparative example 3 with comparative example 1.
(comparative example 4)
Be made as the composition of the Al-Fe line aluminium alloy shown in table 1, and make rolling rate greater than 50% and to carry out 4 coincidences below 60% rolling in creating conditions, the paper tinsel that is made as 30 μ m is thick, and adopt the shaping packaging material of the formation shown in table 2, similarly obtain in addition the shaping packaging material of comparative example 4 with comparative example 3.
In embodiment 1～embodiment 4 and comparative example 1～comparative example 4, for the shaping packaging material that adopt respectively above-mentioned condition to produce, observational technique, the formability evaluation method of the assay method of the average crystal grain particle diameter that employing then illustrates, the crystal grain (coarse grain) of cross-wise direction are estimated.
(assay method of average crystal grain particle diameter)
At first, outside as shown in Figure 2 Al-Fe aluminum series alloy paper tinsel volume 24, produce the sample of overall width * 500mm width, then from the both ends (W, D) of width, the section sample 26 that central portion (C) is cut to the size of easy grinding.
The section sample 26 that has cut off is imbedded in resin, uses rotary grinder polishing to grind.
Adopt known anodizing to carry out macroscopical etching through the Al-Fe line aluminium alloy foil sample that grinds.
By the such anodic oxidation of polarized light microscope observing sample, measure size of microcrystal.With 200 times of observations, set the mensuration zone of 100 μ m φ, calculate the wherein number of contained crystal grain.Moreover measuring in the zone has the situation of a whole crystal grain to count 1 fully, touches the situation at the edge of measuring the zone and counts 1/2.
N crystal grain, in the area of 100 μ m φ, average crystal grain particle diameter r tries to achieve by following formula.
[formula 1]
π(50)
2/n=πr
2
[formula 2]
r=[(50)
2/n]
1/2
(assay method of sowing discord distance between the maximum length of coarse grain and coarse grain)
By the operation same with the assay method of average crystal grain particle diameter, prepare anodic oxidation section sample 26.
Then, by the polarized light microscope observing sample 26 of cutting into slices, have or not the coarse grain of the cross-wise direction in cross-section shown in Figure 1 cross section to implement by 100～500 times of observations from A direction shown in Figure 3.Regard as coarse grain with measuring the situation that contains a whole coarse grain in the zone fully.In addition, in the situation that observe an even number n coarse grain more than 2, will have the coarse grain of the long distance of n/2 each other as coarse grain 1 and coarse grain 2, with the distance between them as the distance between final coarse grain.In the situation that observe an odd number m coarse grain more than 3, will have the coarse grain of the long distance in (m+1)/2 each other as coarse grain 1 and coarse grain 2, with the distance between them as the distance between final coarse grain.Moreover the distance between coarse grain is that the distance of measuring between the center (C) of coarse grain is tried to achieve.In addition, the center of coarse grain (C) is set as the central point of line of the maximum length of diameter.
(formability evaluation method)
To be shaped and be sampled as blank (blank) shape of 80mm * 120mm with packaging material, utilize forming height freely straight mould carry out the deep drawing one-phase and be shaped, use the pin hole detector of Nonopaque type to confirm the having or not of pin hole of the formed products that forming height has changed.
Formed products is made 10, does not all have the forming height of the situation of pin hole generation to estimate formability with 10.
In addition, formability is that forming height is changed by 0.5mm, with the situation that obtains the forming height more than 5mm as the good product of formability, will be lower than the situation of 5mm as the cob webbing product.
In this formability evaluation method, use the mould with following shape.
Punch shape (external dimensions): long limit 54mm, minor face 33mm
Drift shoulder R2mm, angle R2mm
Mould shape (inside dimension): long limit 55mm, minor face 34mm,
Mould shoulder R1mm
(R: bending radius)
With the Al-Fe line aluminium alloy paper tinsel that produces in embodiment 1～embodiment 4 and comparative example 1～comparative example 4 be shaped with the table 2 that the results are shown in of the observation of the particle diameter (coarse grain) of the mensuration of the average crystal grain particle diameter of the above-mentioned explanation in packaging material, cross-wise direction, formability evaluation.
As shown in table 2, in embodiment 1～embodiment 4, the average crystal grain particle diameter of Al-Fe line aluminium alloy paper tinsel is 5 μ m～20 μ m, and the maximum length of coarse grain be the paper tinsel of Al-Fe line aluminium alloy paper tinsel thick more than 0.6 times and lower than 0.8 times, sow discord distance for more than 1mm between coarse grain.This is that the treatment temperature when making intermediate annealing is 380～400 ℃, and the processing time is 1.5～2.5 hours, and the rolling rolling rate of paper tinsel is that 30～50% scope is caused.
On the other hand, in comparative example 1 and 2, although the average crystal grain particle diameter is 5 μ m～20 μ m, coarse grain 1 and 2 maximum length be paper tinsel thick more than 0.6 times and lower than 0.8 times, sow discord distance lower than 1mm between coarse grain.In addition, in comparative example 3, although the average crystal grain particle diameter is 5 μ m～20 μ m, the maximum length of coarse grain 1 be paper tinsel thick more than 0.6 times and lower than 0.8 times, but to be paper tinsel thick for the maximum length of coarse grain 2 more than 0.8 times, and, sow discord distance lower than 1mm between coarse grain.In addition, in comparative example 4, although the average crystal grain particle diameter is 5 μ m～20 μ m, coarse grain 1 and 2 maximum length be paper tinsel thick more than 0.8 times, sow discord distance lower than 1mm between coarse grain.Like this, comparative example 1～4 breaks away from from scope of the present utility model, is that the treatment temperature during due to intermediate annealing surpasses the scope of 380～400 ℃, and the rolling rolling rate of paper tinsel surpasses 30～50% scope.
In addition, in embodiment 1～embodiment 4, forming height is 6.5～9.0mm, and on the other hand, forming height is 4.0 in comparative example 1 and 2, and to compare formability low with embodiment.Comparative example 1 and 2 formability are low is owing to sowing discord distance lower than 1mm between coarse grain.In addition, the forming height of comparative example 3 is 3.0, and to compare formability low with embodiment.This be the maximum length due to coarse grain 2 be paper tinsel thick more than 0.8 times, sow discord distance lower than 1mm between coarse grain.In addition, the forming height of comparative example 4 is 3.5, and to compare formability low with embodiment.This be due to coarse grain 1 and 2 be all maximum length be paper tinsel thick more than 0.8 times, between coarse grain sow discord the distance lower than 1mm.
Claims (10)
1. shaping packaging material, is characterized in that, possessing resin bed, used thickness in table is the shaping packaging material of the Al-Fe line aluminium alloy paper tinsel of 30 μ m～120 μ m,
In described Al-Fe line aluminium alloy paper tinsel, the average crystal grain particle diameter of contained crystal grain is 5 μ m～20 μ m, and exist a plurality of paper tinsels that have described Al-Fe line aluminium alloy paper tinsel in the paper tinsel rolling direction cross section of described Al-Fe line aluminium alloy paper tinsel on the thickness direction of described Al-Fe line aluminium alloy paper tinsel thick more than 0.6 times and lower than the crystal grain of the maximum length of 0.8 times, these are more than a plurality of crystal grain mutual distance 1mm.
2. shaping packaging material according to claim 1, is characterized in that, at least one of the resin bed in described table is heat stable resin, used the stretched film that is made of polyamide or polyester film as described heat stable resin.
3. shaping packaging material according to claim 1 and 2, it is characterized in that, at least one of resin bed in described table is stretched film, and described stretched film is dry lamination binding agent and described Al-Fe line aluminium alloy paper tinsel bonding by biliquid curing type urethanes.
4. shaping packaging material according to claim 1 and 2, it is characterized in that, be at least one surface to described Al-Fe line aluminium alloy paper tinsel, implemented that chemical conversion that the chromium phosphate hydrochlorate processes is processed or with acrylic resin or the acrylic acid series water-soluble resin material with the crosslinked base treatment of slaine.
5. shaping packaging material according to claim 1, it is characterized in that, the one of the resin bed in described table is heat stable resin, another one is adhesion resin, perhaps both are heat stable resin, and, the one side at least of described Al-Fe line aluminium alloy paper tinsel has been implemented the chemical conversion processing, have tack coat between the described Al-Fe line aluminium alloy paper tinsel of processing through chemical conversion and described resin bed.
6. shaping packaging material according to claim 5, it is characterized in that, described tack coat is the dry lamination adhesive layer of modified polypropene system or modified polypropene and the polyacrylic coextrusion resin bed that makes the mode of described chemical conversion treated side side bonding modified polypropene.
7. a lithium secondary battery, is characterized in that, possesses the battery exterior body that the described shaping of claim 1 or 2 is shaped and forms with packaging material.
8. a lithium secondary battery, is characterized in that, possesses the battery exterior body that shaping claimed in claim 3 is shaped and forms with packaging material.
9. a lithium secondary battery, is characterized in that, possesses the battery exterior body that shaping claimed in claim 4 is shaped and forms with packaging material.
10. a lithium secondary battery, is characterized in that, possesses the battery exterior body that the described shaping of claim 5 or 6 is shaped and forms with packaging material.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP014057/2012 | 2012-01-26 | ||
| JP2012014057 | 2012-01-26 |
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| CN203267345U true CN203267345U (en) | 2013-11-06 |
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| CN103223753B (en) * | 2012-01-26 | 2016-05-11 | 昭和电工包装株式会社 | Be shaped with packaging material and lithium secondary battery |
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| KR102281543B1 (en) * | 2013-12-02 | 2021-07-26 | 다이니폰 인사츠 가부시키가이샤 | Battery-packaging material |
| US9899639B2 (en) * | 2013-12-11 | 2018-02-20 | Dai Nippon Printing Co., Ltd. | Packaging material for cell |
| JP6331482B2 (en) * | 2014-03-03 | 2018-05-30 | 大日本印刷株式会社 | Battery packaging materials |
| JP6366964B2 (en) * | 2014-03-13 | 2018-08-01 | 昭和電工パッケージング株式会社 | Exterior material for electrochemical device and electrochemical device |
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| KR101861888B1 (en) * | 2014-05-13 | 2018-05-28 | 주식회사 엘지화학 | Case for Secondary Battery with High Formability and Method of Manufacturing the Same |
| CN106663751B (en) * | 2014-07-17 | 2020-02-07 | 大日本印刷株式会社 | Packaging material for battery |
| CN106716672B (en) * | 2014-09-26 | 2019-11-26 | 大日本印刷株式会社 | Battery use packing material |
| JP6859662B2 (en) * | 2015-10-28 | 2021-04-14 | 大日本印刷株式会社 | Battery packaging materials, batteries, battery packaging material manufacturing methods, and aluminum alloy foil |
| JP2017084787A (en) * | 2015-10-28 | 2017-05-18 | 大日本印刷株式会社 | Battery-packaging material, battery, method for manufacturing battery-packaging material, and aluminum alloy foil |
| WO2017073774A1 (en) * | 2015-10-28 | 2017-05-04 | 大日本印刷株式会社 | Battery packaging material, battery, battery packaging material manufacturing method, and aluminum alloy foil |
| JP6922185B2 (en) * | 2016-02-09 | 2021-08-18 | 大日本印刷株式会社 | Battery packaging materials, batteries, battery packaging material manufacturing methods, and aluminum alloy foil |
| CN114156573A (en) * | 2016-04-12 | 2022-03-08 | 大日本印刷株式会社 | Battery packaging material, method for producing same, and battery |
| JP6973414B2 (en) * | 2016-12-28 | 2021-11-24 | 大日本印刷株式会社 | Aluminum alloy foil for battery packaging materials, battery packaging materials, and batteries |
| KR102515102B1 (en) | 2017-10-24 | 2023-03-27 | 삼성에스디아이 주식회사 | Case for rechargeable battery and rechargeable battery comprising the same |
| JP6673394B2 (en) * | 2018-04-27 | 2020-03-25 | 大日本印刷株式会社 | Battery packaging material |
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| JP2023538295A (en) | 2020-08-19 | 2023-09-07 | エルジー エナジー ソリューション リミテッド | Pouch type battery case and pouch type secondary battery |
| US20230352773A1 (en) | 2020-08-19 | 2023-11-02 | Lg Energy Solution, Ltd. | Pouch-Type Secondary Battery |
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| US20230318093A1 (en) | 2020-08-19 | 2023-10-05 | Lg Energy Solution, Ltd. | Pouch-Type Secondary Battery and Method for Manufacturing the Same |
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| US20240014472A1 (en) | 2020-08-19 | 2024-01-11 | Lg Energy Solution, Ltd. | Pouch Type Battery Case and Pouch Type Secondary Battery |
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| JP2754263B2 (en) * | 1989-10-03 | 1998-05-20 | 株式会社神戸製鋼所 | Aluminum foil and its manufacturing method |
| JP3596666B2 (en) * | 1999-12-14 | 2004-12-02 | 日本製箔株式会社 | Manufacturing method of secondary battery-like exterior material |
| JP4627138B2 (en) * | 2003-08-06 | 2011-02-09 | 住友軽金属工業株式会社 | Aluminum laminate material for battery packaging |
| JP4360139B2 (en) * | 2003-08-11 | 2009-11-11 | 東亞合成株式会社 | Battery case packaging material and battery case molded using the same |
| US7462425B2 (en) * | 2003-09-26 | 2008-12-09 | Kabushiki Kaisha Toshiba | Nonaqueous electrolyte secondary battery and battery module |
| JP5525938B2 (en) * | 2010-07-02 | 2014-06-18 | 昭和電工パッケージング株式会社 | Molding packaging material and manufacturing method thereof |
| JP5841537B2 (en) * | 2010-09-16 | 2016-01-13 | 株式会社Uacj | Molded packaging material |
| CN203267345U (en) * | 2012-01-26 | 2013-11-06 | 昭和电工包装株式会社 | Packaging material for forming and lithium secondary battery |
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| CN103223753B (en) * | 2012-01-26 | 2016-05-11 | 昭和电工包装株式会社 | Be shaped with packaging material and lithium secondary battery |
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| Publication number | Publication date |
|---|---|
| JP6022956B2 (en) | 2016-11-09 |
| JP2017071220A (en) | 2017-04-13 |
| JP2013174010A (en) | 2013-09-05 |
| CN103223753A (en) | 2013-07-31 |
| JP6361075B2 (en) | 2018-07-25 |
| CN103223753B (en) | 2016-05-11 |
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