CN103311491A - Electrode lead wire member for nonaqueous battery - Google Patents
Electrode lead wire member for nonaqueous battery Download PDFInfo
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- CN103311491A CN103311491A CN2013100703464A CN201310070346A CN103311491A CN 103311491 A CN103311491 A CN 103311491A CN 2013100703464 A CN2013100703464 A CN 2013100703464A CN 201310070346 A CN201310070346 A CN 201310070346A CN 103311491 A CN103311491 A CN 103311491A
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- Prior art keywords
- electrode cable
- protective layer
- cable parts
- metal
- battery
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/531—Electrode connections inside a battery casing
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/74—Terminals, e.g. extensions of current collectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
- H01M50/124—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/543—Terminals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/571—Methods or arrangements for affording protection against corrosion; Selection of materials therefor
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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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- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to an electrode lead wire member for a nonaqueous battery, wherein even the electrolyte of the lithium ion battery reacts with water to produce hydrofluoric acid which enhances corrosivity, the bad influence of the high corrosivity can also be prevented, the service life of the lithium ion battery can be prolonged, and the corrosion resistance is improved. The electrode lead wire 18 member is guided from a container for the nonaqueous battery which is formed by laminated body constituted by laminated membranes of aluminum foils and resin membranes. Solution containing polyving akohol resin or polyvinyl ether resin and compound containing fluorin is pasted on the outer surface of a stripe metal board and is dried to form a protective layer 22. The compound containing fluorin is water-soluble. The protective layer 22 forms a stripe pattern on the stripe metal board 21 through printing.
Description
Technical field
The electrode cable parts that the present invention relates to use in the electrolyte for the lithium ion battery of secondary cell or double electric layer capacitor (below be called capacitor) etc. the non-aqueous batteries of organic bath to use.
Background technology
In recent years, along with the increase of World Environment Problems, effective utilization of the natural energy resources such as the popularizing of electric motor car, wind power generation solar power generation becomes problem.Accompany with it, in these technical fields, as the storage battery for store electrical energy, secondary cell or the capacitor of lithium ion battery etc. get most of the attention.And, in the outer packaging container of taking in the lithium ion battery that electric motor car etc. uses, the exterior flat bag made from layered product of battery that use obtains aluminium foil and resin molding lamination, or use through being shaped by punch forming (Twisted り) or the container molding of expansion molding formation, seek slim lightweight.
But the electrolyte of lithium ion battery had not water-fast minute or the character of light.Therefore, for the exterior material that lithium ion battery is used, the substrate layer and water proofing property aluminium foil laminate, that have excellence and the exterior layered product of using of battery of light-proofness that use polyamide or polyester to consist of.
In using so exterior accommodating container made from layered product of battery, in taking in lithium ion battery, for example use container 30 as shown in Figure 3A.At first use the exterior layered product of using of battery, by punch forming etc. the hypocrateriform container 30 with recess 31 is shaped, the accessories such as lithium ion battery (without diagram) and electrode are accommodated in the recess 31 of this pallet (container 30).Then, shown in Fig. 3 B, will be covered and the parcel battery from the top by the exterior lid 33 that consists of with layered product of battery, with side edge part 34 heat-sealings of the four direction of the flange part 32 of pallet and lid 33 and with cell sealing.The accommodating container 35 that the method for utilization by such recess 31 that battery is loaded into pallet forms is because can take in battery from the top, so high productivity.
In the container 30 of the lithium ion battery shown in above-mentioned Fig. 3 A, in small-scale lithium ion cell, be about 5～6mm before the degree of depth of pallet (below the situation that the degree of depth of pallet is called " punching press degree " is arranged).But, in recent years, in the purposes of electric vehicle etc., require than in the past larger large-sized battery accommodating container.Making large-sized battery with in the accommodating container, must form the pallet of darker punching press degree, increased technical difficulty.
And, invade in the situation of moisture in the inside of lithium ion battery, electrolyte and reaction of moisture, electrolyte decomposition produces strong acid (hydrofluoric acid etc.).In this case, have the strong acid of generation from the exterior inboard infiltration with layered product of battery, aluminium foil is corroded by strong acid and deteriorated possibility.As a result, the leakage of electrolyte occurs, not only battery performance descends, the possibility that also has lithium ion battery to catch fire.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese Patent Laid-Open 2000-357494 communique
Summary of the invention
[problem that invention will solve]
Consist of above-mentioned battery exterior with the aluminium foil of layered product and the superficial layer of electrode cable parts, as the countermeasure that prevents the strong acid corrosion, disclose in the Japanese Patent Laid-Open 2000-357494 communique by the surface of aluminium foil being implemented the chromate processing and formed chromaking processing coverlay, promoted the countermeasure of corrosion resistance.But, because chromate is processed the chromium that uses as heavy metal, therefore not preferred from the viewpoint of environmental protection.So because the chromium of sexavalence is can not use the harmful substance that human body impacts, therefore use the chromate treatment fluid of 3 valency chromium.And, to process chemical conversion type coating in addition by chromate and process, the effect that corrosion resistance is improved is little.
In addition, existing electrode cable parts are in positive pole and two electrodes of negative pole, electrolyte resistance as the aluminium of the electrod assembly of positive pole is good, as the copper coin of the electrod assembly of negative pole, even give nickel coating on the top layer and implement chromic chromate and process, electrolyte resistance is also very inferior.
The present invention uses for reference above-mentioned situation and carries out.Even the purpose of this invention is to provide the electrolyte of lithium ion battery and reaction of moisture and produce hydrofluoric acid, corrosivity increases, also can avoid its bad impact, prolong the life-span of lithium ion battery, the electrode cable parts that the non-aqueous batteries that corrosion resistance is improved is used.
[solving the method for problem]
The present invention with following content as technological thought: in electrolyte, use the non-aqueous batteries of organic bath with in the accommodating container; on the outer surface of the metal-made flat board bonding part, that make strip of the laminated film layered product of exterior material and electrode cable parts; by printing protective layer is formed banded pattern, the corrosion resistance for corrosivity electrolyte is improved.Solution coat and dry form of this protective layer for containing polyvinyl alcohol resin or polyvinylether resinoid and fluorochemical.
In order to solve above-mentioned problem; the invention provides a kind of electrode cable parts; the electrode cable parts that it is drawn with accommodating container for the non-aqueous batteries that forms for exterior material from the laminated film layered product with aluminium foil and resin molding; on the outer surface of the metal-made flat board of making strip, will contain the solution coat of polyvinyl alcohol resin or polyvinylether resinoid and fluorochemical and dry and form protective layer.
And above-mentioned fluorochemical is preferably water-soluble.
And, preferably above-mentioned protective layer is formed banded pattern by printing on the outer surface of above-mentioned metal-made flat board.
And, preferably above-mentioned protective layer is carried out crosslinked or noncrystallineization by heat treatment, have a water resisting property.
And, the invention provides a kind of non-aqueous batteries accommodating container, it uses above-mentioned electrode cable parts.
And, preferably with above-mentioned electrode cable parts, from being rolled along the both ends of observing with the cross section at the junction surface of above-mentioned exterior material, make it compare cross section central portion thin thickness.
[invention effect]
The protective layer of electrode cable parts is carried out crosslinked or noncrystallineization by heat treatment, thereby make it to have a water resisting property; Described protective layer obtains its dry protective layer that forms contain the solution of polyvinyl alcohol resin or polyvinylether resinoid and fluorochemical by coating after.The result is can suppress electrolyte and invade inner from the both ends of observing in the cross section of electrode cable parts to leakage or the moisture the atmosphere of outside.
When the both ends of observing in the cross section of electrode cable parts are rolled, when making it compare cross section central portion thin thickness, electrode cable parts and combining closely of laminated film layered product improve, and space part tails off, and electrolyte is invaded inner the minimizing to leakage or the moisture in the atmosphere of outside.
Description of drawings
Fig. 1 is for showing the battery stereogram of an example of accommodating container.
Fig. 2 is for showing that battery is with the summary sectional view of the battery that uses in the accommodating container with an example of exterior layered product.
Fig. 3 A is for showing in order the stereogram that lithium ion battery is accommodated in the 1st operation in the accommodating container.
Fig. 3 B is for showing in order the stereogram that lithium ion battery is accommodated in the 2nd operation in the accommodating container.
Fig. 4 A is the stereogram of an example of demonstration electrode cable parts of the present invention.
Fig. 4 B is the sectional view along the S-S line of Fig. 4 A.
Fig. 5 is the vertical view of an example of demonstration electrode cable parts of the present invention.
Fig. 6 is the test result with differential thermal analysis device to test protective layer.
Symbol description
The exterior layered product of using of 10 batteries
11 substrate layers
12 aluminium foils
13 resin moldings
15,16 adhesive phases
17 lithium ion batteries
18 electrode cable parts
19 side edge parts
The outer packaging container of 20 batteries
21 metal-mades are dull and stereotyped
22 protective layers
23 sealant layers
30 battery carrying containers
35 battery accommodating containers
Embodiment
Referring to figs. 1 through Fig. 6 electrode cable parts of the present invention are described.
In addition, illustrate from using the exterior lithium ion battery with the layered product manufacturing of battery with the electrode cable parts of drawing the accommodating container.
As shown in Figure 1, electrode cable parts 18 of the present invention and lithium ion battery 17 be included in battery exterior with layered product 10(with reference to Fig. 2) the folding and battery made is with in the outer packaging container 20.
Battery is heat-sealed with the side edge part 19 of three directions of outer packaging container 20 and makes bag-shaped.Electrode cable parts 18 are drawn with outer packaging container 20 from battery.In addition, the lithium ion battery that uses electrode cable parts 18 of the present invention to make being accommodated in battery is shown among Fig. 3 A and Fig. 3 B with the method in the accommodating container.
As shown in Figure 2, exterior substrate layer 11, aluminium foil 12, the resin molding 13 with layered product 10 of the battery that is made of the laminated film layered product is bonding successively via adhesive phase 15,16 respectively.
Shown in Fig. 4 A and Fig. 4 B; electrode cable parts 18 are; on the strip metal flat board 21 processed with aluminum or the copper coin system that coats by nickel plating; lamination matcoveredn 22; described protective layer 22 makes after by the solution coat that will contain polyvinyl alcohol resin or polyvinylether resinoid (below, the situation of abbreviation " polyvinyl alcohol resin " is arranged) and fluorochemical it dry and form.Surperficial upper strata at this protective layer 22 is pressed with sealant layer 23.
The fluorochemical that formed by the metal fluoride or derivatives thereof and polyvinyl alcohol resin are crosslinked to be formed protective layer 22 in order to make, and its water-resistance is increased, and make the surface active of metal-made flat board 21, and corrosion resistance increased.But even do not contain the metal fluoride or derivatives thereof, the corrosion resistance of protective layer 22 also can increase.
And, containing just like the such free aobvious acid material under aqueous solution state of metal fluoride by making protective layer 22, the activated metal surface not only increases corrosion resistance, and makes outer surface and protective layer 22 strong bindings of metal-made flat board 21.
In addition, the known general gas barrier property of polyvinyl alcohol resin with polyvinyl alcohol skeleton is good.Because the protective layer 22 usefulness polyvinyl alcohol resins of electrode cable parts of the present invention form; therefore the resin internal voids that consists of protective layer 22 is few; special under the low atmosphere of humidity, the gas molecule little for molecular dimension as hydrogen also has gas barrier property.Therefore, can think in the battery of the such use nonaqueous electrolyte of lithium battery, capacitor, in not having the inside battery member of formation of moisture, use in the situation of protective layer 22 of the present invention, for the resistive height of electrolyte or moisture.Therefore, owing to making material resistive also high of corrosion for hydrofluoric acid etc., therefore anticipation has etch-proof effect.Like this, by making the protective layer 22 that is consisted of by polyvinyl alcohol resin crosslinked, can seek the increase of corrosion resistance.
The metal-made flat board 21 of electrode cable parts 18 is the anodal aluminium sheet that uses usually, and negative pole uses the metal that coats copper coin by nickel plating.In order to make the battery that is consisted of by the aluminium lamination press mold exterior easy with the thermal bonding of electrode cable parts 18 with layered product 10, form in advance sealant layer 23 in the bonding part of electrode cable parts 18.Sealant layer 23 preferably according to from the positive back side (table is wrapped up in) sandwich metal-made flat board 21 like that at the two sides lamination.
If, do not form on the top layer of metal-made flat board 21 in the situation of protective layer 22 of corrosion resistance, because electrolyte has on the top layer of metal-made flat board 21 to the infiltration of electrode cable parts 18, the possibility of moisture and electrolyte reaction generation hydrofluoric acid.By the hydrofluoric acid corroding metal flat board 21 processed that produces, has the bonding deteriorated possibility that makes metal-made dull and stereotyped 21 and sealant layer 23.Therefore, preferred formation at the top layer face of battery one side of metal-made flat board 21 at least will contain the protective layer 22 that after the solution coat of polyvinyl alcohol resin and fluorochemical its drying is obtained.Shown in Fig. 4 B, with the bonding part of exterior material (battery exterior with layered product 10) in, need to be at the whole peripheral part lamination protective layer 22 in dull and stereotyped 21 cross sections of whole metal-made.
In the prior art, as the antiseptic countermeasure of the electrolyte of being correlated with for the aluminum metal-made that uses in the electrode cable parts dull and stereotyped 21, be widely used chromate and process.But, compare with aluminum metal-made flat board 21, the metal-made flat board 21 that obtains for implementing nickel plating at copper, the effect that chromate is processed is little.Yet electrode cable parts 18 of the present invention as can be known are even the metal-made flat board 21 that obtains for implementing nickel plating at copper also has the anticorrosion ability for electrolyte.
Thus, can think that it is different processing from the chromate of prior art by the etch-proof anticorrosion mechanism for electrolyte of protective layer 22 of the present invention.
In addition, the protective layer 22 of electrode cable parts of the present invention is by making solution coat and dry formation that contains polyvinyl alcohol resin and fluorochemical.The manufacture method of polyvinyl alcohol resin does not limit especially, can use known method manufacturing.For example, with polymer or its copolymer saponification of vinyl esters monomer, can make polyvinyl alcohol resin.In the present invention, polyvinyl alcohol resin is at least a water-soluble resin that is selected from polyvinyl alcohol resin and modified polyvinylalcohol resin.Herein, polymer or its copolymer as the vinyl esters monomer, can enumerate the fatty acid vinyl ester of vinyl formate, vinylacetate, vinyl butyrate etc., homopolymers or the copolymer of the vinyl esters monomer of the aromatic ethenyl ester of vinyl benzoate etc. etc., and can with copolymer of other monomer of these copolymerization etc.As other monomer that can copolymerization, for example can enumerate, the olefines of ethene, propylene etc., the monomer that contains ether of alkyl vinyl ether etc., the monomer that contains carbonyl (ketone group) of diacetone acrylamide, two acetone (methyl) acrylate, acetoacetic acid allyl ester, acetoacetic ester etc., the unsaturated carboxylic acid class of acrylic acid, methacrylic acid, maleic anhydride etc., the ethylene halide class of vinyl chloride, vinylidene chloride etc., and the unsaturated sulfonic acid class etc.Preferred 90～100 % by mole usually of the saponification degrees of polyvinyl alcohol resin are more preferably more than 95 % by mole.
As operable polyvinyl alcohol resin and derivative thereof among the present invention; can enumerate alkyl oxide modified polyvinyl alcohol resin, carbonyl modified polyvinylalcohol resin, acetoacetyl modified polyvinylalcohol resin, acetamide modified polyvinyl alcohol resin, acrylonitrile modified polyvinylalcohol resin, carboxy-modified polyvinyl alcohol resin, silicone modified polyvinylalcohol resin, ethene modified polyvinylalcohol resin etc.Wherein preferred alkyl ether modified polyvinylalcohol resin, carbonyl modified polyvinylalcohol resin, carboxy-modified polyvinyl alcohol resin, acetoacetyl modified polyvinylalcohol resin.
Commercially available product as the general polyvinyl alcohol resin that can access, can enumerate the J-ポ バ ー Le DF-20(trade name of the G Port リ マ ー resin (trade name) of Japanese synthetic chemistry (strain) system, Japanese jealous woman PVC ポ バ ー Le (strain) system), the Network ロ ス マ ー H シ リ ー ズ (trade name) of Japanese カ ー バ イ De industry (strain) system etc.Polyvinyl alcohol resin can use one kind or two or more mixture.
And, the Network ロ ス マ ー H シ リ ー ズ (trade name) of Japan's カ ー バ イ De industry (strain) system is although also be known as polyvinylether resinoid (vinethene polymer), but, in the present invention, replace having the polyvinyl alcohol resin of hydroxyl, can use the polyvinylether resinoid that has hydroxyl or do not have hydroxyl.As the polyvinylether resinoid, can enumerate, homopolymers or the copolymer of the aliphatic ethylene base ether of ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether, IVE, 2-ethylhexyl vinyl ethers, cyclohexyl vinyl ether, norborny vinyl ethers, allyl vinyl ether, norbornene vinyl ethers, 2-ethoxy vinyl ethers, diethylene glycol mono vinyl ether etc., and can with copolymer of other monomer of its copolymerization etc.As can with other monomer of vinyl ethers monomer copolymerization, can enumerate and material that can be same with other monomer of above-mentioned vinyl esters monomer polymerization.
Polyvinylether resinoid single vinethene of 2-ethoxy vinyl ethers, diethylene glycol mono vinyl ether, 2-hydroxypropyl vinyl ethers, other various ethylene glycol or polyalcohol etc., that in monomer, contain the aliphatic ethylene base ether with hydroxyl, owing to having water-soluble, and the cross-linking reaction for hydroxyl can occur, therefore can suitably be used for the present invention.
These polyvinylether resinoids, owing to can in manufacturing (polymerization) operation of resin, utilize vinyl ether monomers, so it is from different via the polyvinyl alcohol resin of vinyl ester polymers manufacturing, processes and can make without saponification.In addition, can use the copolymer that contains vinyl ester monomer and vinyl ethers monomer, or vinyl alcohol-vinyl ether copolymers that its saponification is obtained.Can use polyvinylether resinoid polyvinyl alcohol resin and glymes resin blend thing in addition.
In addition, preferably contain in the protective layer 22 as the metal fluoride or derivatives thereof, make the crosslinked material that obtains of polyvinyl alcohol resin.Therefore the fluorochemical of metal fluoride or derivatives thereof etc. preferably has water-soluble owing to need to mix with water miscible polyvinyl alcohol resin.Object lesson as the metal fluoride or derivatives thereof, can enumerate, such as the fluoride of charomic fluoride, ferric flouride, zirconium fluoride, titanium fluoride, hafnium fluoride, hydrofluoric acid zirconium (acid of ジ Le コ Application Off ッization water element) and salt thereof, hydrofluoric acid titanium (acid of チ タ Application Off ッization water element) and salt thereof etc.These metal fluoride or derivatives thereofs not only are to make the crosslinked material of polyvinyl alcohol resin, and for containing the F of the fluoride that forms passive state aluminium
-The material of ion.Its result can think that the surface of metal-made flat board 21 is passivated in the situation that metal-made dull and stereotyped 21 is aluminum, and corrosion resistance increases.
On the face of the top layer of described metal-made flat board 21; in order to form protective layer 22; for example; use is with polyvinyl alcohol resin (Japanese synthetic chemistry (strain) system of 0.2～6wt%; trade name: G Port リ マ ー resin; Japan's jealous woman PVC ポ バ ー Le (strain) system; trade name: J-ポ バ ー Le DF-20; Japan's カ ー バ イ De industry (strain) system; Network ロ ス マ ー H シ リ ー ズ etc.) and the aqueous solution that obtains of the charomic fluoride (III) of 0.1～3wt% dissolving trade name:; so that dried thickness is the mode of approximately 0.1～5 μ m be coated with after; by further in baking oven, carrying out heat drying and baking is adhered to bonding and Cross-linked, can form protective layer 22 thus.
An example that shows the result who obtains with differential thermal analysis device mensuration protective layer among Fig. 6; described protective layer is for using polyvinyl alcohol resin (Japanese synthetic chemistry (strain) system with 3wt%; G Port リ マ ー resin) and the aqueous solution that obtains of 1wt% charomic fluoride (III) dissolving trade name:; be coated with in the mode of dried thickness as 0.6 μ m, further in 200 ℃ baking oven, carry out heat drying and process and form.Since there is not the peak of fusing point when confirming fusing point, therefore crosslinked as can be known.
Like this, owing to being pressed with protective layer 22 at the top layer of metal-made flat board 21 surface layer, the compressive resistance of protective layer 22 is high, even therefore will thinly for the thickness system of the polypropylene layer of sealant layer 23 or polyethylene layer also can keep compressive resistance.Therefore, tail off owing to invading from the marginal portion (side edge part) of metal-made flat board 21 to the moisture of inside lithium ion cell, the electrolyte of lithium ion battery through the time deteriorated minimizing, so the product life of battery is elongated.
In addition; even if divide the intrusion inside battery at Trace water; thereby electrolyte and reaction of moisture and then electrolyte decomposition produce in the situation of hydrofluoric acid; the protective layer 22 that is made of the polyvinyl alcohol resin of lamination on the face of the top layer of metal-made flat board 21 is because the space is few; gas barrier property is high; along sealant layer 23, can so that the hydrofluoric acid that produces spread to outside batteries.In addition, even the contact of the hydrofluoric acid of trace is as the surface of the aluminium sheet of metal-made flat board 21, owing to preventing the corrosion of metal-made flat board 21 by the passivating film that forms in surface of aluminum plate, the intensity that keeps the ply adhesion between 23 layers of metal-made dull and stereotyped 21 and the sealant layers, kept compressive resistance, therefore the leakage of battery has not occured yet.
Can be 50～300 μ m with the thickness of the sealant layer 23 of the surface engagement of protective layer 22, consider that water proofing property is preferably 50～150 μ m.If the thickness of metal-made flat board 21 is more than 200 μ m, because rigidity is strong, at the side edge part (edge part) of metal-made flat board 21 through hole appears, have the fully situation of hermetic electrolyte liquid.So shown in Fig. 4 B, from along the situation of observing with the cross section at the junction surface of above-mentioned exterior material, preferably the two end portions 24 with metal-made flat board 21 is rolled, and makes it compare cross section central portion thin thickness.Thus, can make thickness attenuation with the sealant layer 23 of the surface engagement of protective layer 22.
The thickness of the protective layer 22 that is made of polyvinyl alcohol resin is preferably 0.1～5.0 μ m, more preferably 0.5～3 μ m.If protective layer 22 is the thickness of such degree, the performance of moisture resistance, bonding strength improves.
By printing process, form protective layer 22 at the necessary part of the outer surface of metal-made flat board 21.As mode of printing, can use the known printing process of ink-jetting style, distributor mode, spraying method etc.Operable printing process is arbitrarily among the present invention, but owing to not being two surfaces of metal-made flat board 21, and the edge part (edge part) of observing in the cross section of electrode cable parts also needs printing, therefore preferred ink-jetting style and distributor mode.Especially, especially in the distributor mode, can test with the dispense tip that the wide narrow width of about 10mm prints by using, judge that the distributor mode is optimal mode.
Use the same material of the resin molding 13 that uses with innermost layer at aluminium lamination press mold 10 with the sealant layer 23 of the surface engagement of the protective layer 22 of electrode cable parts is preferred, or similar resin molding.Resin molding 13 is in the polyacrylic situation of normal operation, sealant layer 23 is for cast polypropylene (CPP), separately for the film of maleic anhydride modified propylene or be separately the monomer modified polyacrylic film with epoxy-functional of glycidyl methacrylate etc., perhaps can be these and polyacrylic multilayer film.Resin molding 13 is in the poly situation, sealant layer 23 can be for polyethylene, maleic anhydride modified polyethylene or is separately the monomer modified polyethylene with epoxy-functional with glycidyl methacrylate etc., can also be the multilayer film of these and polyethylene and copolymer thereof.In this case, with face that electrolyte contacts on, can be for maleic anhydride, acrylic acid copolymer, with polyethylene of the modifications such as glycidyl methacrylate etc.
As the non-aqueous batteries that the present invention uses, can exemplify the material that in electrolyte, uses organic bath of the lithium ion battery, double electric layer capacitor etc. that are 2 primary cells.As organic bath, be generally the material take the carbonates of propylene carbonate (PC), diethyl carbonate (DEC), ethylene carbonate etc. as medium, but not only be defined in this.
[embodiment]
(method of testing)
The metal-made flat board of electrode cable parts and the method for testing of the bonding strength of sealant layer: use the specimen at sealant layer heat-sealing aluminium lamination press mold, measure according to the method for testing of stipulating among the JIS C6471 " flexible printing terminal block copper clad laminate test method ".
The assay method of electrolyte strength retention ratio (Electricity separates liquid Strong degree conservation rate): use the exterior layered product of use of battery, making 50mm * 50mm(heat seal width is 5mm) the four directions bag, to the LiPF that has wherein added the 1mol/ liter
6PC/DEC electrolyte in add the pure water of 0.5wt%, it is measured the 2cc packing.In this four directions bag, print protective layer in the distributor mode in the part of the outer surface of the metal-made flat board of electrode cable parts.Put into the electrode cable parts of laminating seal agent layer on this protective layer by heat-sealing, storage was measured the protective layer of electrode cable parts and the layers cementing intensity (k2) of sealant layer after 100 hours in the baking oven of 60 ° of C.
At this, be exposed to the protective layer before the electrolyte and be compared to electrolyte strength retention ratio K=(k2/k1) * 100(%) for the plunger bond strength (k1) of the polypropylene of sealant layer (PP) film and between the plunger bond strength (k2) after being exposed to electrolyte what measure in advance.
(testing apparatus)
Bond strength test device: Shimadzu Seisakusho Ltd.'s system, model: AUTOGRAPH AGS-100A tensile test apparatus
(embodiment 1)
Dull and stereotyped with the metal-made of electrode cable parts as lithium battery, using thickness is the aluminium flake that the aluminium sheet of 200 μ m is cut into the size of 50mm * 60mm.On the surface of this aluminium flake after the degreasing washing; use is with polyvinyl alcohol resin (Japanese synthetic chemistry (strain) system of 3wt%; G Port リ マ ー resin) and the aqueous solution that obtains of the charomic fluoride (III) of 1wt% dissolving trade name:; so that dried thickness is the mode of 1 μ m; with the distributor two sided coatings of the wide type of 10mm, lamination protective layer.Further, with 200 ℃ baking oven heat drying, make its Cross-linked in the time of burn-back (the baked I is paid the け Ru) protective layer resin.At this moment, the top layer on two surfaces of metal-made flat board is not only in affirmation, and the side edge part of metal-made flat board (both ends of the surface) also forms protective layer.
Then; on the surface of the protective layer of the outer surface of this metal-made flat board; utilize heat-sealing that monofilm (using polypropylene-based resin (trade name/ア ド マ ー QE060) masking of Mitsui Chemicals being made by the film film-making machine is the film that the 100 μ m obtain) two sides of maleic anhydride modified polypropylene screen is engaged, obtain the electrode cable parts of embodiment 1.
On the sealant layer of the electrode cable parts of embodiment 1, the thickness that will be made of aluminium foil (thickness 20 μ m)/maleic anhydride modified polypropylene screen (thickness 100 μ m) is the aluminium lamination press mold heat-sealing of 120 μ m, makes the specimen of the electrode cable parts that use embodiment 1.
The bond strength test test film that employing is obtained by the specimen of this embodiment 1 when measuring the dull and stereotyped bonding strength with sealant layer of metal-made, shows the bonding strength of 46N/ inch.
In addition, for the specimen of embodiment 1, the result that mensuration electrolyte strength retention ratio K obtains is K=88%.
(embodiment 2)
Dull and stereotyped with the metal-made of electrode cable parts as lithium battery; take the thickness of 2-5 μ m the sulfamic acid nickel coating is plated on thickness and (is of a size of the surface of 50mm * 60mm) as the copper coin sheet of 200 μ m; on its part; use is with polyvinyl alcohol resin (Japanese synthetic chemistry (strain) system of 3wt%; G Port リ マ ー resin) and the aqueous solution that obtains of the charomic fluoride (III) of 1wt% dissolving trade name:; so that being the mode of 1 μ m, dried thickness is coated with the lamination protective layer.Further, with 200 ℃ baking oven heat drying, in burn-back protective layer resin, make its Cross-linked.
Then; on the surface of the protective layer of the outer surface of this metal-made flat board; with maleic anhydride modified polypropylene screen individual layer (using polypropylene-based resin (trade name/ア ド マ ー QE060) masking of Mitsui Chemicals being made by the film film-making machine is the film that 100 μ m obtain) two sides thermal bonding, obtain the electrode cable parts of embodiment 2 by heat-sealing.
Use the electrode cable parts of embodiment 2, similarly to Example 1, the heat-sealing of aluminium lamination press mold is obtained the specimen of embodiment 2, when measuring the bonding strength of metal-made flat board and sealant layer, show the bonding strength of 44N/ inch.
In addition, for the part of the battery outer case of embodiment 2, measuring the result that electrolyte strength retention ratio K obtains is K=78%.
(embodiment 3)
The aqueous solution as a part of coating the metal-made flat board; use is with polyvinyl alcohol resin (Japanese jealous woman PVC ポ バ ー Le (strain) system of 2wt%; trade name: J-ポ バ ー Le DF-20); dissolve the aqueous solution that obtains with the charomic fluoride (III) of 2wt%; so that being the mode of 0.8 μ m, dried thickness is coated with, the lamination protective layer, in addition; similarly to Example 2, obtain electrode cable parts and the specimen of embodiment 3.
For electrode cable parts and the specimen of embodiment 3, when measuring the bonding strength of metal-made flat board and sealant layer, show the bonding strength of 44N/ inch.
In addition, for the part of the battery outer case of embodiment 3, measuring the result that electrolyte strength retention ratio K obtains is K=74%.
(embodiment 4)
The aqueous solution as a part of coating the metal-made flat board; use is with polyvinyl alcohol resin (Japanese カ ー バ イ De industry (strain) system of 2wt%; trade name: Network ロ ス マ ー H); dissolve the aqueous solution that obtains with the charomic fluoride (III) of 2wt%; so that being the mode of 0.8 μ m, dried thickness is coated with, the lamination protective layer, in addition; similarly to Example 2, obtain electrode cable parts and the specimen of embodiment 4.
For electrode cable parts and the specimen of embodiment 4, when measuring the bonding strength of metal-made flat board and sealant layer, show the bonding strength of 46N/ inch.
In addition, for the part of the battery outer case of embodiment 4, measuring the result that electrolyte strength retention ratio K obtains is K=77%.
(comparative example 1)
Except aluminium sheet not the lamination protective layer, similarly to Example 1, obtain electrode cable parts and the specimen of comparative example 1, when measuring the dull and stereotyped bonding strength with sealant layer of metal-made, show the bonding strength of 54N/ inch.And for the specimen of comparative example 1, the result that mensuration electrolyte strength retention ratio K obtains is below the K=10%.
(comparative example 2)
Dull and stereotyped with the metal-made of electrode cable parts as lithium battery; the about sulfamic acid nickel coating of 2-5 μ m is plated on the copper coin sheet that thickness is 200 μ m (is of a size of the surface of 50mm * 60mm); on its part; use is with polyvinyl alcohol resin (Japanese synthetic chemistry (strain) system of 3wt%; trade name: the coating that G Port リ マ ー resin) is mixed to get with the charomic fluoride (III) of 1wt%; so that being the mode of 1 μ m, dried thickness is coated with the lamination protective layer.Except not carrying out behind the lamination heat drying processes, obtain similarly to Example 1 electrode cable parts and the specimen of comparative example 2.
For electrode cable parts and the specimen of comparative example 2, when measuring the bonding strength of metal-made flat board and sealant layer, show the bonding strength of 46N/ inch.And for the specimen of comparative example 2, the result who measures electrolyte strength retention ratio K is below the K=10%.After measuring the electrolyte strength retention ratio, owing to being exposed to electrolyte, the metal-made flat board of generating electrodes wire guiding member and the peeling (leafing) of sealant layer.
Above result is summed up and is shown in Table 1.In table 1, incite somebody to action " the metal-made flat board of electrode cable parts and the bonding strength of sealant layer " referred to as " bonding strength ".
[table 1]
Embodiment 1 and embodiment 2 use Japanese synthetic chemistry (strain) system, trade name: G Port リ マ ー resin as polyvinyl alcohol resin.Embodiment 3 uses Japanese jealous woman PVC ポ バ ー Le (strain) system, trade name: J-ポ バ ー Le DF-20 as polyvinyl alcohol resin.Embodiment 4 uses Japanese カ ー バ イ De industry (strain) system, trade name: Network ロ ス マ ー H シ リ ー ズ as polyvinyl alcohol resin.In embodiment 1～4; the coating that use is mixed to get the charomic fluoride (III) of these polyvinyl alcohol resins of 3wt% or 2wt% and 1wt% or 2wt%; coat on the metal-made flat board of electrode cable parts; form protective layer; thus, the dull and stereotyped bonding strength with sealant layer of the metal-made of electrode cable parts is the 40N/ inch.And the electrode cable parts that the coating protective layer obtains between sealant layer and metal-made flat board have tolerance for the electrolyte of lithium battery, and compressive resistance is also high.
On the other hand; comparative example 1 is not for forming the situation of protective layer at the electrode cable parts; the dull and stereotyped bonding strength with sealant layer of the metal-made of electrode cable parts is the high value of 54N/ inch, and electrolyte strength retention ratio K does not have the electrolyte tolerance below 10%.
In addition; although comparative example 2 is not for still there being the situation of heat drying at electrode cable parts coating protective layer; the dull and stereotyped bonding strength with sealant layer of the metal-made of electrode cable parts is the 46N/ inch, and electrolyte strength retention ratio K does not have the electrolyte tolerance below 10%.
Claims (7)
1. electrode cable parts; the electrode cable parts that it is drawn with accommodating container for the non-aqueous batteries that forms for exterior material from the laminated film layered product with aluminium foil and resin molding; on the outer surface of the metal-made flat board of making strip, will contain the solution coat of polyvinyl alcohol resin or polyvinylether resinoid and fluorochemical and dry and form protective layer.
2. electrode cable parts according to claim 1, wherein said fluorochemical is water-soluble.
3. electrode cable parts according to claim 1 and 2, wherein said protective layer forms banded pattern by printing on the outer surface of described metal-made flat board.
4. electrode cable parts according to claim 1 and 2, wherein said protective layer carries out crosslinked or noncrystallineization by heat treatment, has a water resisting property.
5. non-aqueous batteries accommodating container, it uses electrode cable parts according to claim 1 and 2.
6. non-aqueous batteries accommodating container, it uses electrode cable parts according to claim 3.
7. non-aqueous batteries accommodating container, it uses electrode cable parts according to claim 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012050679A JP2013187018A (en) | 2012-03-07 | 2012-03-07 | Electrode lead wire member for nonaqueous battery |
| JP2012-050679 | 2012-03-07 |
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| CN103311491A true CN103311491A (en) | 2013-09-18 |
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| JP (1) | JP2013187018A (en) |
| KR (4) | KR101471910B1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2013187018A (en) * | 2012-03-07 | 2013-09-19 | Fujimori Kogyo Co Ltd | Electrode lead wire member for nonaqueous battery |
| US20150140397A1 (en) * | 2013-11-15 | 2015-05-21 | Semiconductor Energy Laboratory Co., Ltd. | Multilayer film, exterior material for secondary battery, secondary battery, and electronic device |
| JP5760138B1 (en) * | 2014-01-17 | 2015-08-05 | ユケン工業株式会社 | Method for manufacturing connecting member of electrochemical energy device, connecting member manufactured by the manufacturing method, and electrochemical energy device including the connecting member |
| JP6334361B2 (en) * | 2014-10-20 | 2018-05-30 | 株式会社フジクラ | Power storage module |
| JP6678036B2 (en) * | 2016-01-27 | 2020-04-08 | Fdk株式会社 | Manufacturing method of laminate type energy storage device |
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- 2013-03-06 CN CN201310070346.4A patent/CN103311491B/en active Active
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20140135936A (en) | 2014-11-27 |
| KR20180134813A (en) | 2018-12-19 |
| JP2013187018A (en) | 2013-09-19 |
| KR102100628B1 (en) | 2020-04-14 |
| KR101929789B1 (en) | 2018-12-17 |
| KR20130102472A (en) | 2013-09-17 |
| KR101816597B1 (en) | 2018-01-09 |
| CN103311491B (en) | 2016-01-06 |
| KR101471910B1 (en) | 2014-12-11 |
| KR20160017024A (en) | 2016-02-15 |
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