CN104756277A - Electrode lead wire member for nonaqueous batteries - Google Patents
Electrode lead wire member for nonaqueous batteries Download PDFInfo
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- CN104756277A CN104756277A CN201280076680.4A CN201280076680A CN104756277A CN 104756277 A CN104756277 A CN 104756277A CN 201280076680 A CN201280076680 A CN 201280076680A CN 104756277 A CN104756277 A CN 104756277A
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- contact conductor
- conductor parts
- sealant
- film
- film coating
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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
- 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
- H01M50/121—Organic material
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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
- H01G11/78—Cases; Housings; Encapsulations; Mountings
- H01G11/80—Gaskets; Sealings
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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
- H01M50/117—Inorganic material
- H01M50/119—Metals
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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
- H01M50/10—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
- H01M50/126—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure comprising three or more layers
- H01M50/129—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure comprising three or more layers with two or more layers of only organic 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
- H01M50/172—Arrangements of electric connectors penetrating the casing
- H01M50/174—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells
- H01M50/178—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells for pouch or flexible bag cells
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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
- H01M50/547—Terminals characterised by the disposition of the terminals on the cells
- H01M50/55—Terminals characterised by the disposition of the terminals on the cells on the same side of the cell
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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
- H01M50/552—Terminals characterised by their shape
- H01M50/553—Terminals adapted for prismatic, pouch or rectangular cells
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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
- H01M50/562—Terminals characterised by the material
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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 present invention relates to an electrode lead wire member (18) which is led out from a container for nonaqueous batteries, said container being obtained using, as an outer package material, a film laminate that is composed of an aluminum foil and a resin film. This electrode lead wire member (18) comprises a lead-out part (21) that is formed of a metal. A thin film coating layer (22), which is formed from a metal fluoride or a derivative thereof and a resin containing a hydroxyl group or a copolymerized resin thereof, and a sealant layer (23) are sequentially laminated on the lead-out part (21). The sealant layer (23) is thermally bonded onto the surface of the lead-out part (21), and contains a thermally bondable polyolefin resin having an epoxy functional group at least in a portion that is on the side of the interface between the sealant layer (23) and the lead-out part (21).
Description
Technical field
The present invention relates to as secondary cell lithium ion battery, double electric layer capacitor (hereinafter referred to as capacitor) etc., the contact conductor parts of the nonaqueous battery that employs organic bath in the electrolytic solution.
Background technology
In recent years, improve along with to the attention rate of Global Environmental Problems, universal and wind power generation, the solar power generation etc. of electric automobile effectively utilize the method for natural energy to become problem.Accompany therewith, in these technical fields, as the storage battery for store electrical energy, the secondary cells such as lithium ion battery and capacitor receive much concern.In addition, for the exterior package container of the lithium ion batteries used in storage electric automobile etc., use the flat bag that has and utilize and aluminium foil and the stacked exterior duplexer of battery of resin film are made and/or realize slim lightweight by drawing and forming or the convex shaping made container molding of drum.
But the electrolyte of lithium ion battery has the character of not resistance to moisture and light.Therefore, the exterior material of lithium ion battery use the stacked substrate layer that is made up of polyamide and/or polyester and aluminium foil, the exterior duplexer of battery of water proofing property and light-proofness excellence.
In order to receive lithium ion battery using so exterior duplexer of battery in the accommodating container made, such as, use mounting container 30 as shown in Figure 3A.That is, use the exterior duplexer of battery in advance, be shaped to the hypocraterimorphous shape with recess 31 by drawing and forming etc., in the recess 31 of this pallet, receive the adjuncts such as lithium ion battery (not shown) and electrode 36.Then, as shown in Figure 3 B, wrap up battery from the top cover material 33 that is made up of the exterior duplexer of battery of overlap, the flange part 32 of pallet and the side edge part 34 of four sides of cover material 33 to be sealed and battery is airtight.The accommodating container 35 that the method that battery is placed in the recess 31 of pallet by this utilization is formed, owing to can receive battery from top, so productivity ratio is high.
In the mounting container 30 of the lithium ion battery shown in above-mentioned Fig. 3 A, in the past, the degree of depth (following, sometimes the degree of depth of pallet to be called " depth ") of pallet was about 5 ~ 6mm in small-sized lithium ion battery.But, in recent years, in the purposes such as electric automobile, require the accommodating container for accommodating battery larger than ever.In order to manufacture the accommodating container of large-sized battery, the pallet that necessary shaping depth is darker, technical difficulty increases.
In addition, when moisture invades inside lithium ion cell, electrolyte produces strong acid because moisture occurs to decompose.Now, the strong acid produced from the inner side of the exterior duplexer of battery permeates, its result, has aluminium foil to corrode because of strong acid and deteriorated possibility., there is the leakage of electrolyte in its result, not only the performance of battery reduces, and lithium ion battery also may be on fire.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2000-357494 publication
Summary of the invention
Technical problem
As the method that the superficial layer of the aluminium foil and/or contact conductor parts that prevent from forming the exterior duplexer of above-mentioned battery corrodes because of strong acid; Patent Document 1 discloses by implementing chromate process to the surface of aluminium foil and form diaphragm, improving the method for corrosion resistance.But, because chromate process is used as the chromium of heavy metal, so have problems in environmental protection, because Cr VI is the harmful substance impacted human body, so cannot use.Therefore, use containing chromic chromate treating solution.In addition, in the chemical conversion treatment beyond chromate process, the effect improving corrosion resistance is low.
In addition, in existing contact conductor parts, the electrolyte resistance of the aluminium as anode electrode parts in the electrode of positive pole and this two side of negative pole is good, even but carry out nickel plating as the copper coin of negative electrode parts on top layer, and implement chromic chromate process, its electrolyte resistance is also lower.
In addition, in order to laminated film duplexer and electrod assembly be sealed, make the part being thermally bonded in this electrod assembly with the resin film of the fluid sealant same resin kind of laminated film duplexer.At this moment, use and there is the resin film with the cementability of metal, the resin film of the vistanex of such as ionomer, ethene and acrylic acid copolymer resins (EAA), maleic anhydride graft copolymerization etc., but in order to have sufficient bonding force, need at high temperature to carry out long-time heating, productivity ratio is low.
The present invention makes in view of the foregoing, its object is to provide raising corrosion resistance, even if thus the electrolyte of lithium ion battery and reaction of moisture and produce hydrofluoric acid, corrosivity increases, also can avoid its harmful effect, extend life-span of lithium ion battery, and the high and contact conductor parts of the nonaqueous battery that productivity ratio is high of moisture barrier.
Technical scheme
For the present invention, in battery accommodating container, in advance that resin types is identical with the fluid sealant of laminated film duplexer resin film is heat-bonded to the laminated film duplexer of exterior material and the part of contact conductor part bonding as sealant.Sealing layer is multilayer or individual layer, and at least sealant with the part of the interface side of contact conductor parts containing the thermal bonding vistanex with epoxy-functional.If have this to contain to have the sealant of the thermal bonding vistanex of epoxy-functional, then fast with the speed of metal lead-wire components heat bonding, productivity ratio is high, and adhesive strength is high, therefore, it is possible to improve the sealing to moisture.
In order to solve above-mentioned problem, the invention provides a kind of contact conductor parts, from employing the contact conductor parts of drawing in the nonaqueous battery accommodating container of the laminated film duplexer of aluminium foil and resin film exterior material, possesses metal leading-out portion, this leading-out portion stacks gradually the film coating and sealant that are made up of metal fluoride or derivatives thereof and the resin containing hydroxyl or its copolymer resins, above-mentioned sealant is the film of multilayer or individual layer, its heat bonding is on the surface of above-mentioned leading-out portion, and at least above-mentioned sealant with the part of the interface side of above-mentioned leading-out portion containing the thermal bonding vistanex with epoxy-functional.
In addition, preferred above-mentioned metal fluoride or derivatives thereof makes above-mentioned resin containing hydroxyl or its copolymer resins be cross-linked and make the material of the surface passivation of aluminium.
In addition, preferred above-mentioned film coating is formed as pattern-like by printing on the surface of above-mentioned leading-out portion.Thus; at the non-cohesive electrolyte resistance diaphragm of joint and/or series, parallel bonding part with inside battery current-collecting member; thus the interface when ultrasonic bonding, electric resistance welding joint etc. engages does not have electrolyte resistance diaphragm, therefore has the advantage that connectivity is good.
In addition, the film coating being preferably formed in the surface of above-mentioned leading-out portion by heat treatment crosslinked or decrystallized be able to water-fast.
In addition, preferred above-mentioned film coating and above-mentioned sealant are being formed, until at least both adhesive strengths are more than 10N/ inch by the heat treatment of thermal adhesive layer poststack or room temperature preservation.
Should illustrate, N/ inch is equivalent to N/25.4mm.
In addition, the thickness of preferred above-mentioned sealant is 50 μm ~ 300 μm and the thickness of above-mentioned film coating is 0.01 ~ 1.0 μm, the interlaminar strength of above-mentioned film coating and stacked above-mentioned sealant is thereon measured, more than 10N/ inch by the stripping assay method A of JIS (Japanese Industrial Standards) C6471 defined.
In addition, the above-mentioned contact conductor parts of preferred conquassation, cross-section to both ends and make Thickness Ratio cross section central portion thin.
Beneficial effect
Contact conductor parts, crosslinked or decrystallized and be able to water-fast by heat treatment by metal fluoride or derivatives thereof and the film coating formed containing the resin of hydroxyl or its copolymer resins.Its result, can suppress electrolyte from contact conductor parts, cross-section to both ends immerse.
In addition, if conquassation contact conductor parts, cross-section to both ends and make Thickness Ratio cross section central portion thin, then contact conductor parts and the closely sealed of laminated film duplexer become good, and space part tails off, and reduce the immersion of electrolyte.
Accompanying drawing explanation
Fig. 1 is the stereogram of the example representing battery accommodating container.
Fig. 2 is the schematic section of the example representing the exterior duplexer of battery that can use in battery accommodating container.
Fig. 3 A is the stereogram representing operation lithium ion battery being accommodated in accommodating container.
Fig. 3 B is the stereogram representing operation lithium ion battery being accommodated in accommodating container.
Fig. 4 A is the stereogram of the example representing contact conductor parts of the present invention.
Fig. 4 B is the sectional view of the S-S line along Fig. 4 A.
Fig. 5 is the vertical view of the example representing contact conductor parts of the present invention.
Symbol description
10 ... the exterior duplexer of battery,
11 ... substrate resin film,
12 ... aluminium foil,
13 ... sealant,
15,16 ... bond layer,
17 ... lithium ion battery,
18 ... contact conductor parts,
19 ... side edge part,
20 ... battery exterior package container,
21 ... leading-out portion,
22 ... film coating,
23 ... sealant,
30 ... battery mounting container,
35 ... battery accommodating container.
Embodiment
For the contact conductor parts of drawing in the accommodating container of the lithium ion battery manufactured from using the exterior duplexer of battery, seeing figures.1.and.2 and contact conductor parts of the present invention are described.
As shown in Figure 1, contact conductor parts 18 of the present invention and lithium ion battery 17 are installed in folding for exterior for battery duplexer 10 and in the battery exterior package container 20 made.
And the side edge part 19 of three sides of the exterior container of battery 20 is made bag-shaped by heat-sealing.Contact conductor parts 18, as Fig. 1, are drawn from battery exterior package container 20.Should illustrate, the lithium ion battery using contact conductor parts 18 of the present invention to manufacture is put into the accommodation method of battery accommodating container as shown in figs.3 a and 3b.
As shown in Figure 2, the substrate resin film 11 of the exterior duplexer of the battery be made up of laminated film duplexer 10, aluminium foil 12 and sealant 13 are bonding respectively by bond layer 15,16.
As illustrated in figures 4 a and 4b, contact conductor parts 18 possess the leading-out portion 21 of aluminum, sequentially laminated with film coating 22 and sealant 23 on the surface of this leading-out portion 21, described film coating 22 is formed by metal fluoride or derivatives thereof and containing the resin of hydroxyl or its copolymer resins.
Preferably chromate process is carried out in the formation of film coating 22, wherein, the process that the following solution of preferred utilization carries out, that is, this solution contain make to be made up of metal fluoride or derivatives thereof, being principal component with the resin containing hydroxyl or its copolymer resins, film coating is cross-linked and makes the material of the surface passivation of aluminium.Wherein, even if not containing metal fluoride or derivatives thereof in treatment fluid, the corrosion resistance of coating also improves.Film coating 22 is formed as pattern-like by printing on the surface of above-mentioned leading-out portion 21.The film coating 22 formed on the surface of above-mentioned leading-out portion 21 is crosslinked or decrystallized and be able to water-fast by heat treatment.
Contact conductor parts normally positive pole use aluminium sheet, and negative pole is used in the metal that copper coin is covered by nickel plating.In order to easily carry out the heat bonding of the exterior duplexer of battery (laminated film duplexer) 10 and contact conductor parts 18, form at the leading-out portion 21 of contact conductor parts 18 and the bonding portion of laminated film duplexer 10 sealant 23 that the resin film identical by the sealant 13 of resin types and laminated film duplexer 10 form in advance.Sealing layer 23 is single or multiple lift, is laminated with the sealant containing the thermal bonding vistanex with epoxy radicals at the sealant in the face of the interface side of the leading-out portion 21 with lead member.
In the present invention, when sealant 23 is individual layer, it is overall containing thermal bonding vistanex.When sealant 23 is multilayer, at least contain thermal bonding vistanex with leading-out portion 21 or the layer that connects with film coating 22, in addition, other layer also can contain thermal bonding vistanex.When sealant 23 is multilayer, except except leading-out portion 21 or the layer that connects with film coating 22, other resin such as vistanex and/or acid-modified polyolefin resin can not having an epoxy radicals by common polyethylene, polypropylene etc. is formed.In addition, can only be made up of the thermal bonding vistanex with epoxy radicals containing the layer of thermal bonding vistanex in sealant 23, or can be the mixture of itself and other resin, compound and/or polymer alloy etc.
Sealant is made to be the interlayer laminating method that the method for multilayer can use based on extruding laminating method, also can when by sealant filming, the film making multilayer is stacked to carry out.
If do not form the film coating of corrosion resistance on the surface of contact conductor parts, then cause moisture and electrolyte to react on the surface of contact conductor parts because of the infiltration of electrolyte, produce hydrofluoric acid and cause contact conductor component corrosion, its result, the bonding force of contact conductor parts and sealant may reduce.Therefore, the preferred at least stacked film coating be made up of the resin containing hydroxyl or its copolymer resins on the surface of the internal layer side of contact conductor parts.In addition, the peripheral part integral layer laminate film coating in the cross section of contact conductor parts is needed.
The also method of the known aluminum contact conductor component corrosion deterioration as preventing from being caused by electrolyte, chromate process can be used in the prior art, but should process, the effect in the contact conductor parts of copper/nickel plating is less than the effect in the contact conductor parts at aluminum.But, in contact conductor parts of the present invention, even if clearly for the contact conductor parts of copper/nickel plating, can also have the effect of electrolyte resistance.Therefore, the diaphragm that existing chromate process may be utilized to be formed is different from the anticorrosion mechanism of the film coating of corrosion resistance of the present invention.
As shown in Figure 5, can with the stacked sealant 23 of mode across positive pole and this two side of negative pole.Thereby, it is possible to obtain the positive pole contact conductor parts integrated with negative pole.In addition, the anticorrosion ability of film coating 22 can all be obtained for various metallic plates such as aluminium sheet and nickel plating copper coins, the therefore preferred leading-out portion 21 film coating 22 being arranged at positive pole and this two side of negative pole.
In the film coating 22 being applied to contact conductor parts of the present invention, as the resin containing hydroxyl or its copolymer resins, the polymer enumerating vinyl esters system monomer or the resin that its copolymer saponification is obtained representativity.As vinyl esters system monomer, the aromatic vinyl such as fatty acid vinyl ester and the vinyl benzoate esters such as vinyl formate, vinyl acetate, vinyl butyrate can be enumerated.As other monomer carrying out copolymerization, the unsaturated acids such as ethene, propylene, alpha-olefines, acrylic acid, methacrylic acid, maleic anhydride can be enumerated, the ethylene halide such as vinyl chloride and vinylidene chloride base class etc.As commercially available product, the G fluoropolymer resin (trade name) of Japanese synthetic chemistry Co., Ltd. can be enumerated.
In addition, preferably in film coating 22, utilize chromate treating solution, the chromate treating solution that particularly performance is good contains makes the film coating 22 being made up of metal fluoride or derivatives thereof, being made up of the resin containing hydroxyl or its copolymer resins be cross-linked, and makes the material of the surface passivation of aluminium foil.Metal fluoride or derivatives thereof is the F of the fluoride containing the aluminium forming passivation
-the material of ion, such as, can enumerate the fluorides such as charomic fluoride, ferric flouride, zirconium fluoride, titanium fluoride, hafnium fluoride, fluorine zirconic acid and their salt, fluotitanic acid and their salt.
In order to the face, top layer of the leading-out portion 21 at these contact conductor parts forms film coating 22, such as, use non-crystalline polymer (Japanese synthetic chemistry Co., Ltd. system with the polyvinyl alcohol skeleton containing hydroxyl of 0.01 ~ 1wt%, trade name: G fluoropolymer resin) and the charomic fluoride (III) of 0.02 ~ 3wt% dissolve and the aqueous solution made, after the mode being about 0.01 ~ 1 μm with dried thickness is coated with, carries out heat drying further in an oven, toast bonding and Cross-linked.By this process, film coating 22 can be formed.
Like this, if be laminated with film coating 22 on the surface of contact conductor parts, then because the compressive resistance of film coating 22 is high, even if so make the lower thickness of polypropylene resin layer as the sealant 13 of laminated film duplexer 10 or polyvinyl resin layer, also can compressive resistance be kept.Therefore, the immersion of moisture from the marginal portion (side edge part) of contact conductor parts to inside lithium ion cell tails off, the electrolyte of lithium ion battery through time deterioration reduce, therefore, it is possible to extend the life of product of battery.
In addition, even if immerse inside battery at the moisture because of trace, electrolyte and reaction of moisture and cause electrolyte decomposition, thus when producing hydrofluoric acid, due to be layered in the face, top layer of contact conductor parts, the free volume of film coating 22 that is made up of the resin containing hydroxyl or its copolymer resins is few and barrier properties for gases is high, so hydrofluoric acid externally can not spread along sealant 13.In addition, even if the hydrofluoric acid contact of trace is as the surface of the aluminium sheet of the leading-out portion 21 of contact conductor parts 18, also the corrosion of contact conductor parts can be prevented by the passivating film being formed in surface of aluminum plate, the layers cementing intensity of holding electrode lead member 18 and sealant 13, maintain high compressive resistance hold mode, therefore also can not produce the problems such as battery leakage.
The sealant 23 being thermally bonded in contact conductor parts in advance is preferably made to be the thickness of 50 ~ 300 μm, if consider water proofing property, then the most preferably thickness of 30 ~ 150 μm.If the thickness of the leading-out portion 21 of contact conductor parts 18 is more than 200 μm, then sometimes produces through hole at the edge of contact conductor parts, the sealing of electrolyte cannot be carried out.In this case, by carrying out fragmentation processing to the edge of contact conductor parts, thus the lower thickness of the sealant 23 of heat bonding in advance can be made.
The thickness of the film coating 22 be made up of the resin containing hydroxyl or its copolymer resins is preferably 0.01 ~ 1 μm, is more preferably 0.1 ~ 0.5 μm, if the thickness of such film coating, then the performance of moisture resistance and adhesive strength increases.
Film coating 22 is formed in the part required for contact conductor parts by printing.As printing process, ink-jetting style, known printing process such as coating (dispenser) mode, spraying method etc. can be used.The printing process that can use in the present invention is arbitrary, but consider not only on the top layer of the surface back side of contact conductor parts, and contact conductor parts cross-section to edge part also need to print, therefore preferably ink-jetting style and coating method.Particularly, in coating method, the dispense tip that can print about using width thinning one-tenth 10mm width is tested, and result is judged as most suitable mode.
The sealant 23 being thermally bonded in contact conductor parts in advance preferably uses the resin film that resin types is identical with the sealant 13 of laminated film duplexer 10.Such as, when the sealant of laminated film duplexer is the polyethylene film usually used, the monofilm of polyethylene film that can be maleic anhydride modified polyethylene film or carry out modification by glycidyl methacrylate etc. and obtained, in addition, can also be these resin films and the multilayer film of the resin film be made up of polyethylene film and copolymer thereof.In addition, when the sealant of laminated film duplexer is polypropylene film, can be the monofilm that the polymer alloy of the polyethylene and random copolymer polypropylene having carried out modification by glycidyl methacrylate etc. is made, or can be stacked polypropylene film and the multilayer film obtained on this monofilm.
As nonaqueous battery used in the present invention, the battery employing organic bath in the electrolytic solution of the lithium ion battery and double electric layer capacitor etc. as secondary cell can be enumerated.As organic bath, normally propylene carbonate (PC), diethyl carbonate (DEC), ethylene carbonate etc. take carbonates as the organic bath of medium, but are not particularly limited.
Embodiment
(assay method)
The assay method of the leading-out portion of contact conductor parts and the adhesive strength of sealant: the assay method according to JIS (Japanese Industrial Standards) C6471 " flexible printed circuit board copper-clad plate test method " defined measures.
The assay method of electrolyte strength retention: use the exterior duplexer of battery, make the cubic bag of 50 × 50mm (heat seal width is 5mm), with the addition of the LiPF of 1mol/ liter wherein
6pC/DEC electrolyte in add and account for the pure water of 0.5wt%, weigh 2cc, pack after being filled into cubic bag.In this cubic bag, put into the part utilizing coating method film coating to be printed onto contact conductor parts, this film coating is laminated with by heat-sealing the contact conductor parts of sealant, preserve in the baking oven of 60 DEG C after 100 hours, measure the layers cementing intensity (k2) of contact conductor parts and sealant.
At this, using the ratio of layers cementing intensity (k1) and layers cementing intensity (k2) as electrolyte strength retention K=(k2/k1) × 100 (%), described layers cementing intensity (k1) be measure in advance, be exposed to the contact conductor parts before electrolyte and the layers cementing intensity as polyethylene (PE) film of sealant, described layers cementing intensity (k2) is the layers cementing intensity after being exposed to electrolyte.
(determinator)
The determinator of adhesive strength uses the tensile test apparatus of model for AUTOGRAPHAGS-100A of Shimadzu Seisakusho Ltd..
(embodiment 1)
As the contact conductor parts of lithium battery, using thickness is the aluminium flake that size that the aluminium sheet of 200 μm cuts into 50mm × 60mm obtains.On the surface of this aluminium flake through cleaning by degreasing, use non-crystalline polymer (Japanese synthetic chemistry Co., Ltd. system with the polyvinyl alcohol skeleton containing hydroxyl of 1wt%, trade name: G fluoropolymer resin) and 2wt% charomic fluoride (III) dissolve the aqueous solution, 10mm width type coating machine is utilized to coat two sides with the thickness of 0.5 μm, laminate film coating, in the baking oven of 200 DEG C, carry out heat drying further and baking of resin, carry out Cross-linked simultaneously and obtain the contact conductor parts of embodiment 1.Now, confirm not only to be coated with film coating on the top layer of the surface back side of the contact conductor parts of embodiment 1, be also coated with film coating in the both ends of the surface of contact conductor parts.
In addition, on the film coating of the contact conductor parts of embodiment 1, with 200 DEG C × 1 second × 0.2MPa condition, make the monofilm of epoxy-modified polyethylene film (film of 100 μm of thickness made by the resin that use utilizes film-making machine the commodity of Sumitomo Chemical Co to be called BONDFAST) two-sided joint by heat-sealing, preserve 48 hours in the hot-air oven of 50 DEG C.Next, seal thereon be made up of nylon film 25 μm/polyurethane adhesive 3 μm/aluminium foil (thickness 40 μm)/maleic anhydride modified polyethylene film (thickness 50 μm), thickness is that the aluminium lamination press mold of 118 μm is to make a part for the battery outer case of embodiment 1.
From a part for the battery outer case of this embodiment 1, choose the test film of determining bonding strength, measure the adhesive strength of laminated film duplexer and contact conductor parts, result shows the adhesive strength of 56N/ inch.
In addition, electrolyte strength retention K is measured to a part for the battery outer case of embodiment 1, result K=89%.
(embodiment 2)
As the contact conductor parts of lithium battery, it is the surface of the copper coin sheet (size 50mm × 60mm) of 200 μm at thickness, with the thickness plating nickel sulfamic acid of 1 ~ 5 μm, in its part, use non-crystalline polymer (Japanese synthetic chemistry Co., Ltd. system with the polyvinyl alcohol skeleton containing hydroxyl of 1wt%, trade name: G fluoropolymer resin) and 3wt% charomic fluoride (III) dissolve the aqueous solution, be coated with the thickness of 0.5 μm, laminate film coating, heat drying baking of resin is passed through further in the baking oven of 200 DEG C.
In addition, on the film coating of these contact conductor parts, with the heat seal condition of 200 DEG C × 1 second × 0.2MPa, two-layer epoxy-modified polyethylene film (is used with the blending ratio of 6:4 Sumitomo Chemical BONDFAST (ProductName) and random copolymer polypropylene resin (ProductName) is mixing and after carrying out polymer-alloying, the film of 100 μm is made with film-making machine) Double-side hot is bonding, preserves 48 hours in the hot-air oven of 50 DEG C.According to mode similarly to Example 1, obtain a part for the battery outer case of embodiment 2, measure the adhesive strength of laminated film duplexer and contact conductor parts, result shows the adhesive strength of 54N/ inch.
In addition, electrolyte strength retention K is measured to a part for the battery outer case of embodiment 2, result K=88%.
(embodiment 3)
As the contact conductor parts of lithium battery, it is the surface of the copper coin sheet (size 50mm × 60mm) of 200 μm at thickness, with the thickness plating nickel sulfamic acid of 1 ~ 5 μm, in its part, use non-crystalline polymer (Japanese synthetic chemistry Co., Ltd. system with the polyvinyl alcohol skeleton containing hydroxyl of 1wt%, trade name: G fluoropolymer resin) and 3wt% charomic fluoride (III) dissolve the aqueous solution, be coated with the thickness of 0.5 μm, laminate film coating, further heat drying and baking of resin in the baking oven of 200 DEG C.
In addition, on the film coating of these contact conductor parts, with the heat seal condition of 200 DEG C × 1 second × 0.2MPa, by two-layer epoxy-modified polypropylene film, (use utilizes film-making machine by ADMER (ProductName) resin in Mitsui Chemicals, Inc, the epoxy compounds (ProductName/Mitsubishi Chemical Epikote 1001) containing hydroxyl of composite 1.5wt% in maleic anhydride modified acrylic resin, it is made to react with the maleic anhydride functional groups of acrylic resin and the acrylic resin having imported epoxy radicals makes 100 μm and the film obtained) Double-side hot is bonding, preserve 48 hours in the hot-air oven of 50 DEG C.According to mode similarly to Example 1, obtain a part for the battery outer case of embodiment 3, measure the adhesive strength of laminated film duplexer and contact conductor parts, result shows the adhesive strength of 65N/ inch.
In addition, electrolyte strength retention K is measured to a part for the battery outer case of embodiment 3, result K=105%.
(comparative example 1)
On aluminium sheet, form film coating similarly to Example 1, on the film coating of these contact conductor parts, by the heat-sealing of 200 DEG C × 1 second × 0.2MPa by bonding for maleic anhydride modified polyethylene film individual layer (use and Mitsui Chemicals ADMER (ProductName) resin film-making machine individual layer is made the film of 100 μm) Double-side hot, preserve 48 hours in the hot-air oven of 50 DEG C.Utilize method similarly to Example 1 to obtain the contact conductor parts of comparative example 1 and a part for battery outer case, measure the adhesive strength of aluminium lamination press mold and contact conductor parts, result shows this lower adhesive strength of 7N/ inch.In addition, electrolyte strength retention K is measured to a part for the battery outer case of comparative example 1, below result K=50%.
(comparative example 2)
As the contact conductor parts of lithium battery, it is the nickel sulfamic acid of the coating surface about 2 ~ 5 μm of the copper coin sheet (size 50mm × 60mm) of 200 μm at thickness, in its part, use non-crystalline polymer (the Japanese synthetic chemistry Co., Ltd. system with the polyvinyl alcohol skeleton containing hydroxyl being mixed with 1wt%, trade name: G fluoropolymer resin) and the charomic fluoride (III) of 2wt% and the coating obtained, be coated with the thickness of 0.5 μm, laminate film coating, then after carrying out the process of heat drying with the baking oven of 200 DEG C, Double-side hot is carried out bonding by the heat-sealing of 200 DEG C × 1 second × 0.2MPa, preserve 48 hours in the hot-air oven of 50 DEG C.According to mode similarly to Example 1, obtain the contact conductor parts of comparative example 2 and a part for battery outer case.
The contact conductor parts of comparative example 2 and a part for battery outer case are measured to the adhesive strength of laminated film duplexer and contact conductor parts, result shows the adhesive strength of 6N/ inch.In addition, measure electrolyte strength retention K to a part for the battery outer case of comparative example 2, result is below K=30%.In addition, owing to exposing in the electrolytic solution after the mensuration of electrolyte strength retention, so the phenomenon (layering) that generating electrodes lead member and sealant are peeled off.
Above result is shown in table 1.
Table 1
In embodiment 1 ~ 3, owing to using non-crystalline polymer (the Japanese synthetic chemistry Co., Ltd. system with the polyvinyl alcohol skeleton containing hydroxyl being mixed with 1wt%, trade name: G fluoropolymer resin) and the charomic fluoride (III) of 2wt% and the coating obtained, coat contact conductor parts, laminate film coating, thereon, by the heat-sealing of 200 DEG C × 1 second × 0.2MPa, the polyolefin film with epoxy radicals is thermally bonded in two sides, preserve 48 hours in the hot-air oven of 50 DEG C, so the adhesive strength of contact conductor parts and sealant is more than 50N/ inch.Preserve 48 hours if not in the hot-air oven of 50 DEG C, then adhesive strength is below 10N/ inch, and adhesive strength is not enough.In addition, the contact conductor parts only obtained by sealant heat bonding also have patience to the electrolyte of lithium battery, and adhesive strength is also high.
Utilizability in industry
Raising corrosion resistance can be provided, even if thus the electrolyte of lithium ion battery and reaction of moisture and produce hydrofluoric acid, corrosivity increases, also can avoid its harmful effect, extend life-span of lithium ion battery, and the high and contact conductor parts of the nonaqueous battery that productivity ratio is high of moisture barrier.
Claims (6)
1. contact conductor parts, the contact conductor parts from the laminated film duplexer of aluminium foil and resin film is used as to draw the nonaqueous battery accommodating container of exterior material, possesses metal leading-out portion, this leading-out portion stacks gradually the film coating and sealant that are made up of metal fluoride or derivatives thereof and the resin containing hydroxyl or its copolymer resins
Described sealant is the film of multilayer or individual layer, its heat bonding on the surface of described leading-out portion, and at least described sealant with the part of the interface side of described leading-out portion containing the thermal bonding vistanex with epoxy-functional.
2. contact conductor parts according to claim 1, wherein, described metal fluoride or derivatives thereof makes described resin containing hydroxyl or its copolymer resins be cross-linked and make the material of the surface passivation of aluminium.
3. contact conductor parts according to claim 1 and 2, wherein, described film coating is formed as pattern-like by printing on the surface of described leading-out portion.
4. contact conductor parts according to claim 1 and 2, wherein, the film coating being formed in the surface of described leading-out portion is crosslinked or decrystallized and be able to water-fast by heat treatment.
5. contact conductor parts according to claim 1 and 2, wherein, described film coating and described sealant are being heat-treated by thermal adhesive layer poststack or room temperature preservation and being formed, until at least both adhesive strengths are more than 10N/ inch.
6. contact conductor parts according to claim 1 and 2, wherein, the thickness of described sealant is 50 μm ~ 300 μm and the thickness of described film coating is 0.01 ~ 1.0 μm, the interlaminar strength of described film coating and stacked described sealant is thereon measured, more than 10N/ inch by the stripping assay method A of Japanese Industrial Standards C6471 defined.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2012/081979 WO2014091544A1 (en) | 2012-12-10 | 2012-12-10 | Electrode lead wire member for nonaqueous batteries |
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| CN104756277A true CN104756277A (en) | 2015-07-01 |
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| CN201280076680.4A Pending CN104756277A (en) | 2012-12-10 | 2012-12-10 | Electrode lead wire member for nonaqueous batteries |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5856693B2 (en) |
| KR (1) | KR101657202B1 (en) |
| CN (1) | CN104756277A (en) |
| WO (1) | WO2014091544A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106920915A (en) * | 2015-12-25 | 2017-07-04 | 住友电气工业株式会社 | Lead member and the battery using the lead member |
| CN107949420A (en) * | 2015-09-07 | 2018-04-20 | 日本光电工业株式会社 | Electrode pack and sealing device |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7316755B2 (en) * | 2018-02-05 | 2023-07-28 | 藤森工業株式会社 | Electrode lead wire member and battery |
| CN114725629A (en) * | 2020-12-22 | 2022-07-08 | 双叶电子工业株式会社 | Tab lead and nonaqueous electrolyte device |
| KR102572385B1 (en) * | 2021-01-08 | 2023-09-01 | 동원시스템즈 주식회사 | Method for manufacturing electrode tab attachment for secondary battery |
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- 2012-12-10 JP JP2014551756A patent/JP5856693B2/en active Active
- 2012-12-10 WO PCT/JP2012/081979 patent/WO2014091544A1/en active Application Filing
- 2012-12-10 KR KR1020157007157A patent/KR101657202B1/en active IP Right Grant
- 2012-12-10 CN CN201280076680.4A patent/CN104756277A/en active Pending
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| CN106920915B (en) * | 2015-12-25 | 2019-08-30 | 住友电气工业株式会社 | Lead member and the battery for using the lead member |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2014091544A1 (en) | 2014-06-19 |
| KR20150095608A (en) | 2015-08-21 |
| KR101657202B1 (en) | 2016-09-19 |
| JPWO2014091544A1 (en) | 2017-01-05 |
| JP5856693B2 (en) | 2016-02-10 |
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