CN206236710U - Electrical storage device exterior member - Google Patents

Abstract

The utility model is related to electrical storage device exterior member, it at least possesses substrate layer, bond layer, metal foil layer and sealant, wherein, sealant contains inorganic system's filler, and ratio in section in the stacking direction for the gross thickness of sealant shared by inorganic system's filler is 5~50%.According to the utility model, using the teaching of the invention it is possible to provide even if sealant to be also able to maintain that the electrical storage device exterior member of good insulating properties in the case of thin layer.In addition, according to the utility model, using the teaching of the invention it is possible to provide the exterior member of the short circuit generation at the top of also not only suppressing in the composition that sealant is less than 35 μm in sealing, side seal, degassing heat-sealing but also the reduction without lamination strength, sealing intensity required by sealant.

Description

Electrical storage device exterior member

Technical field

The utility model is related to electrical storage device exterior member.

Background technology

As electrical storage device, it is known that such as secondary cell such as lithium ion battery, Ni-MH battery and lead accumulator and double electricity The electrochemical capacitors such as layer capacitor.Due to the miniaturization or the limitation etc. of installation space of portable equipment, it is desirable to electrical storage device Further miniaturization, energy density lithium ion battery high has attracted attention.As the exterior member used in lithium ion battery, Be previously used metal tank, but gradually using lightweight, thermal diffusivity it is high, can be with the multilayer film of low-cost production (for example, base Material layer/metal foil layer/sealant is such to be constituted) (for example, patent document 1：Japanese Unexamined Patent Publication 2013-157287 publications).

Then, as one of means of slimming for realizing electrical storage device exterior member, can include carries out sealant It is thin layer.But, in the case of making sealant thin layer according to the prior art of the grade of patent document 1, due to implementing top Lug lead is provided easy access to the distance of metal level during sealing, it is therefore possible to be short-circuited.In addition, also allowing for due to thin layer Change development, the flowing of the resin by sealant side of (top sealing, side seal and degassing heat-sealing) is drawn when being susceptible to heat-sealing The variation of the thickness for rising, it easily causes short circuit.It should be noted that top sealing mentioned here refers to that clamping lug is drawn The position of line is sealed, and side seal refers to that the position beyond this is sealed, and degassing heat-sealing refers to carry out these heat Seal and be made for seal such as exterior member middle body after injecting electrolyte in bag-shaped exterior member.

Utility model content

Therefore, the utility model is in view of above-mentioned actual conditions, it is therefore intended that even if providing by the thin layer feelings of sealant Also the electrical storage device exterior member of good insulating properties is able to maintain that under condition.

To achieve these goals, the utility model provides electrical storage device exterior member, and it at least has substrate layer, glues Oxidant layer, metal foil layer and sealant are connect, wherein, sealant contains inorganic system's filler, and in the section along stacked direction Ratio for the gross thickness of sealant shared by inorganic system's filler is 5~50%.Thus, even if by sealant thin layer In the case of change, it is also possible to maintain good insulating properties.

In the utility model, the content of preferably inorganic system's filler is 5~35 mass % on the basis of the gross mass of sealant. Thus, inorganic system's filler is easily fully played as the effect of sept, and easily suppresses the reduction of cementability.

Sealant is preferably made up of the layer of more than 2, and at least 1 layer therein is free of above-mentioned inorganic system's filler.For not having The layer of inorganic system's filler is added, the drop of the original characteristic of sealant of the appearance caused by containing inorganic system's filler can be suppressed It is low.

The thickness of the layer containing inorganic system's filler is more than 50% preferably with respect to the gross thickness of sealant.If in the model Enclose outer, then there is the flowing for being susceptible to resin, the tendency for being susceptible to short circuit in the case of applying heat, pressure in heat-sealing.

In sealant, the layer for preferably comprising inorganic system's filler is held in the layer without inorganic system's filler.Thereby, it is possible to Manifest insulation characterisitic in the case of not hindering cementability, heat seal property with metal foil layer 13.

Layer containing inorganic system's filler is preferably the layer being made up of acid modified polyolefin.Thus, improve and inorganic system's filler Adaptation, even if heat is applied with heat-sealing, in the case of pressure also it is easy to ensure that lazy flow.

Inorganic system's filler is preferably the inorganic system's filler being surface-treated.Thus, the resin and nothing of sealant are formed The adaptation of machine system filler is improved, and can further reduce Resin Flow during melting.

According to the utility model, using the teaching of the invention it is possible to provide even if good exhausted sealant is also able to maintain that in the case of thin layer The electrical storage device exterior member of edge.Additionally, according to the utility model, using the teaching of the invention it is possible to provide in the composition that sealant is less than 35 μm In also not only suppress top sealing, side seal, degassing heat-sealing in short circuit generation and also without the layer required by sealant Compressive Strength, the exterior member of the reduction of sealing intensity.

Brief description of the drawings

Fig. 1 is the summary section of the electrical storage device exterior member of an implementation method of the present utility model.

Fig. 2 is the summary section of the electrical storage device exterior member of another implementation method of the present utility model.

Fig. 3 is the signal of the calculation method for illustrating the ratio for the gross thickness of sealant shared by inorganic system's filler Figure.

Fig. 4 is the schematic diagram of the preparation method for illustrating the evaluation sample in embodiment.

Fig. 5 A~Fig. 5 C are the schematic diagram of the preparation method for illustrating the evaluation sample in embodiment.

Fig. 6 A and Fig. 6 B are the schematic diagram of the preparation method for illustrating the evaluation sample in embodiment.

Symbol description

10,20 electrical storage devices exterior member (exterior member), 11 substrate layers,

12 first bonding agents layer, 13 metal foil layers, 14 corrosion-proof layers,

15 sealants, 16 inorganic system's fillers, 17 second bonding agents layer.

Specific embodiment

Preferred embodiment explained to of the present utility model referring to the drawings.It should be noted that accompanying drawing In to same or considerable part mark same symbol, the repetitive description thereof will be omitted.In addition, the dimensional ratios of accompanying drawing are not limited to diagram Ratio.

[electrical storage device exterior member]

Fig. 1 is the profile of the implementation method for showing schematically electrical storage device exterior member of the present utility model.Such as Shown in Fig. 1 like that, the exterior member (electrical storage device exterior member) 10 of present embodiment is by substrate layer 11, in the base material First bonding agents layer 12, the formation on the face opposite with substrate layer 11 of first bonding agents layer 12 formed in the one side of layer 11 Metal foil layer 13, the metal foil layer 13 and the corrosion-proof layer 14 formed on 12 opposite face of first bonding agents layer, The layered product that the sealant 15 formed on the face opposite with metal foil layer 13 of the corrosion-proof layer 14 is stacked gradually. The substrate layer 11 of exterior member 10 is outermost layer, and sealant 15 is innermost layer.That is, exterior member 10 is so that substrate layer 11 is towards storage The outer side of electric installation, sealant 15 is set to be used towards the private side of electrical storage device.Each layer is illustrated below.

The ＞ of ＜ substrate layers 11

When the heat resistance that substrate layer 11 is in order in sealing process when reply electrical storage device is manufactured is assigned, processed, circulating Purpose as generable pin hole and design, preferably use the resin bed with insulating properties.As such resin bed, energy It is enough that for example the stretching of polyester film, PA membrane, polypropylene screen etc. or unstretching film are laminated as individual layer or by more than 2 layers Multilayer film use.More specifically, can use and use polyethylene terephthalate film (PET) and nylon membrane (Ny) Adhesive resin implements the coextruded multilayer stretched film of stretch processing after being coextruded.

The thickness of substrate layer 11 is preferably 6~40 μm, more preferably 10~25 μm.If the thickness of substrate layer 11 is 6 μm More than, there is the tendency of the pinhole resistance and insulating properties that can improve electrical storage device exterior member 10.

12 ＞ of ＜ first bonding agents layer

First bonding agents layer 12 is by the layer be bonded with metal foil layer 13 of substrate layer 11.As composition first bonding agents layer 12 Material, specifically, for example, can enumerate PEPA of sening as an envoy to, PPG, acrylic acid series multiple alcohol, carbonic ester many Polyurethane resin etc. obtained from isocyanate compound the effect more than hosts such as first alcohol and 2 functions.

PEPA is obtained using more than one of more than one and following dihydroxylic alcohols of following binary acid, institute It is the aliphatic such as butanedioic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, tridecandioic acid to state binary acid It is binary acid；The fragrant family binary acid such as M-phthalic acid, terephthalic acid (TPA), naphthalenedicarboxylic acid.The dihydroxylic alcohols is ethylene glycol, third Glycol, butanediol, neopentyl glycol, methyl pentanediol, hexylene glycol, heptandiol, ethohexadiol, nonanediol, decanediol, dodecanediol Etc. fatty family dihydroxylic alcohols；The ester ring type system dihydroxylic alcohols such as cyclohexanediol, hydrogenation benzene dimethanol；The two of the fragrant families such as benzene dimethanol First alcohol.

In addition, as PEPA, the polyester polyols that will be obtained using above-mentioned binary acid and dihydroxylic alcohols can be included The hydroxyl of two ends of alcohol carries out polyester polyurethane polyol of chain etc. using following substances：For example, selected from 2,4- or 2,6- toluene di-isocyanate(TDI)s, XDI, 4,4 '-methyl diphenylene diisocyanate, methylene two are different Cyanate, isopropylidene diisocyanate, LDI, 2,2,4- or 2, the isocyanide of 4,4- tri-methyl hexamethylene two Acid esters, 1,6- hexamethylene diisocyanates, methylcyclohexane diisocyanate, IPDI, 4,4 '-two rings The list of the isocyanate compound among hexyl methane diisocyanate, isopropylidene dicyclohexyl -4,4 '-diisocyanate etc. Body；Or selected from addition body, biuret body, the isocyanuric acid ester that at least one above-mentioned isocyanate compound of the above is constituted Body.

As PPG, it is possible to use make the ether such as polyethylene glycol, polypropylene glycol system's polyalcohol and as chain extender Above-mentioned isocyanate compound effect polyether-polyurethane polyalcohol.

As acrylic acid series multiple alcohol, it is possible to use the acrylic acid series tree being polymerized with above-mentioned acrylic monomer Fat.

As carbonate polyol, carbonate products can be made to be reacted with glycol and obtained.As carbonate products, Dimethyl carbonate, diphenyl carbonate, ethylene carbonate etc. can be used.On the other hand, as dihydroxylic alcohols, can include and use Ethylene glycol, propane diols, butanediol, neopentyl glycol, methyl pentanediol, hexylene glycol, heptandiol, ethohexadiol, nonanediol, decanediol, The aliphatic diols such as dodecanediol；The ester ring type glycol such as cyclohexanediol, hydrogenation benzene dimethanol；The aromatic diols such as benzene dimethanol Deng more than a kind mixture carbonate polyol or using above-mentioned isocyanate compound implement chain increase Polycarbonate polyurethane polyalcohol long.

Above-mentioned various polyalcohols can be according to required by exterior member function, performance and be used alone or by 2 kinds Above and use and use.Alternatively, it is also possible to use above-mentioned isocyanates based compound to be used as solidification by these hosts Agent and used as urethane adhesive.

And then, for the purpose of promoting bonding, carbodiimide compound, oxazolines can be coordinated in above-mentioned polyurethane resin Compound, epoxide, phosphorus compound, silane coupler etc..

As carbodiimide compound, for example, can include N, N '-two-toluoyl base carbodiimide, N, N '-diphenyl Carbodiimide, N, N '-two -2,6- 3,5-dimethylphenyls carbodiimide, N, N '-bis- (2,6- diisopropyl phenyl) carbodiimide, N, N '-dioctyl decyl carbodiimide, N- toluyls-N '-carbodicyclo hexylimide, N, N '-two -2,2- di-tert-butyl-phenyl carbon Diimine, N- toluyls-N '-phenyl carbodiimide, N, the p-nitrophenyls of N '-two carbodiimide, N, the p-aminophenyls of N '-two Carbodiimide, N, the p-hydroxybenzenes of N '-two carbodiimide, N, N '-dicyclohexylcarbodiimide, N, the toluoyl base carbon of N '-two Diimine etc..

Zuo Wei oxazoline compounds, for example, can include 2- oxazolines, 2- methyl -2- oxazolines, 2- phenyl -2- oxazoles Quinoline, 2,5- dimethyl -2- oxazolines, the mono- oxazoline compounds of 2,4- diphenyl -2- oxazoline Deng, 2,2 '-(1,3- phenylene) - Double (2- oxazolines), 2,2 '-(1,2- ethylidene)-bis- (2- oxazolines), 2,2 '-(Isosorbide-5-Nitrae-butylidene)-bis- (2- oxazolines), 2, 2 '-(Isosorbide-5-Nitrae-phenylene)-bis- (2- oxazolines) Deng bisoxazoline compounds.

As epoxide, for example, can include fat as 1,6- hexylene glycols, neopentyl glycol, PAG The diglycidyl ether of the glycol of race, sorbierite, sorbitan, polyglycereol, pentaerythrite, two glycerine, glycerine, trihydroxy methyl It is the polyglycidyl ether of the ester ring type polyalcohol such as polyglycidyl ether, cyclohexanedimethanol of the aliphatic polyols such as propane, right The aliphatic such as phthalic acid, M-phthalic acid, naphthalene dicarboxylic acids, trimellitic acid, adipic acid, decanedioic acid, aromatic polybasic carboxylic acid 2-glycidyl ester or many ethylene oxidic esters, resorcinol, double-(p-hydroxybenzene) methane, 2,2- it is double-(p-hydroxybenzene) The diglycidyl ethers of polyhydric phenols or many such as propane, three-(p-hydroxybenzene) methane, 1,1,2,2- tetra- (p-hydroxybenzene) ethane Glycidol ether, N, N '-diglycidylaniline, N, N, N- diglycidyl toluidines, N, N, N ', N '-four shrinks sweet Oil base-bis--N- the glycidyl derivatives of amine, triglycidyl group of amino phenols as (p-aminophenyl) methane derives Thing, triglycidyl group three (2- hydroxyethyls) isocyanuric acid ester, triglycidyl isocyanurate, orthoresol type asphalt mixtures modified by epoxy resin Fat, phenol novolak type epoxy resin.

As phosphorus compound, for example, can include phosphorous acid three (2,4- di-tert-butyl phenyl) ester, four (2,4- di-tert -s Butyl phenyl) 4, it is 4 '-biphenylene phosphinate, double (2,4- di-tert-butyl phenyl) pentaerythrites-two-phosphite ester, double (2,6- di-tert-butyl -4- aminomethyl phenyls) pentaerythrite-two-phosphite ester, 2,2- di-2-ethylhexylphosphine oxides (4,6- di-tert-butyl benzenes Base) octyl group phosphite ester, 4,4 '-butylidene-bis- (3- methyl-6-tert-butyl phenyls-two-tridecyl) phosphite ester, 1,1, 3- tri- ((tridecyl) phosphite ester -5- tert-butyls of 2- methyl -4- two-phenyl) butane, three (the single nonyl of mixing and dinonyl Phenyl) phosphite ester, three (nonyl phenyl) phosphite esters, 4,4 '-isopropylidene double (phenyl-dialkyl phosphites) etc..

As silane coupler, for example, can use VTES, (the 'beta '-methoxy ethoxy of vinyl three Base) silane, γ-methacryloxypropyl trimethoxy silane, vinyltriacetoxy silane, γ-glycidol oxygen Base propyl trimethoxy silicane, γ-glycidoxypropyl triethoxysilane, β-(3,4- epoxycyclohexyl) ethyl front three TMOS, γ-chloropropylmethoxysilane, vinyl trichlorosilane, γ mercaptopropyitrimethoxy silane, gamma-amino third The various silane couplers such as ethyl triethoxy silicane alkane, N- β (amino-ethyl)-gamma-amino propyl trimethoxy silicane.

In addition, the performance according to required by bonding agent, can coordinate other various additions in above-mentioned polyurethane resin Agent, stabilizer.

To first bonding agents layer 12 thickness be not particularly limited, from obtain desired adhesive strength, tracing ability and add From the viewpoint of work etc., for example, it is preferable to be 1~10 μm, more preferably 3~7 μm.

The ＞ of ＜ metal foil layers 13

Metal foil layer 13 has the water vapor barrier property of the inside for preventing moisture from immersing electrical storage device.In addition, metal foil layer 13 have ductility to carry out deep-draw shaping.As metal foil layer 13, it is possible to use the various metal foils such as aluminium, stainless steel, From quality (proportion), moisture resistance, processability and cost aspect, preferably aluminium foil.

As aluminium foil, it is possible to use general soft aluminium foil, but during in order to assign further pinhole resistance and shaping Ductility, preferably uses the aluminium foil comprising iron.Counted by 100 mass % of aluminium foil, the content of iron is preferably 0.1~9.0 in aluminium foil Quality %, more preferably 0.5~2.0 mass %.Content by iron is more than 0.1 mass %, can be obtained with more excellent Pinhole resistance and ductility exterior member 10.Content by iron is below 9.0 mass %, can obtain flexibility more Excellent exterior member 10.

In addition, as aluminium foil, from the aspect of ductility when can assign desired shaping, more preferably implementing The soft aluminium foil (aluminium foil being for example made up of 8021 materials described in JIS standards, 8079 materials) of annealing.

Thickness to metal foil layer 13 is not particularly limited, but considers barrier, pinhole resistance, processability, is preferably set to 9~200 μm, more preferably it is set to 15~100 μm.

In the case where aluminium foil is used for into metal foil layer 13, as aluminium foil, it is possible to use untreated aluminium foil, but from imparting From the point of view of in terms of electrolyte resistance, the aluminium foil for implementing ungrease treatment is preferably used.As ungrease treatment, if generally distinguish Words can enumerate wet type ungrease treatment and dry type ungrease treatment.

As wet type ungrease treatment, sour degreasing, alkali degreasing etc. can be included.As the acid that sour degreasing is used, for example may be used The inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid are included, these inorganic acids can be used alone, also can be by two or more simultaneously With.In addition, from from the viewpoint of the etch effect for improving aluminium foil, can as needed with the confession for synthesizing Fe ions, Ce ions etc. To the various slaines in source.The alkali used as alkali degreasing, for example, can include the strong etch pattern such as NaOH.In addition, can To use the material for having coordinated the material of weak base system, surfactant.The degreasing of these materials uses infusion process, spraying process Come carry out.

As dry type ungrease treatment, the side that ungrease treatment is carried out in the operation made annealing treatment to aluminium can be included Method.In addition, in addition to ungrease treatment, flame treatment, sided corona treatment etc. can also be carried out.And then, can also include using photograph The ultraviolet of penetrating specific wavelength and the active oxygen that produces are by polluter oxidation Decomposition and the ungrease treatment for removing.

It should be noted that in the case of carrying out ungrease treatment to aluminium foil, one side that can be only to aluminium foil implements ungrease treatment, Also ungrease treatment can be implemented to two sides.

The ＞ of ＜ corrosion-proof layers 14

Corrosion-proof layer 14 is the hydrogen fluorine in order to prevent from being produced by electrolyte or by the reaction of electrolyte and moisture The corrosion of the metal foil layer 13 caused by acid and the layer that sets.Corrosion-proof layer 14 is for example converted by ungrease treatment, hot water Combinations for the treatment of, anodized, chemical conversion treatment or these treatment are formed.Corrosion-proof layer can be in metal foil layer Formed on the face of 13 12 side of first bonding agents layer, can also be formed on the two sides of metal foil layer 13.On the two sides of metal foil layer 13 In the case of foring corrosion-proof layer, two compositions of corrosion-proof layer can be with identical, also can be different.

As ungrease treatment, sour degreasing or alkali degreasing can be included.As sour degreasing, can include using sulfuric acid, nitric acid, Independent or their mixed liquor method of the inorganic acids such as hydrochloric acid, hydrofluoric acid etc..In addition, as sour degreasing, by using with Above-mentioned inorganic acid makes the sour degreasing agent that the fluorochemicals such as a sodium fluoram dissolve, and aluminium foil particularly is being used for into metal In the case of layers of foil 13, the fluoride of the degreasing effect and the aluminium for passive state that do not only have aluminium can be formed, in hydrofluoric acid resistance Aspect is effective.As alkali degreasing, the method using NaOH etc. can be included.

As hot water conversion processing, for example, can include and aluminium foil is impregnated in the boiling water for the addition of triethanolamine The boehmite treatment for the treatment of.

As anodized, for example, can include alumite (alumite) treatment.

As chemical conversion treatment, immersion-type, application type can be included.As the chemical conversion treatment of immersion-type, for example, can include Chromic acid salt treatment, zirconium treatment, titanium treatment, vanadium treatment, molybdenum treatment, the treatment of phosphoric acid Calcium treatment, strontium hydroxide, cerium treatment, ruthenium treatment Or the various chemical conversion treatments of the mixing phase composition by them.On the other hand, as the chemical conversion treatment of application type, can include The method of smears of the coating with Corrosion Protection on metal foil layer 13.

In these anti-corrosion treatments, in any one formation using hot water conversion processing, anodized, chemical conversion treatment In the case of at least a portion of corrosion-proof layer, above-mentioned ungrease treatment is preferably carried out in advance.It should be noted that making With the metal foil of ungrease treatment as metal foil layer 13 in the case of, it is not necessary to re-started in the formation of corrosion-proof layer Ungrease treatment.

The smears used in the chemical conversion treatment of application type preferably comprises trivalent chromium.In addition, choosing can be contained in smears At least a kind polymer in the group that freely cation property copolymer described later and anionic polymer are constituted.

In addition, in above-mentioned treatment, particularly hot water conversion processing, anodized inorganic agent are to make aluminium foil surface molten Solution, the aluminium compound (boehmite, alumite) for forming excellent corrosion resistance.Therefore, because as from having used aluminium foil Metal foil layer 13 forms the form of co-continuous structure to corrosion-proof layer 14, therefore is contained in the definition of chemical conversion treatment, But can also be formed at anticorrosion only with the pure coating gimmick being not included in as described later in the definition of chemical conversion treatment Reason layer 14.As the method, for example, can include as the anticorrosion ability (inhibitor effect) with aluminium and in environment side Material that face also is adapted for and use the colloidal sol of average grain diameter rare earth element system oxide as the cerium oxide of below 100nm Method.By using the method, that is, use general coating method, it is also possible to anticorrosion effect is assigned to metal foils such as aluminium foils Really.

As the colloidal sol of above-mentioned rare earth element system oxide, for example, can include and use water system, alcohol system, hydrocarbon system, ketone The colloidal sol of the various solvents of system, ester system, ether system etc..Wherein, the preferred colloidal sol of water system.

In the colloidal sol of above-mentioned rare earth element system oxide, generally for its dispersion stability is made, nitric acid, salt can be used The organic acid such as the inorganic acids such as acid, phosphoric acid or its salt, acetic acid, malic acid, ascorbic acid, lactic acid is used as stably dispersing agent.These In stably dispersing agent, can particularly expect phosphoric acid that there are following effects in exterior member 10：(1) stably dispersing of colloidal sol Change, (2) make use of phosphoric acid aluminium sequestering power with raising, (3) of the adaptation of metal foil layer 13 by catching because of hydrofluoric acid Imparting, (4) of influence and electrolyte resistance produced by the aluminium ion (passive state is formed) of dissolution are even if by also easy at low temperature The dehydrating condensation that causes phosphoric acid and raising of cohesiveness of corrosion-proof layer 14 (oxide skin(coating)) for producing etc..

As above-mentioned phosphoric acid or its salt, orthophosphoric acid, pyrophosphoric acid, metaphosphoric acid or their alkali metal salt, ammonium can be included Salt.Wherein, the condensed phosphoric acid such as three metaphosphoric acids, four metaphosphoric acids, hexa metaphosphoric acid, super metaphosphoric acid or their alkali metal salt and ammonium salt It is preferred that function in exterior member 10 is manifested.In addition, if consideration is adopted using the colloidal sol of above-mentioned rare-earth oxide Film making properties (drying capacity, heat are dried when forming the corrosion-proof layer being made up of rare-earth oxide with various rubbing methods Amount), from low temperature under dehydrating condensation it is excellent from the aspect of, more preferably sodium salt.As phosphate, preferably water miscible salt.

Phosphoric acid (or its salt) is relative to the match ratio of rare earth element oxide：Relative to rare earth element oxide 100 mass parts, preferably 1~100 mass parts.If above-mentioned match ratio is 1 relative to the mass parts of rare earth element oxide 100 More than mass parts, then rare earth element oxide sol becomes more to stablize, and the function of exterior member 10 becomes more good.On It is more than 5 mass parts that match ratio is stated more preferably relative to the mass parts of rare earth element oxide 100.In addition, if above-mentioned cooperation Than being the then function of rare earth element oxide sol below 100 mass parts relative to the mass parts of rare earth element oxide 100 Improve, prevent the excellent performance of the etch of electrolyte.Above-mentioned match ratio is more preferably relative to the mass of rare earth element oxide 100 Part is below 50 mass parts, below more preferably 20 mass parts.

The corrosion-proof layer 14 formed by above-mentioned rare-earth oxide colloidal sol due to the aggregate for inorganic particulate, therefore Even across the operation of dry solidification, the cohesiveness of layer itself is also possible to reduce.Therefore, at for the anticorrosion of this situation Reason layer 14, in order to supplement cohesiveness, its Composite is made preferably by following anionic polymers or cation property copolymer.

As anionic polymer, the polymer with carboxyl can be included, for example, can include poly- (methyl) propylene Sour (or its salt) or the copolymer of copolymerization is carried out as principal component using poly- (methyl) acrylic acid.As the copolymer Copolymer composition, can include (methyl) alkyl acrylate system monomer (as alkyl, can include methyl, ethyl, n-propyl, Isopropyl, normal-butyl, isobutyl group, the tert-butyl group, 2- ethylhexyls, cyclohexyl etc.)；(methyl) acrylamide, N- alkyl (methyl) Acrylamide, N, N- dialkyl group (methyl) acrylamide (as alkyl, can include methyl, ethyl, n-propyl, isopropyl, just Butyl, isobutyl group, the tert-butyl group, 2- ethylhexyls, cyclohexyl etc.), N- alkoxies (methyl) acrylamide, N, N- dialkoxies (methyl) acrylamide, (as alkoxy, methoxyl group, ethyoxyl, butoxy, isobutoxy etc. can be included), N- methylols The monomers containing acylamino- such as (methyl) acrylamide, N- phenyl (methyl) acrylamide；(methyl) acrylic acid 2- hydroxy methacrylates, The monomers containing hydroxyl such as (methyl) acrylic acid 2- hydroxy propyl esters；(methyl) glycidyl acrylate, allyl glycidol The monomer containing glycidyl such as base ether；(methyl) acryloxypropyl trimethoxy silane, (methyl) acryloxy The monomer containing silane such as propyl-triethoxysilicane；(methyl) acryloxypropyl isocyanates etc. contains NCO Monomer etc..

These anionic polymers are played to be made using corrosion-proof layer obtained from rare earth element oxide sol The stability-enhanced effect of 14 (oxide skin(coating)s).This is to protect hard and crisp oxide skin(coating) by with acrylic resin composition Effect and catch from phosphatic ionic contamination (particularly sodium ion) contained in rare-earth oxide colloidal sol (sun Ion capturing agent) effect realizes.That is, if the corrosion-proof layer obtained from using rare earth element oxide sol Containing the particularly alkali metal ion such as sodium, alkaline-earth metal ion in 14, then make to prevent with the place comprising the ion as starting point Corrosion treatment layer 14 becomes easily deterioration.Therefore, by will be contained in rare-earth oxide colloidal sol with anionic polymer The immobilizations such as sodium ion, so that the tolerance of corrosion-proof layer 14 is improved.

The corrosion-proof layer 14 that anion based polymer and rare earth element oxide sol are combined have with The equal Corrosion Protection of the corrosion-proof layer 14 that chromic acid salt treatment is implemented to aluminium foil and is formed.Anionic polymer is excellent Elect the structure that will be essentially water miscible polyanion based polymer crosslinking as.Used as in the formation of the structure Crosslinking agent, can for example include with NCO, glycidyl, carboxyl, oxazolinyls compound.

As the compound with NCO, for example, can include toluene di-isocyanate(TDI), phenylenedimethylidyne two different It is cyanate or its hydride, hexamethylene diisocyanate, 4,4 '-methyl diphenylene diisocyanate or its hydride, different The diisocyanates such as isophorone diisocyanate；Or make the polyol reactions such as these isocyanates and trimethylolpropane The polyisocyanate such as addition product, biuret body obtained from by being reacted with water or the isocyanuric acid ester body as tripolymer Cyanate；Or by the blocked polyisocyanates of the closures such as these polyisocyanates alcohols, lactams, oximes Deng.

As the compound with glycidyl, for example, can enumerate ethylene glycol of sening as an envoy to, diethylene glycol (DEG), triethylene glycol, poly- second two The glycols such as alcohol, propane diols, DPG, tripropylene glycol, polypropylene glycol, BDO, 1,6- hexylene glycols, neopentyl glycol with The epoxide of epichlorohydrin effect；Make the polyalcohols such as glycerine, polyglycereol, trimethylolpropane, pentaerythrite, sorbierite The epoxide that class is acted on epichlorohydrin；Make the dicarboxylic acids such as phthalic acid, terephthalic acid (TPA), oxalic acid, adipic acid with Epoxide of epichlorohydrin effect etc..

As the compound with carboxyl, for example, can include various aliphatic or aromatic dicarboxylic acid etc..In addition, Poly- (methyl) acrylic acid, poly- (methyl) acrylic acid alkali (great soil group) slaine can be used.

As the compound of Ju You oxazolinyls, can for example include with Shang 2 Yi oxazoline unit it is degraded Make (methyl) acrylic acid, (methyl) third in the case of compound or the polymerizable monomer as using Yi Bing Xi oxazolins The compound of the acrylic monomer copolymerization such as olefin(e) acid Arrcostab, (methyl) acrylic acid hydroxy alkyl ester.

In addition, in anionic polymer, amine can be made to be reacted with functional group selectivity, made as silane coupler Crosslinking points turn into siloxanes key.In this case, it is possible to use γ-glycidoxypropyltrime,hoxysilane, γ-epoxy third Epoxide propyl-triethoxysilicane, β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane, γ-chloropropylmethoxysilane, Vinyl trichlorosilane, γ mercaptopropyitrimethoxy silane, γ aminopropyltriethoxy silane, N- β (amino-ethyl)- Gamma-amino propyl trimethoxy silicane, γ-NCO propyl-triethoxysilicane etc..Wherein, particularly when consideration and the moon Ionic polymers or its copolymer it is reactive when, preferably epoxy silane, amino silane, isocyanato silanes.

These crosslinking agents are relative to the ratio of anionic polymer：Relative to the mass parts of anionic polymer 100, Preferably 1~50 mass parts, more preferably 10~20 mass parts.If the ratio of crosslinking agent is relative to anionic polymer 100 mass parts are more than 1 mass parts, to be then easily adequately formed cross-linked structure.If the ratio of crosslinking agent be relative to the moon from The sub- mass parts of property polymer 100 are the then working life raising of coating liquid below 50 mass parts.

The method that anionic polymer is crosslinked is not limited to above-mentioned crosslinking agent, or titanium, zirconium compounds is used Form method of ionomer etc..

As cation property copolymer, the polymer with amine can be included, polyethyleneimine can be included, by polyethylene Ion high-molecular complex that imines and the polymer with carboxylic acid are formed, in acrylic acid series main framing form grafting of primary amines The cation property copolymer such as grafting of primary amines acrylic resin, polyallylamine or their derivative, amino phenols.

Cation property copolymer preferably can be with the functional group of amine/imine reaction with carboxyl, glycidyl etc. Crosslinking agent is used in combination.As the crosslinking agent with cation property copolymer, it is also possible to using with polyethyleneimine formed from The polymer of the carboxylic acid of sub- high-molecular complex, can for example include the polycarboxylic acids such as polyacrylic acid or its ion salt (salt) or The polysaccharides with carboxyl such as copolymer, carboxymethylcellulose calcium or its ion salt of comonomer have been imported among them Deng.As polyallylamine, for example, can include allylamine, allylamine amido sulfuric acid salt, diallylamine, dimethyl allylamine etc. Homopolymers or copolymer etc..Can be free amine, or the stabilisation formed with acetic acid or hydrochloric acid for these amine Thing.In addition, as copolymer composition, it is also possible to use maleic acid, sulfur dioxide etc..And then can also use by making primary amine Part methoxylation and impart thermally crosslinkable type, alternatively, it is also possible to use amino phenols.Particularly preferred allylamine or its spread out It is biological.

In present embodiment, cation property copolymer is also recited as constituting an inscape of corrosion-proof layer 14.Its Reason for this is that, using for assigning electrolyte resistance, variousization of hydrofluoric acid resistance required by electrical storage device exterior member Compound has made intensive studies, and as a result distinguishes that cation property copolymer itself is also that can assign electrolyte resistance, hydrofluoric acid resistant The compound of property.Speculate itself main reason is that, by with cationic base catch fluorine ion (anion catching agent), so as to press down Aluminium foil damage is made.

Cation property copolymer is also highly preferred material in terms of cementability is improved.In addition, cationic is polymerized Thing more preferably forms cross-linked structure and assigns water resistance due to being water solubility in the same manner as above-mentioned anionic polymer. Crosslinking agent when cross-linked structure is formed in cation property copolymer can use anionic polymer is illustrated above Content in illustrated crosslinking agent.In the case where rare-earth oxide colloidal sol is used as into corrosion-proof layer, as its guarantor Sheath, can be used cation property copolymer to come instead of using above-mentioned anionic polymer.

Corrosion-proof layer 14 with aluminium foil due to forming obtained from by being processed as the chemical conversion treatment for representing with chromate Incline structure, therefore especially using having coordinated the chemical conversion treatment agent of hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid or their salt to aluminium Paper tinsel implementation is processed, and chromium system or the compound of non-chromium is played a role, so as to chemical conversion treatment layer is formed on aluminium foil. But, above-mentioned chemical conversion treatment due in chemical conversion treatment agent using acid, therefore deterioration with operating environment and apparatus for coating Corrosion.On the other hand, the corrosion-proof layer 14 of foregoing application type is different from the chemical conversion treatment for being processed as representing with chromate, Incline structure need not be formed for the metal foil layer 13 for having used aluminium foil.Therefore, the proterties of smears will not be subject to acid, alkali The restriction of property, neutrality etc., can realize good operating environment.Additionally, from environmental sanitation, require replacement case in terms of examine Consider, using the chromic acid salt treatment of chromium compound it is also preferred that the corrosion-proof layer 14 of application type.

Content more than, as the example of the combination of the anti-corrosion treatment of above-mentioned application type, can include (1) Only rare-earth oxide colloidal sol, (2) only have anionic polymer, (3) and only have cation property copolymer, (4) terres rares oxygen (stacking is multiple for compound colloidal sol+anionic polymer (stacking Composite), (5) rare-earth oxide colloidal sol+cation property copolymer Combination), (6) (rare-earth oxide colloidal sol+anionic polymer：Stacking Composite)/cation property copolymer (multiple stratification), (7) (rare-earth oxide colloidal sol+cation property copolymer：Stacking Composite)/anionic polymer (multiple stratification) etc..Its In, preferred (1) and (4)~(7), particularly preferred (4)~(7).But, present embodiment is not limited to combinations thereof.For example, As the example of the selection of anti-corrosion treatment, cation property copolymer due to from it is aftermentioned to sealing adhesive linkage (sealant or Second bonding agents layer) modified polyolefin resin cited in the explanation that is carried out the good aspect of cementability from the point of view of be very Preferred material, therefore in the case where sealing adhesive linkage is constituted with modified polyolefin resin, can be with sealing adhesive linkage The face for connecting sets cation property copolymer (for example constituting the composition of (5) and (6) etc.) such design.

In addition, corrosion-proof layer 14 is not limited to above-mentioned layer.For example, can technology as is commonly known application type chromium Hydrochlorate like that, is formed using the inorganic agent of phosphoric acid and chromium compound has been coordinated in resinoid bond (amino phenols etc.). If using the inorganic agent, the layer for having both corrosion proof function and adaptation concurrently can be formed.Further it is necessary to consider coating liquid Stability, but can use rare-earth oxide colloidal sol is single in advance with polycationic polymer or polyanion polymer Smears obtained from component has the layer of both corrosion proof function and adaptation concurrently to be formed.

The quality of the per unit area of corrosion-proof layer 14 in the case of any one of sandwich construction or single layer structure all Preferably 0.005~0.200g/m², more preferably 0.010~0.100g/m².If the quality of above-mentioned per unit area is 0.005g/m²More than, then easily assign corrosion proof function to metal foil layer 13.Even if in addition, the quality of above-mentioned per unit area More than 0.200g/m², corrosion proof function also less changes.On the other hand, in the case where rare-earth oxide colloidal sol has been used, If applying thickness, the solidification caused by heat during as drying becomes insufficient, it is possible to the decline of cohesiveness.Need explanation , for the thickness of corrosion-proof layer 14, can be converted by its proportion.

The ＞ of ＜ sealants 15

Sealant 15 is the layer that the sealing produced by heat-sealing is assigned to exterior member 10.As the material for constituting sealant 15 Matter, for example, can include vistanex or acid-modified polyolefin resin.It should be noted that (that is, not having in exterior member 10 There is the composition of second bonding agents layer 17 described later：Heat lamination) in the case of, when sealant 15 is individual layer, preferably use acid modified Vistanex (SPP).In addition, sealant 15 be multilayer when, preferably at least with the metal foil layer 13 as outermost layer side The side for connecting uses acid-modified polyolefin resin, in other layers, vistanex and acid-modified polyolefin resin can be used Any one.And in exterior member described later 20 (that is, with the composition of second bonding agents layer 17：Dry lamination) in the case of, The layer for not relying on sealant 15 constitutes (single or multiple lift), can be modified poly- using vistanex and acid in whole layers Any one of olefin resin.

Acid-modified polyolefin resin is that acidic groups is imported into resin obtained from vistanex.As acidic groups, can arrange Enumerate carboxyl, sulfonic group etc., particularly preferred carboxyl.Sour modified polyolefin obtained from vistanex has been imported as by carboxyl Hydrocarbon resin, the ester that can for example enumerate send as an envoy to unsaturated carboxylic acid or its acid anhydrides or unsaturated carboxylic acid or its acid anhydrides draws in free radical The acid-modified polyolefin resin of graft modification is carried out in the presence of hair agent to vistanex.Below sometimes by unsaturated carboxylic The ester of acid or its acid anhydrides and unsaturated carboxylic acid or its acid anhydrides is collectively referred to as graft compound.

It should be noted that as vistanex, low density polyethylene (LDPE), medium density polyethylene, high density can be included Polyethylene, ethylene-alpha-olefin copolymer, homo-polypropylene, block polypropylene, random polypropylene, propylene-alpha olefin copolymer etc..

As unsaturated carboxylic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, lemon health can be included Acid, tetrahydrophthalic acid, bicyclic [2,2,1] hept-2-ene" -5,6- dicarboxylic acids etc..As the acid anhydrides of unsaturated carboxylic acid, can enumerate Go out maleic anhydride, itaconic anhydride, citraconic anhydride, tetrabydrophthalic anhydride, bicyclic [2,2,1] hept-2-ene" -5,6- dicarboxylic anhydrides Deng.As unsaturated carboxylic acid or the ester of its acid anhydrides, methyl acrylate, methyl methacrylate, methacrylic acid second can be included Ester, butyl methacrylate, dimethyl maleate, monomethyl maleate, DEF, dimethyl itaconate, citraconic acid Diethylester, tetrabydrophthalic anhydride dimethyl ester, bicyclic [2,2,1] hept-2-ene" -5,6- dimethyl dicarboxylates etc..

The ratio of the graft compound in acid-modified polyolefin resin is：Relative to the mass parts of vistanex 100, preferably It is 0.2~100 mass parts.The temperature conditionss of graft reaction are preferably 50~250 DEG C, more preferably 60~200 DEG C.Reaction time Also by manufacture method or so, but in the case where melting graft reaction is carried out using double screw extruder, the reaction time is preferred For in the holdup time of extruder.In particular, it is preferred that being 2~30 minutes, more preferably 5~10 minutes.Graft reaction can be with Normal pressure, pressurization it is any under the conditions of implement.

As radical initiator, organic peroxide can be included.As organic peroxide, for example, can include Oxidation of alkyl, peroxidating aryl, acyl peroxide, ketone peroxide, peroxy ketal, peroxy carbonates, perester, hydroperoxides Deng.These organic peroxides can suitably be selected according to temperature conditionss and reaction time.Squeezed in above-mentioned use twin-screw In the case of going out the melting graft reaction that machine is carried out, preferably alkyl, peroxy ketal, perester, more preferably peroxidating two The tert-butyl group, 2,5- dimethyl -2,5- di-tert -s butyl peroxy-hexin -3, dicumyl peroxide.

Used as acid-modified polyolefin resin, preferably with maleic anhydride modified vistanex, for example Mitsui Chemicals is public " ADMER ", " MODIC " of Mitsubishi Chemical Ind's manufacture of manufacture etc. is taken charge of to be adapted to.Such acid-modified polyolefin resin composition by In with various metals, the polymer with various functional groups it is reactive excellent, therefore, it is possible to using the reactivity and to seal Layer 15 assigns adaptation, it is possible to increase electrolyte resistance.

Sealant 15 contains inorganic system's filler 16.For inorganic system's filler 16, it is desirable to insulating properties, electrolyte resistance, heat-resisting Property the heat of reply when heat-sealing (), hardness (pressure during reply heat-sealing), (reply is by electrolyte and water reaction produced for acid resistance Hydrogen fluoride) etc. characteristic, preferably further requirement thermal conductivity (can low-temperature heat-sealing, can expect as the radiating of battery Property).

As inorganic system's filler 16, can include by aluminum oxide, silica, magnesia, zirconium oxide, calcium carbonate, zirconium silicate, The filler of the compositions such as zinc oxide, titanium oxide, tin oxide, iron oxide, antimony oxide, boron nitride, aluminium nitride, silicon nitride.Among these, From from the viewpoint of electrolyte resistance, acid resistance, heat resistance, hardness, thermal conductivity, preferably aluminum oxide or boron nitride.

It should be noted that inorganic system's filler 16 be as comprising 1 filler (independent filler), 2 fillers (fill out by cohesion Material) both term define.As the shape (shape of independent filler) of inorganic system's filler 16, it is not particularly limited, can Preferably to use the filler of the shape such as spherical, tabular, needle-like, fiber, column, unsetting.For example, as inorganic system's filler 16, In the case where spherical filler is employed, its average primary particle diameter can be made to be 0.5~20 μm or so.

These inorganic system's fillers 16 are more preferably the inorganic system's filler being surface-treated.If using silane coupled material Deng surface treatment is implemented to inorganic system's filler 16, then the adaptation raising of the resin and inorganic system's filler 16 of sealant 15 is constituted, Resin Flow reduction during melting can further be made.Thus, even if being applied with heat in heat-sealing, in the case of pressure, The flowing of resin can be suppressed, short circuit is prevented from.It should be noted that for surface treatment, also in the presence of following viewpoint：Easily Prevent inorganic system's filler 16 from being come off from sealant 15.

In present embodiment, in the section along stacked direction of electrical storage device exterior member, relative to sealant Ratio for 15 gross thickness shared by these inorganic system's fillers 16 is 5~50%.Thus, even if thin layer in sealant 15 In the case of, it is also possible to maintain good insulating properties.Its reason is illustrated briefly below.

Due to making heat, pressure during heat-sealing during electrical storage device, it is however generally that melting can occur in sealant 15, squeeze It is broken.For example, in the sealing of top, due to there is sealant 15 melting, rack, therefore the distance of lug lead and metal level becomes Closely, it is susceptible to short circuit.In this regard, by the inorganic system's filler 16 that there is ormal weight in sealant 15, even if so that apply heat, Pressure, it is also difficult to the melting of sealant 15 occurs, racks, can be produced between lug lead and metal level more than certain away from From.Thereby, it is possible to suppress the generation of short circuit.

In addition, if the thin layer of sealant 15 is developed, then the single resistance of layer diminishes, therefore due to the change of thickness Change, a small amount of crackle, insulating properties are also easily reduced.Especially, it is thus identified that be considered heat-sealing when (top sealing, side seal and Degassing heat-sealing) thickness change produce influence short circuit.Therefore, by adding inorganic system's filler 16, protected so as to be played in filler While holding the effect in gap, intermolecular interaction can be utilized to suppress the resin flowing that melting during by sealing causes, can To prevent short circuit.

If it should be noted that the ratio for the gross thickness of sealant 15 shared by inorganic system's filler 16 is less than 5%, then become insufficient as the effect of sept, because lug lead and metal level are approached, it is therefore possible to be short-circuited. In addition, if the ratio is bigger than 50%, because the content of filler is excessive, therefore formation sealant 15 becomes difficult, simultaneously because Contact area diminishes, the cementability reduction of interlayer.In addition, heat seal strength reduction.From such a viewpoint, aforementioned proportion is more excellent Elect 20~30% as.

When on the basis of the gross mass of sealant 15, the content of inorganic system's filler 16 is preferably 5~35 mass %.If contained Amount is less than 5 mass %, then become insufficient as the effect of sept, and because lug lead and metal level are close, therefore have can Can be short-circuited.In addition, if content is few, then the viscosity of sealant 15 is easily reduced, and there is control mobility becomes difficulty Tendency.On the other hand, if the content is more than 35 mass %, because contact area tails off, therefore cementability is easily reduced.Separately Outward, because heat seal strength is easily reduced, the excess stickiness of sealant 15 is raised, therefore inclining of having that masking processability is easily reduced To.From such a viewpoint, the content of inorganic system's filler 16 is more preferably 15~25 mass %.

Sealant 15 can be monofilm, or make multilayer laminated multilayer film.According to required function, example Such as, from from the aspect of assigning moisture resistance, can be used and there is the resins such as ethylene-cyclic olefin copolymer, polymethylpentene therebetween Multilayer film.

In present embodiment, it is preferred to use following manner：Sealant 15 is made up of the layer of more than 2, at least 1 layer therein Without inorganic system's filler 16.Sealant 15 is constituted by with more than 2 layers of multilayer, for without the inorganic system's filler 16 of addition Layer, is not in that, by the reduction containing the original characteristic of sealant 15 caused by inorganic system's filler 16, can manifest insulation Property.

The thickness of the layer containing inorganic system's filler 16 is preferably more than 50% relative to the gross thickness of sealant 15.If contained There is the gross thickness of the thickness relative to sealant 15 of layer of inorganic system's filler less than 50%, be then applied with heat, pressure in heat-sealing In the case of, there is the flowing for being susceptible to resin, the tendency for being susceptible to short circuit.Therefore, the ratio be more preferably 60% with On.It should be noted that obtained from order to enjoy by making sealant 15 for multilayer, setting the layer without inorganic system's filler Above-mentioned advantage, can make the higher limit of the ratio reach 90%.

In the case that sealant 15 is made up of the layer of more than 2, the layer for preferably comprising inorganic system's filler 16 is held in not Layer (such as the intermediate layer in 3 layers composition) containing inorganic system's filler 16.Thereby, it is possible to manifest the cementability with metal foil layer 13, Manifest insulation characterisitic in the case where heat seal property is not hindered.It should be noted that being for example made the sealing of such 3 layers of composition In the case of layer 15, naturally it is also possible to configure in outer layer side or internal layer side the layer containing inorganic system's filler 16, but the former In the case of there is the tendency that is easily reduced with the cementability of metal foil layer 13, there is sealing intensity in the latter case and easily drop Low tendency.

In the case that sealant 15 is made up of the layer of more than 2, each layer can be suitably used each composition of described above To be separately formed.That is, the resin material for for example constituting each layer can be with identical, it is also possible to which different, the thickness of each layer can be with identical Can also be different.But, though from improve with the adaptation of inorganic system's filler 16, apply heat, pressure in heat-sealing in the case of Also it is easy to ensure that from the viewpoint of lazy flow, the layer preferably at least containing inorganic system's filler 16 is to be formed by acid modified polyolefin Layer.

Various additives can be coordinated in sealant 15, such as fire retardant, slipping agent, antiblocking agent, antioxidant, light are steady Determine agent, tackifier etc..

The thickness of sealant 15 is preferably 10~100 μm, more preferably 20~50 μm.It is made up of multilayer in sealant 15 In the case of, the aggregate thickness (gross thickness) of preferably each layer is within the range.

Preferred embodiment having been described in detail to electrical storage device exterior member of the present utility model, but this reality above Such particular implementation is not limited to new, the main idea of the present utility model recorded in patent claims In the range of, various modifications and change can be carried out.

For example, showing that the face in the side of sealant 15 of metal foil layer 13 forms the feelings of corrosion-proof layer 14 in Fig. 1 Shape, but also corrosion-proof layer 14 can be formed in the face of 12 side of the first bonding agents of metal foil layer 13 layer, can also be in metal foil The two sides of layer 13 forms corrosion-proof layer 14.In the case where the two sides of metal foil layer 13 forms corrosion-proof layer 14, The composition of the corrosion-proof layer 14 formed in 12 side of first bonding agents layer of metal foil layer 13 and the sealing in metal foil layer 13 The composition of the corrosion-proof layer 14 that 15 side of layer are formed can be with identical, also can be different.

In addition, in Fig. 1, showing directly be laminated metal foil layer 13 and sealant 15 (via corrosion-proof layer 14) Situation, but also electrical storage device exterior member 20 second bonding agents layer 17 can be like that used by metal foil layer as shown in Figure 2 13 and sealant 15 be laminated.Second bonding agents layer 17 is illustrated below.

17 ＞ of ＜ second bonding agents layer

Second bonding agents layer 17 is will to form the layer that the metal foil layer 13 and sealant 15 of corrosion-proof layer 14 are bonded. In second bonding agents layer 17, the general bonding agent for metal foil layer 13 and sealant 15 to be bonded can be used.

Have comprising selected from above-mentioned cation property copolymer and anionic polymer in corrosion-proof layer 14 In the case of at least a kind layer of polymer, second bonding agents layer 17 is preferably comprising contained upper with corrosion-proof layer 14 Stating polymer has the layer of compound (hereinafter also referred to " reactive compounds ") of reactivity.

For example, corrosion-proof layer 14 include cation property copolymer in the case of, second bonding agents layer 17 include with Cation property copolymer has the compound of reactivity.In the case where corrosion-proof layer 14 includes anionic polymer, Second bonding agents layer 17 includes the compound with anionic polymer with reactivity.In addition, being wrapped in corrosion-proof layer 14 In the case of cation polymer and anionic polymer, second bonding agents layer 17 is included to be had with cation property copolymer The compound for having reactivity and the compound with anionic polymer with reactivity.But, second bonding agents layer 17 may not Comprising above-mentioned 2 kinds of compounds, can also include has reactivity with both cation property copolymer and anionic polymer Compound." having reactivity " mentioned here refers to form covalent bond with cation property copolymer or anionic polymer. In addition, second bonding agents layer can further include acid-modified polyolefin resin.

There is reactive compound as with cation property copolymer, can include selected from polyfunctional isocyanate's chemical combination At least a kind compound among thing, glycidyl compound, the compound with carboxyl, the compound of Ju You oxazolinyls.

As these polyfunctional isocyanate compounds, glycidyl compound, the compound with carboxyl, Ju You Evil The compound of oxazoline base, can include as making cation property copolymer turn into the crosslinking agent of cross-linked structure and above institute The polyfunctional isocyanate compound that exemplifies, glycidyl compound, the compound with carboxyl, Ju You oxazolinyls Compound etc..Among these compounds, from high with the reactivity of cation property copolymer, examined in terms of easily forming cross-linked structure Consider, preferably polyfunctional isocyanate compound.

As with anionic polymer have reactivity compound, can include selected from glycidyl compound, At least a kind compound among the compound of Ju You oxazolinyls.As these glycidyl compounds, Ju You oxazolinyls Compound, can include as make cation property copolymer turn into cross-linked structure crosslinking agent and above it is illustrated go out Glycidyl compound, the compound of Ju You oxazolinyls etc..Among these compounds, from anionic polymer From the aspect of reactivity is high, preferred glycidyl compound.

In the case where second bonding agents layer 17 is comprising acid-modified polyolefin resin, reactive compounds preferably also change with acid Property vistanex in acidic groups there is reactivity (that is, with acidic groups formed covalent bond).Thus, with corrosion-proof layer Cementability is further improved.Additionally, acid-modified polyolefin resin turns into cross-linked structure, the solvent resistance of exterior member 10 is further Improve.

The content of reactive compounds is：Relative to the acidic groups in acid-modified polyolefin resin, preferably equivalent is to 10 Times equivalent.More than equivalent, reactive compounds fully react with the acidic groups in acid-modified polyolefin resin.It is another Aspect, if it exceeds 10 times of equivalent, become insufficient with the cross-linked structure of acid-modified polyolefin resin, above-mentioned solvent resistance etc. Physical property has the anxiety of reduction.

Acid-modified polyolefin resin is obtained from acidic groups has been imported in vistanex.As acidic groups, can arrange Enumerate carboxyl, sulfonic group etc., particularly preferred carboxyl.As acid-modified polyolefin resin, it is possible to use with as institute in sealant The same resin of the resin that goes out illustrated in the modified polyolefin resin for using.

Can coordinate fire retardant, slipping agent, antiblocking agent, antioxidant, light stabilizer, tackifier in second bonding agents layer 17 Etc. various additives.

It should be noted that in for the general bonding agent for making metal foil layer 13 and the bonding of sealant 15, including sometimes Silane coupler.Because, by coordinating silane coupler, so as to promote bonding, improve adhesive strength.But, if made With the bonding agent for having coordinated silane coupler, because the species of functional group contained in silane coupler is different, it is possible to bonding agent There is side reaction in the composition in layer beyond contained silane coupler, the cross-linking reaction to original target is produced with silane coupler It is raw to hinder.Therefore, in for the bonding agent for making metal foil layer 13 and the bonding of sealant 15, preferably without silane coupler.

By second bonding agents layer 17 include above-mentioned reactive compounds, so as to being polymerized in corrosion-proof layer 14 Thing forms covalent bond, and corrosion-proof layer 14 is improved with the adhesive strength of second bonding agents layer 17.Therefore, in second bonding agents layer In 17, in order to promote bonding, it is not necessary to coordinate silane coupler, second bonding agents layer 17 to be preferably free of silane coupler.

The thickness of second bonding agents layer 17 is preferably 3~50 μm, more preferably 3~10 μm.If second bonding agents layer 17 Thickness more than lower limit, to be then readily available excellent cementability.If the thickness of second bonding agents layer is below higher limit, Then reduce the amount of moisture passed through from the side end face of exterior member.

The electrical storage device composition of exterior member 20 and electrical storage device exterior member 10 beyond second bonding agents layer 17 Equally.It should be noted that the thickness of the sealant 15 in electrical storage device exterior member 20 is according to second bonding agents layer 17 Thickness adjust.Thickness to the sealant 15 in electrical storage device exterior member 20 is not particularly limited, for example, it is preferable to It is 5~100 μm of scope, more preferably 10~80 μm of scope.

[manufacture method of exterior member]

Next, being illustrated to an example of the manufacture method of the exterior member 10 shown in Fig. 1.Need explanation It is that the manufacture method of exterior member 10 is not limited to following method.

The manufacture method of the exterior member 10 of present embodiment includes following operations to generally comprise：In metal foil layer 13 It is upper stacking corrosion-proof layer 14 operation, make substrate layer 11 and metal foil layer 13 laminating operation, be further laminated sealant 15 make the operation and the layered product to obtaining is heat-treated if necessary operation of layered product.

(lamination process of corrosion-proof layer 14 is laminated on metal foil layer 13)

This operation is the operation that corrosion-proof layer 14 is formed for metal foil layer 13.As its method, can include as It is above-mentioned that ungrease treatment, hot water conversion processing, anodized, chemical conversion treatment or applying implenent are implemented to metal foil layer 13 like that There is method of the smears of Corrosion Protection etc..

In addition, in the case where corrosion-proof layer 14 is multilayer, for example, lower layer side (side of metal foil layer 13) can will be constituted The coating fluid (smears) of corrosion-proof layer coat metal foil layer 13, be sintered and after forming ground floor, will constitute The coating fluid (smears) of the corrosion-proof layer of upper layer side coats ground floor, is sintered and forms the second layer.In addition, the Two layers can also form in the lamination process of sealant described later 15.

For ungrease treatment, spraying process or infusion process can be used；For hot water conversion processing, anodized, can adopt Use infusion process；For chemical conversion treatment, infusion process, spraying process, rubbing method etc. can be properly selected according to the type of chemical conversion treatment Carry out.

Rubbing method on the smears with Corrosion Protection, it is possible to use gravure coating process, reverse rubbing method, roller coat The various methods such as method, stick coating method.

As described above, various treatment can carry out one side on any one of the two sides to metal foil layer 13 or one side In the case for the treatment of, its process face is preferable to carry out in the side of the stacking of sealant 15.It should be noted that as requested also can be right Implement above-mentioned treatment in the surface of substrate layer 11.

Coating weight for forming the smears of ground floor and the second layer is preferably 0.005~0.200g/m², more preferably It is 0.010~0.100g/m²。

In addition, in the case where dry solidification is needed, can according to the drying condition of the corrosion-proof layer 14 for using, with Mother metal temperature is that 60~300 DEG C of scope is carried out.

(bonding process of substrate layer 11 and metal foil layer 13)

This operation is will to be provided with the metal foil layer 13 and substrate layer of corrosion-proof layer 14 via first bonding agents layer 12 The operation of 11 laminatings.As the method for laminating, using gimmicks such as dry lamination, non-solvent lamination, wet type laminations, using in composition The material of the first bonding agents layer 12 stated fits both.First bonding agents layer 12 is arranged to be calculated as 1 with drying coated amount~ 10g/m²Scope, more preferably 3~7g/m²In the range of.

(lamination process of sealant 15)

This operation is the operation that sealant 15 is formed in the corrosion-proof layer 14 formd by operation above.Make It is its method, the method that interlayer lamination is carried out to sealant 15 using extrusion laminating machine can be included.And then, it is also possible to by adopting Extrude sealant 15 to be laminated with series connection laminating, coetrusion.

By this operation, obtain shown in Fig. 1 by the layer anticorrosion of 12/ metal foil layer 13/ of the first bonding agents of substrate layer 11/ The order of the sealant 15 of process layer 14/ is by the layered product of each layer stackup.

In addition, in the case where the corrosion-proof layer 14 of multilayer is formed, if possessing and can be coated with extrusion laminating machine The unit of grappling coating, then can be coated with the second layer of corrosion-proof layer 14 with the unit.

(heat treatment step)

This operation is the operation being heat-treated to layered product.It is heat-treated by layered product, it is possible to increase metal Adaptation between the sealant 15 of 13/ corrosion-proof layer of layers of foil 14/, assigns more excellent electrolyte resistance, hydrofluoric acid resistance, In addition, can also obtain the effect of the generation of albinism when the carrying out of the crystallization for suppressing sealant 15, suppression are molded.Cause This, in this operation, preferably carries out being heat-treated to following degree：Do not promote while the adaptation of above-mentioned each interlayer is improved The degree of the crystallization of sealant 15.The temperature-independent of heat treatment in the species of material etc. for constituting sealant 15, as index, It is preferred that be heat-treated in the way of 20~100 DEG C higher than the fusing point of sealant 15 of the maximum temperature reached of layered product, more preferably It is heat-treated in the way of 20~60 DEG C high of the fusing point than sealant 15.If the maximum temperature reached of layered product is less than the model Enclose, then nucleus residual, readily facilitates crystallization.On the other hand, if the maximum temperature reached of layered product exceedes the scope, having can The thermal contraction of such as substrate layer after thermal expansion, the laminating of metal foil can occur, make processability, characteristic reduction.Therefore, it is heat-treated Time Dependent is preferably carried out in treatment temperature with the short time (such as less than 30 seconds).

In addition, for cooling, in order to suppress crystallization, preferably hastily being cooled down.As cooling velocity, preferably 50~100 DEG C/sec or so.

The exterior member 10 of the present embodiment shown in Fig. 1 can like this be manufactured.

Next, being illustrated to an example of the manufacture method of the exterior member 20 shown in Fig. 2.Need explanation , the manufacture method of exterior member 20 is not limited to following method.

The manufacture method of the exterior member 20 of present embodiment is generally constituted comprising following operations：In metal foil layer 13 It is upper stacking corrosion-proof layer 14 operation, substrate layer 11 and metal foil layer 13 are fitted operation, via second bonding agents layer 17 further stacking sealants 15 and make the operation of layered product and the layered product to obtaining carries out the work of maturation process if necessary Sequence.It should be noted that untill the operation that substrate layer 11 is fitted with metal foil layer 13, can be with above-mentioned exterior member 10 manufacture method is similarly carried out.

(lamination process of second bonding agents layer 17 and sealant 15)

This operation is the corrosion-proof layer that sealant 15 is fitted in metal foil layer 13 via second bonding agents layer 17 The operation of 14 sides.As the method for laminating, wet method can be included.

In the case of wet method, the solution or dispersion liquid that will constitute the bonding agent of second bonding agents layer 17 are coated on anticorrosion (it is temperature more than its fusing point in the case that bonding agent is comprising acid-modified polyolefin resin in the temperature of regulation in process layer 14 Degree) under solvent is dispersed, be sintered.Then, sealant 15 is laminated, exterior member 20 is manufactured.As coating method, can enumerate Go out above illustrated various coating methods.

(maturation process operation)

This operation is the operation that (health) treatment is cured to layered product.Maturation process, energy are carried out by layered product Enough promote the bonding between second bonding agents 17/ sealant 15 of layer of 13/ corrosion-proof layer of metal foil layer 14/.Maturation process can Carried out with the scope of room temperature~100 DEG C.Curing time is, for example, 1~10 day.

The exterior member 20 of the present embodiment shown in Fig. 2 can like this be manufactured.

Preferred embodiment the carrying out with exterior member and its manufacture method to electrical storage device of the present utility model above Describe in detail, but the utility model is not limited to such particular implementation, this reality recorded in patent claims Various modifications and change can be carried out with the range of new main idea.

Electrical storage device exterior member of the present utility model can for example be suitable as lithium ion battery, Ni-MH battery and The exterior member of the electrical storage devices such as the electrochemical capacitor such as the secondary cells such as lead accumulator and double layer capacitor.Wherein, Electrical storage device exterior member of the present utility model is suitable as the exterior member of lithium ion battery.

Embodiment

The utility model is further illustrated below based on embodiment, but the utility model is not limited to following reality Apply example.

[using material]

The material used in embodiment described below and comparative example.

＜ substrate layers (thickness is 15 μm) ＞

Use nylon membrane (Ny) (Japan spins company and manufactures).

＜ first bonding agents layer (thickness is 4 μm) ＞

Use the addition system curing agent for having coordinated relative to PEPA owner's agent toluene di-isocyanate(TDI) Urethane adhesive (manufacture of Toyo Ink company).

＜ corrosion-proof layers ＞

Use with distilled water as solvent, be adjusted to " the polyphosphoric acids stable sodium that solid component concentration is 10 mass % Change cerium oxide sol ".It should be noted that sodium polyphosphate stabilizes cerium oxide sol by relative to the mass of cerium oxide 100 Part coordinates the sodium ascorbyl phosphate of 10 mass parts and obtains.

＜ metal foil layers (thickness is 35 μm) ＞

Use the soft aluminium foil (manufacture of aluminium company of Japan, " 8079 material ") of annealed ungrease treatment.

＜ second bonding agents layer (thickness is 4 μm) ＞

Use relative to the mass parts of maleic anhydride modified vistanex 100 dissolved in toluene, coordinated 10 matter Measure bonding agent obtained from the polyisocyanate compound of part (solid constituent ratio) isocyanurate structure.

＜ sealants (thickness is to be recorded in table) ＞

SPP：Maleic anhydride modified polypropylene (ADMER that Mitsui Chemicals, Inc.'s system is made)

PP：Polypropylene (PRIMEPOLYPRO of bottoming Polymer Company (Prime Polymer Co., Ltd.) manufacture)

The inorganic system's filler ＞ of ＜

Aluminum oxide：Denki Kagaku Kogyo kabushiki manufactures (spherical)

Silicon nitride：Japanese CERATEC companies manufacture (unsetting)

Boron nitride：Sumitomo 3M companies manufacture (tabular)

Silica：Denki Kagaku Kogyo kabushiki manufactures (spherical)

Titanium oxide：Fuji Titanium Industry manufactures (spherical)

The surface treatment of inorganic system's filler：Silane coupler (Dong Li-Dow Corning Corporation's manufacture)

[embodiment 1] (sealant：Heat lamination)

Used in the one side of metal foil layer micro gravure coating method be coated with sodium polyphosphate stabilize cerium oxide sol with Drying coated amount is set to turn into 70mg/m², sintering processes are implemented at 200 DEG C in drying unit.Thus, in metal foil layer shape Into the first corrosion-proof layer.

Next, micro gravure coating method coating sodium polyphosphate is also adopted by the another side of metal foil layer stabilizes oxygen Change cerium colloidal sol so that drying coated amount turns into 70mg/m², sintering processes are implemented at 200 DEG C in drying unit.Thus, exist Metal foil layer forms the second corrosion-proof layer.

Next, the first corrosion-proof layer side of the metal foil layer for being provided with the first and second corrosion-proof layers is adopted With dry lamination gimmick substrate layer is pasted on using urethane adhesive (first bonding agents layer).It is positioned in extrusion lamination Machine rolls out portion, is coextruded under 290 DEG C, the processing conditions of 100m/ minutes by the second corrosion-proof layer, from And it is laminated the sealant for constituting -1 (thickness is 35 μm).It should be noted that for sealant, double screw extruder is used in advance To make desired layer, by water-cooled and the operation of granulation, above-mentioned extrusion lamination is used in.It should be noted that sealant Composition as shown in tables 1 and 2.

For the layered product for so obtaining, by heat lamination come implement heat treatment with cause the layered product up to up to temperature Degree turns into 190 DEG C, so as to manufacture exterior member (substrate layer/first bonding agents layer/the first corrosion-proof layer/metal foil layer/the The layered product of two corrosion-proof layers/sealant).

[embodiment 2~31, comparative example 1~3] (sealant：Heat lamination)

Used the sealant of each composition shown in Tables 1 and 2 replace constitute -1 sealant beyond, with embodiment 1 similarly manufactures exterior member.

[embodiment 32~40] (sealant：Dry lamination)

Substrate layer/first bonding agents layer/the first corrosion-proof layer/metal foil layer/the second is made similarly to Example 1 The layered product of corrosion-proof layer.Next, using dry lamination method coating adhesive (second in the second corrosion-proof layer Bond layer) to cause that drying coated amount is 4~5g/m², be dried with after masking, adhesive seal layer.It should be noted that Bonding agent binding face to sealant implements sided corona treatment.Then, the curing of 5 days is carried out at 40 DEG C, exterior member is manufactured (substrate layer/first bonding agents layer/the first corrosion-proof layer/metal foil layer/the second corrosion-proof layer/second bonding agents layer/ The layered product of sealant).

Table 1

Table 2

It should be noted that in table, the shared ratio in the gross thickness of sealant of inorganic system's filler according to such as Fig. 3 in institute Show like that to calculate.

First, the section of the sealant for being cut out to the stacked direction along exterior member with microscope is photographed, and is carried out Image procossing.Now, determine the measuring point of n=1 as arbitrary starting point.Measuring point is from the off per 0.1mm scales in face Side sets up at 9 points, it is determined that the total 10 points measuring point comprising starting point.Next, as illustrated, for example In the measuring point of n=1, the vertical direction of the total thickness t and inorganic system's filler (in the measuring point of n=1 two) of sealant is determined Cumulative length x+y.Then, by calculating (x+y)/t × 100 (%), so as to determine close at the measuring point of arbitrary n=1 Ratio (length of vertical direction) in the gross thickness of sealing shared by inorganic system's filler.By the measure for n=2~n=10 Point carries out the operation, obtains its average value such that it is able to determine the shared ratio in the gross thickness of sealant of inorganic system's filler.

＜ evaluates ＞ for the exterior member obtained in embodiment and comparative example, has carried out following evaluation test.

(electrolyte layer Compressive Strength)

To be added in the mixed solution of ethylene carbonate/diethyl carbonate/dimethyl carbonate=1/1/1 (mass ratio) LiPF₆It is filled into teflon (registration mark) container with the electrolyte as 1M, is put into is cut into exterior member wherein The sample of 15mm × 100mm, takes care of 24 hours after embolism sealing at 85 DEG C.Then, wash altogether, (INSTRON is public for service-test machine Department's manufacture) (T-shaped is peeled off by force to determine the lamination strength of metal foil layer/sealing interlayer or metal foil layer/second bonding agents interlayer Degree).Tested according to JIS K6854, under 23 DEG C, 50%RH atmosphere, with peeling rate as 50mm/ minutes.Based on its knot Really, according to following standard evaluation.

A：Lamination strength is more than 9N/15mm

B：Lamination strength is more than 7N/15mm and below 9N/15mm

C：Lamination strength is 5N/15mm less than 7N/15mm

D：Lamination strength is less than 5N/15mm

(electrolyte heat seal strength)

Exterior member is cut into the sample doubling of 60mm × 120mm, by 1 side with sealing strip 10mm wide 190 DEG C, 0.5MPa, heated seal within 3 seconds.Then, remaining 2 side is also heated seal and has been made bag-shaped.By in the bag-shaped exterior structure Be filled with part 1ml in the mixed solution of ethylene carbonate/diethyl carbonate/dimethyl carbonate=1/1/1 (mass ratio) Add LiPF₆After being taken care of 24 hours at 60 DEG C with the pouch of the electrolyte as 1M, by the cutting of the 1st side of heat seal It is 15mm (reference picture 4) wide that service-test machine (manufacture of INSTRON companies) determines sealing intensity (T-shaped peel strength).According to JIS K6854, tested under 23 DEG C, 50%RH atmosphere, with peeling rate as 50mm/ minutes.Based on as a result, according to Under standard evaluation.

A：Sealing intensity is more than 80N/15mm, explosion width more than 5mm

B：Sealing intensity is more than 80N/15mm, burst a width of 3~5mm

C：Sealing intensity is 60N/15mm less than 80N/15mm

D：Sealing intensity is less than 60N/15mm

(degassing heat seal strength)

Exterior member is cut into the sample of 75mm × 150mm and is folded in half into (reference picture 5A) after 37.5mm × 150mm, will 150mm while and seal during 37.5mm, bag.Then, in bag inject 5ml in ethylene carbonate/diethyl carbonate/carbonic acid two LiPF is added in the mixed solution of methyl esters=1/1/1 (mass ratio)₆With the electrolyte as 1M, sealed by heat-sealing, After being taken care of 24 hours at 60 DEG C, heat-sealing (reference picture 5B) is de-gassed with 190 DEG C, 0.3MPa, 2 seconds to bag central portion.In order to Sealing is stabilized, at normal temperatures certainly after 24 hours, degassing sealing 15mm (reference picture 5C) wide is cut into, examination is used Test machine (manufacture of INSTRON companies) and determine heat seal strength (T-shaped peel strength).According to JIS K6854, in 23 DEG C, 50%RH gas Tested under atmosphere, with peeling rate as 50mm/ minutes.Based on as a result, according to following standard evaluation.

A：Sealing intensity is more than 60N/15mm

B：Sealing intensity is 40N/15mm less than 60N/15mm

C：Sealing intensity is 30N/15mm less than 40N/15mm

D：Sealing intensity is less than 30N/15mm

(insulating properties)

It is 37.5mm × 150mm by the sample doubling that exterior member is cut into 75mm × 150mm.Then, clamping lug is close Envelope agent and lug have then carried out side seal come sealing at the top of carrying out (controlling sealing to press using gap).Then, in order that Electrode contact, a part for outer layer is eliminated, and after exposing metal level, is connected the electrode to lug (the point A of Fig. 6 A) and is exposed Metal level (the point B of Fig. 6 A), carry out the applying of 25V, carried out the measure (Insulation Test 1) of resistance value.

Then, the electrolyte of 5ml is entered from remaining 1 marginal not, is sealed by heat-sealing.Taken care of 24 hours at 60 DEG C Afterwards, degassing heat-sealing has been carried out with 190 DEG C, 0.3MPa, 2 seconds for bag central portion.In order that sealing is stabilized, at normal temperatures After having taken care of 24 hours, lug (the point A of Fig. 6 B) and the metal level (the point B of Fig. 6 B) for exposing are connected the electrode to, apply 25V, The measure (Insulation Test 2) of resistance value is carried out.

Based on the result of Insulation Test 1 and 2, according to following standard evaluation.

A：More than 200M Ω

B：More than 100M Ω and 200M below Ω

C：30M Ω are less than 100M Ω

D：Less than 30M Ω

(integrated quality)

The result of above-mentioned each evaluation is shown in table 3.In Table 3 below, for the sample evaluated in the absence of D in each evaluation result Product, it may be said that comprehensive excellent quality.

Table 3

From the result of table 1~3, if the electrical storage device exterior member of embodiment, even if sealant is thin In the case of stratification, it is also possible to realize sufficient heat seal strength, while maintaining good insulating properties.In addition we know, if contained The layer of inorganic system's filler is formed by SPP and is intermediate layer, then can be strong in the especially excellent lamination strength of holding and sealing Good insulating properties is maintained in the case of degree.

Claims (6)

1. electrical storage device exterior member, it at least possesses substrate layer, bond layer, metal foil layer and sealant, wherein, it is described Sealant contains and plays a part of as inorganic system's filler of sept, and relative to described in section in the stacking direction Ratio for the gross thickness of sealant shared by inorganic system's filler is 5~50%, the gross thickness of the sealant for 10~ 100μm。

2. electrical storage device exterior member according to claim 1, wherein, the sealant is made up of the layer of more than 2, The layer of described more than 2 includes the layer containing inorganic system's filler and the layer without inorganic system's filler, therein at least 1 Layer is the layer without inorganic system's filler.

3. electrical storage device exterior member according to claim 2, wherein, for the gross thickness of sealant, contain The thickness for having the layer of inorganic system's filler is more than 50%.

4. electrical storage device exterior member according to claim 2, wherein, in the sealant, containing described inorganic It is that the layer of filler is held in the layer without inorganic system's filler.

5. electrical storage device exterior member according to claim 1, wherein, the layer containing inorganic system's filler is by acid The layer that modified polyolefin resin is made.

6. electrical storage device exterior member according to claim 1, wherein, inorganic system's filler has been carried out at surface Inorganic system's filler of reason.