CN108408245A - A kind of corrosion-resistant finishes, lithium battery flexible packaging material and preparation method thereof - Google Patents
A kind of corrosion-resistant finishes, lithium battery flexible packaging material and preparation method thereof Download PDFInfo
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- CN108408245A CN108408245A CN201810147860.6A CN201810147860A CN108408245A CN 108408245 A CN108408245 A CN 108408245A CN 201810147860 A CN201810147860 A CN 201810147860A CN 108408245 A CN108408245 A CN 108408245A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
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- Life Sciences & Earth Sciences (AREA)
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- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
The invention discloses a kind of corrosion-resistant finishes, lithium battery flexible packaging material and preparation method thereof, lithium battery flexible packaging material includes corrosion-resistant finishes, and corrosion-resistant finishes includes organic coating and the inorganic oxide layer that is overlying on the organic coating wherein one or both sides；Or it includes inorganic oxide layer and the organic coating that is overlying on the inorganic oxide layer wherein one or both sides, the organic coating is the conducting polymer at least doped with acid, and inorganic oxide layer is then made of the nano-particle of inorganic oxide.The corrosion-resistant finishes of the present invention is nanostructure, and composition is controllable, can give full play to the synergistic effect of organo-mineral complexing, has excellent corrosion resistance, to effectively extend the service life of lithium battery flexible packaging material.Coating is free of chromic salts simultaneously, has the advantages that chemical stability is good, environmental pollution is small.
Description
Technical field
The invention belongs to lithium battery flexible packaging Material Field, more particularly to a kind of corrosion-resistant finishes, lithium battery flexible packaging material
Material and preparation method thereof.
Background technology
In recent years, with the development of Miniature electronic technology and the demand to novel environment friendly electrical vehicular power power supply, lithium electricity
Pond sustained production rapid growth, application range are also constantly expanding.The housing material of lithium battery has two kinds of Soft Roll and Hard Roll, with
The Hard Rolls package material such as box hat, aluminum hull is compared, and flexible packing material has made of multilayer film (substrate layer/aluminium foil layer/hot sealing layer)
It is light, capacity is big, safe, can be with unrestricted choice package shape the advantages that.The use process of battery is a constantly charging
The process of electric discharge is constantly carrying out dynamic electrochemical reaction inside battery core.Have inside battery core by highly polar organic solvent
The electrolyte for the lithium salts composition for generating hydrofluoric acid can be decomposed rapidly with water is met.When with permeability, corrosive electrolyte transmission
When hot sealing layer reaches aluminium foil layer, the interlaminar strength between aluminium foil layer and hot sealing layer can be reduced, lithium battery can be caused when serious
Expand leakage.In order to inhibit this phenomenon, the corrosion resistance of lithium battery flexible packaging material is improved, extend material uses the longevity
Life, there has been proposed a variety of aluminium foil surface processing methods.
Most widely used at present is to carry out phosphate, chromic acid salt treatment to aluminium foil surface, is carried out there are many document
Relevant report.The Chinese patent of 103165831 A of Publication No. CN proposes a kind of using chromic salts, the mixed solution of acid, fluoride
Aluminium foil surface is chemically treated, lithium battery is improved in the method for the compact metal oxide film layer that intermediate aluminium foil surface is formed
The electrolyte resistance corrosivity of flexible packing material.The Chinese patent of 107425147 A of Publication No. CN propose using water-base resin,
Phosphoric acid, trivalent chromium form lumarith containing chromium to improve the corrosion resistant ability of aluminium foil layer.In 105463428 A of Publication No. CN
State's patent is related to one kind by water, straight chained alkyl, phosphonic acids, zirconium compounds, titanium compound, phosphoric acid, ammonium salt, nickel salt, hydrofluoric acid or nitre
The aluminium foil surface passivating solution of acid composition.The above method can improve the corrosion resistance of lithium battery flexible packaging material to a certain extent
Can, but Cr VI, trivalent chromium and the hydrofluoric acid used have very strong toxicity, are detrimental to health, seriously pollute environment.Therefore
Seek a kind of excellent anti-corrosion performance, the anti-corrosion method of safety non-pollution is just becoming more and more important.
Conducting polymer is so that it is turned by insulator through chemistry or electrochemistry " doping " by the macromolecule with conjugation pi-pi bond
Become a kind of high molecular material of conductor.It is combined with inorganic nano material by suitable method, can be obtained corrosion-resistant
The composite coating haveing excellent performance realizes the replacement to phosphate, chromic acid salt treatment, to reduce the pollution to environment.
Invention content
The object of the present invention is to provide a kind of excellent anti-corrosion performances, can realize the replacement to phosphate, chromic acid salt treatment,
Coating to reduce environmental pollution.
In order to achieve the above objectives, the technical solution adopted by the present invention is：A kind of corrosion-resistant finishes, it include organic coating and
The inorganic oxide layer being overlying on the organic coating wherein one or both sides；Or it includes inorganic oxide layer and is overlying on
Organic coating on the inorganic oxide layer two sides, the organic coating is the conducting polymer at least doped with acid, inorganic
Oxide skin(coating) is then made of the nano-particle of inorganic oxide.
Optimization, the thickness of the organic coating is 10-500nm.
Optimization, the thickness of the inorganic oxide layer is 10-500nm.
Optimization, the conducting polymer of the organic coating be it is one or more in polyaniline, polypyrrole, polythiophene,
The coating weight of the conducting polymer is 0.001-1g/m2。
Optimization, the acid of the conducting polymer doping of the organic coating is inorganic acid and/or organic acid.
Optimization, the inorganic oxide in the inorganic oxide layer is titanium dioxide, stannic oxide, silica, oxygen
One or more in change aluminium, zinc oxide, iron oxide, the coating weight of the inorganic oxide is 0.001-1g/m2。
The present invention also provides a kind of lithium battery flexible packaging materials, it includes substrate layer, the first adhesive linkage, aluminium foil layer, is set to
Corrosion-resistant finishes, the second adhesive linkage at least one face of the aluminium foil layer and hot sealing layer.
Optimization, the material of substrate layer is one or more, the material of the first adhesive linkage of polyamide, polyester, polyimides
Material is one or more, the aluminium foil of adhesive for polyurethane, epoxy resin adhesive, acrylic resin adhesive, polyester adhesive
Layer 3 is soft single side optical aluminum foil, and the material of the second adhesive linkage is adhesive for polyurethane, epoxy resin adhesive, acrylic resin
Adhesive, polyester adhesive, acid modified resin it is one or more, the material of hot sealing layer be polyolefin, cyclic polyolefin one
Kind is a variety of.
The present invention also provides a kind of preparation methods of lithium battery flexible packaging material, it includes the following steps：
(1) first, organic coating and inorganic oxide layer are deposited on aluminium foil layer, obtain aluminium foil layer/corrosion-resistant finishes group
At laminated body；
(2) with adhesive that substrate layer and aluminium foil layer pressure roller is compound, it obtains by substrate layer/first adhesive linkage/aluminium foil layer/resistance to
The laminated body of corrosion resistant coating composition；
(3) with adhesive that the corrosion-resistant finishes pressure roller of hot sealing layer and laminated body is compound, obtain lithium battery flexible packaging material.
Optimization, in step (1) two layers of sequence interchangeable or be repeated as many times.
Since above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：The present invention's is corrosion-resistant
Coating is nanostructure, and composition is controllable, can give full play to the synergistic effect of organo-mineral complexing, is had excellent corrosion-resistant
Performance, to effectively extend the service life of lithium battery flexible packaging material.Coating is free of chromic salts simultaneously, has chemical stability
Advantage good, environmental pollution is small.
Description of the drawings
Attached drawing 1 is the structural schematic diagram of lithium battery flexible packaging material of the present invention.
Specific implementation mode
The invention will be further described for embodiment shown in below in conjunction with the accompanying drawings.
Corrosion-resistant finishes 4 of the present invention, it includes organic coating 41 and is overlying on the wherein one or both sides of the organic coating 41
On inorganic oxide layer 42；Or it includes inorganic oxide layer 42 and is overlying on 42 two sides of the inorganic oxide layer
Organic coating 41, the organic coating 41 are the conducting polymer at least doped with acid, and inorganic oxide layer 42 is then by inorganic oxygen
The nano-particle of compound forms.Corrosion-resistant finishes is nanostructure, and composition is controllable, can give full play to organo-mineral complexing
Synergistic effect has excellent corrosion resistance, to effectively extend the service life of lithium battery flexible packaging material.Have simultaneously
The advantage that chemical stability is good, environmental pollution is small.
In order to further increase corrosion resistance, following optimize can be made：The conducting polymer of the organic coating 41 is
One or more, the preferably synthetic polyphenyl simple, performance easy-regulating, chemical stability are good of polyaniline, polypyrrole, polythiophene
Amine.The preferred 0.001-1g/m of coating weight of the conducting polymer2.The dopant acid of the conducting polymer be inorganic acid (hydrochloric acid,
Sulfuric acid, nitric acid, phosphoric acid, sulfurous acid, perchloric acid etc.), organic acid (dodecyl benzene sulfonic acid, p-methyl benzenesulfonic acid, polystyrene sulphur
Acid, oxalic acid, camphorsulfonic acid, acetic acid, tartaric acid, phytic acid etc.) it is one or more.The type of dopant acid is to gained conducting polymer
Performance have a significant impact：The conducting polymer that can be dissolved in water can be obtained using polystyrolsulfon acid as dopant acid, be with phytic acid
Dopant acid can obtain the conducting polymer of cross-linked structure.The organic coating 41, which removes, contains conducting polymer beyond the region of objective existence, can also contain
There are the film forming matters such as epoxy resin, acrylic resin, the auxiliary agents such as levelling agent, dispersant, antifoaming agent.The organic coating 41 can be with
It, can also be by metal surface applying conductive polymer solution by being obtained in metal surface electrochemical deposition conducting polymer
Obtain, can also by by conducting polymer be dispersed in epoxy resin (such as bisphenol A type epoxy resin, bisphenol f type epoxy resin,
Glycidyl ester type epoxy resin etc.), acrylic resin (such as polyacrylic acid, polymethylacrylic acid, polyvinyl sulfonic acid, polyphenyl second
Alkene sulfonic acid etc.) in conductive coating is made, on the metal surface coating obtain.The coating be soluble in dimethylformamide,
The organic solvents such as N-Methyl pyrrolidone can also make solvent with environment amenable water.It can also be added in coating polynary
The curing agent such as amine, multicomponent isocyanate realize the crosslinking of resin, to obtain the more excellent organic coating of stability.It is described
The organic coating of the preferred 10-500nm of thickness of organic coating 41, nanostructure have big specific surface area, being capable of good combination
Corrosion resistance is improved in metal surface.The inorganic oxide of the inorganic oxide layer 42 is titanium dioxide, stannic oxide, two
Silica, aluminium oxide, zinc oxide, iron oxide it is one or more.The preferred 0.001-1g/ of coating weight of the inorganic oxide
m2.The inorganic oxide layer 42 can be obtained by the colloidal sol or nano-particle solution of coated inorganic oxide, can also be passed through
The nano-particle of physical vapour deposition (PVD) (such as magnetron sputtering, vacuum evaporation) inorganic oxide obtains.The inorganic oxide layer
The 42 preferred 10-500nm of thickness, the preferred 0.01-50 of mass ratio of the conducting polymer and inorganic oxide.Nanostructure
Corrosion-resistant finishes can give full play to the synergistic effect of organo-mineral complexing, have excellent corrosion resistance and chemical stabilization
Property.
The present invention also provides a kind of lithium battery flexible packaging materials, are bonded as shown in Figure 1, it includes substrate layer 1, first successively
Layer 2, aluminium foil layer 3, corrosion-resistant finishes 4, the second adhesive linkage 5 and hot sealing layer 6.
In the lithium battery flexible packaging material of the present invention, substrate layer 1 is outermost layer, plays heat-resisting effect of insulating.As
The material for forming substrate layer 1, can enumerate polyamide, polyester resin, polyimides etc..1 thickness of substrate layer preferably 5~50
μm.First adhesive linkage 2 is the layer for being disposed there between substrate layer 1 and 3 strong bond of aluminium foil layer.First adhesive linkage 2 makes
As long as bonding agent ingredient can be Nian Jie with aluminium foil layer 3 by substrate layer 1, it is not particularly limited, poly- ammonia can be enumerated
Ester adhesive, epoxy resin adhesive, acrylic resin adhesive, polyester adhesive etc., preferably isocyanide more than difunctional
Bonding agent made of ester compound is had an effect as curing agent and polyester polyol as host agent.The thickness of first adhesive linkage 2
Preferably 1~10 μm of degree.Aluminium foil layer 3 can improve the intensity and mouldability of flexible packing material, moreover it is possible to prevent vapor, oxygen, light etc.
Invade inside battery.Ductility when to improve pinhole resistance and molding is, it is preferable to use the soft machine glazing aluminium containing iron, silicon
Foil.To improve aluminium foil surface wetting capacity, the processing such as degreasing, frosted preferably are carried out to aluminium foil.The thickness of aluminium foil layer 3 preferably 10~
100μm.Second adhesive linkage 5 is the layer for being disposed there between corrosion-resistant finishes 4 and 6 strong bond of hot sealing layer.As
Two adhesive linkages 5, can enumerate adhesive for polyurethane, epoxy resin adhesive, acrylic resin adhesive, polyester adhesive,
Acid modified resin, preferably acid modified polyolefin system resin.Second adhesive linkage 5 can be by coating acid modified polyolefin system resin
Adhesive (auxiliary agents such as cooperation curing agent, levelling agent) obtains, and can also be obtained by resin melting film extrusion.Second adhesive linkage
Preferably 1~10 μm of 5 thickness.Hot sealing layer 6 be to form innermost layer, and when battery assembles can each other thermal welding to by battery
The layer of component seal.As resin component used in hot sealing layer 6 with can thermal welding be limited, polyolefin, ring can be enumerated
Shape polyolefin etc..Hot sealing layer 6 can be formed only by 1 layer, can also form 2 layers or more by identical or different resin component.Heat
Preferably 10~100 μm of the thickness of sealing.
The present invention also provides a kind of preparation methods of lithium battery flexible packaging material：
(1) first, it is sequentially depositing organic coating and inorganic oxide layer on aluminium foil layer, obtains aluminium foil layer/corrosion-resistant painting
The laminated body of layer composition；
(2) with adhesive that substrate layer and aluminium foil layer pressure roller is compound, it obtains by substrate layer/first adhesive linkage/aluminium foil layer/resistance to
The laminated body of corrosion resistant coating composition；
(3) with adhesive that the corrosion-resistant finishes pressure roller of hot sealing layer and laminated body is compound, obtain lithium battery flexible packaging material.
Further, the coating method of adhesive is that inverse roller coating cloth, spraying, intaglio plate coating, steel wire scrape rod coating etc.
Optimization, in step (1) two layers of sequence interchangeable or be repeated as many times.
Below in conjunction with by specific embodiment, the present invention is described in detail.
Embodiment 1
The present embodiment provides a kind of corrosion-resistant finishes, specific preparation process is as follows：
(a) organic coating is deposited：The polystyrene sulphur of 1mg/ml is coated on 3 bright face of aluminium foil layer using inverse roller coating technique
The coating weight of the polyaniline aqueous solution of acid doping, polyaniline is 0.05g/m2, 110 DEG C are dried to obtain organic coating (41).
(b) inorganic oxide layer is deposited：The titanium dioxide of 1mg/ml is coated on organic coating using inverse roller coating technique
The coating weight of Nano sol (PH=1.5), titanium dioxide is 0.05g/m2, 110 DEG C are dried to obtain inorganic oxide layer (42).It leads
The mass ratio of electric polymer and inorganic oxide is 1/1, and the two collectively constitutes corrosion-resistant finishes 4.
Embodiment 2
The present embodiment provides a kind of corrosion-resistant finishes, preparation process with it is almost the same in embodiment 1, unlike：
Dopant acid in step (a) is dodecyl benzene sulfonic acid, and solvent for use is then N-Methyl pyrrolidone.
Embodiment 3
The present embodiment provides a kind of corrosion-resistant finishes, preparation process with it is almost the same in embodiment 1, unlike：
Dopant acid in step (a) is hydrochloric acid, and solvent for use is then N-Methyl pyrrolidone.
Embodiment 4
The present embodiment provides a kind of corrosion-resistant finishes, preparation process with it is almost the same in embodiment 1, unlike：
Organic coating (41) is obtained by coating conductive coating in step (a).Conductive coating is adulterated by dodecyl benzene sulfonic acid
Polyaniline and bisphenol A epoxide resin (epoxide number 0.44) and 651 Versamid of curing agent composition, the amount ratio of three
It is=30：55：15, solvent for use is N-Methyl pyrrolidone.
Embodiment 5
The present embodiment provides a kind of corrosion-resistant finishes, preparation process with it is almost the same in embodiment 1, unlike：
Organic coating (41) is obtained by coating conductive coating in step (a).Conductive coating be by doped hydrochloride polyaniline and
The amount ratio of bisphenol A epoxide resin (epoxide number 0.44) and 651 Versamid of curing agent composition, three is=30：55：
15, solvent for use is N-Methyl pyrrolidone.
Embodiment 6
The present embodiment provides a kind of corrosion-resistant finishes, preparation process with it is almost the same in embodiment 1, unlike：
The PH of titanium dioxide nano sol used is 8 or so in step (b).
Embodiment 7
The present embodiment provides a kind of corrosion-resistant finishes, preparation process with it is almost the same in embodiment 1, unlike：
Inorganic oxide layer (42) is obtained by magnetron sputtering titanium dioxide nano-particle in step (b).
Embodiment 8
The present embodiment provides a kind of corrosion-resistant finishes, preparation process with it is almost the same in embodiment 1, unlike：
The sedimentary sequence of organic coating and inorganic oxide layer is opposite, i.e., first deposits inorganic oxide layer (42), deposit afterwards organic
Coating (41).
Comparative example 1
This comparative example provides a kind of corrosion-resistant finishes, and preparation process is the organic coating (41) of a deposition step (a).
Comparative example 2
This comparative example provides a kind of corrosion-resistant finishes, and preparation process is the inorganic oxide layer of a deposition step (b)
(42)。
Comparative example 3
This comparative example provides a kind of corrosion-resistant finishes, and preparation process is only to carry out chromic acid salt treatment to 3 bright face of aluminium foil layer.
The present invention also provides a kind of lithium battery flexible packaging materials and preparation method thereof：
(1) substrate layer 1：- 6 film of biaxial tension nylon, thickness are 25 μm, sided corona treatment；
First adhesive linkage 2：Biliquid curable polyurethane adhesive (NCO/OH=1.2/1), thickness are 5 μm；
Aluminium foil layer 3：The soft single side optical aluminum foil that Fe contents are 1%, thickness are 40 μm, ungrease treatment；
Second adhesive linkage 5：Maleic anhydride modified acrylic resin adhesive, thickness are 5 μm；
Hot sealing layer 6：Cast polypropylene film, thickness are 40 μm, sided corona treatment.
(2) adhesive for polyurethane, 90 DEG C of drying, the dark face pressure with aluminium foil layer 3 are coated on substrate layer 1 using spraying process
Roller is bonded, and obtains the laminated body of 1/ first adhesive linkage of substrate layer, 2/ aluminium foil layer, 3/ corrosion-resistant finishes 4.
(3) maleic anhydride modified acrylic resin glue is coated on the corrosion-resistant finishes 4 of laminated body using spraying process
Glutinous agent, 100 DEG C of drying, is bonded with 6 pressure roller of hot sealing layer, and 80 DEG C of curings obtain lithium battery flexible packaging material in 3 days.
Evaluation content includes interlaminar strength and electrolyte resistance performance：
(1) interlaminar strength：With reference to GB 8808-88《Soft composite plastics material disbonded test method》, test aluminium foil
The interlaminar strength of layer 3 and hot sealing layer 6, Sample Width 15mm, T-type stripping, rate of extension 200mm/min.
●：Interlaminar strength ＞ 10N/15mm, test curve are steady.
○：Interlaminar strength ＜ 10N/15mm or test curve fluctuate serious up and down.
(2) electrolyte resistance performance：By the batten of 15mm wide in 85 DEG C of electrolyte (EC/DEC/DMC=1/1/1+1mol/L
LiPF6) in impregnate for 24 hours and 48h, the delamination of aluminium foil layer 3 and hot sealing layer 6 is observed after cleaning.
●：48h is impregnated not to be layered yet.
Immersion is not layered for 24 hours, is impregnated 48h and is layered.
○：48h is impregnated to be layered.
Lithium battery flexible packaging material is prepared using the material, method, Examples 1 to 7 is assessed according to the evaluation content
With comparative example 1~3,1 the results are shown in Table.
Table 1
Dopant acid type has a significant impact coating antiseptic effect it can be seen from Examples 1 to 5：Polystyrolsulfon acid
Optimal, dodecyl benzene sulfonic acid is taken second place, and hydrochloric acid is worst.Its reason may solubility property correlation of the polyaniline in coordinative solvent.
For polyaniline per se with conjugated structure, rigidity is greatly, it is difficult to dissolve.Polystyrolsulfon acid is macromolecular acid, can also in addition to doping
Play the role of soft template, polyaniline molecule chain is enable to be dispersed in water.The polyaniline of polystyrolsulfon acid doping has good
Good film forming can match in excellence or beauty chromate coating with electrolyte resistance performance of the titanium dioxide nano coating after compound.Dodecyl
Benzene sulfonic acid carries large scale organic group, and when doping can be embedded in polyaniline molecule interchain, weaken intermolecular interaction,
Improve dissolubility.But the independent film forming of polyaniline of dodecyl benzene sulfonic acid doping is poor, needs to coordinate the film forming such as epoxy resin
Substance can just obtain the good coating of electrolyte resistance performance.As inorganic acid, the PANI dissolubilities of doped hydrochloride, film forming are equal
It is very poor, in the coating be difficult to be uniformly dispersed, cause the porosity of coating to rise, electrolyte resistance performance is poor.Embodiment 6~7 is said
The property of bright titanium dioxide nano-particle also has an impact coating electrolyte resistance performance.Titanium dioxide is amphoteric oxide, solution
PH value can influence the electriferous state on its surface.The isoelectric point of titanium dioxide is about 6.8, under acid condition, TiO 2 sol
Surface is positively charged.And a large amount of negative electrical charges are carried on the polyaniline chain of polystyrolsulfon acid doping, the two passes through electrostatic force in this way
Effect can obtain the excellent composite coating of chemical stability, give full play to synergistic effect caused by organo-mineral complexing, have
Conducive to the raising of electrolyte resistance performance.Embodiment 8 shows to adjust the sedimentary sequence of organic coating and inorganic oxide layer still can be with
Obtain the excellent coating of electrolyte resistance performance.Individual organic coating (comparative example 1) can only partly resist the corrosion of electrolyte, and
Individual inorganic oxide layer (comparative example 2) cannot then resist electrolytic corrosion completely, this illustrates organic coating and inorganic oxide
There is synergistic effect between nitride layer.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of corrosion-resistant finishes, it is characterised in that：It include organic coating and be overlying on the organic coating wherein one side or two
Inorganic oxide layer on face；Or it include inorganic oxide layer and be overlying on the inorganic oxide layer wherein one side or two
Organic coating on face, the organic coating are the conducting polymer at least doped with acid, and inorganic oxide layer is then by inorganic oxygen
The nano-particle of compound forms.
2. corrosion-resistant finishes according to claim 1, it is characterised in that：The thickness of the organic coating is 10-500nm.
3. corrosion-resistant finishes according to claim 1, it is characterised in that：The thickness of the inorganic oxide layer is 10-
500nm。
4. corrosion-resistant finishes according to claim 1, it is characterised in that：The conducting polymer of the organic coating is polyphenyl
One or more in amine, polypyrrole, polythiophene, the coating weight of the conducting polymer is 0.001-1g/m2。
5. corrosion-resistant finishes according to claim 1, it is characterised in that：The conducting polymer doping of the organic coating
Acid is inorganic acid and/or organic acid.
6. corrosion-resistant finishes according to claim 1, it is characterised in that：Inorganic oxide in the inorganic oxide layer
To be one or more in titanium dioxide, stannic oxide, silica, aluminium oxide, zinc oxide, iron oxide, the inorganic oxide
The coating weight of object is 0.001-1g/m2。
7. a kind of lithium battery flexible packaging material, it is characterised in that it include substrate layer, the first adhesive linkage, aluminium foil layer, be set to it is described
Corrosion-resistant finishes, the second adhesive linkage at least one face of aluminium foil layer and hot sealing layer.
8. lithium battery flexible packaging material according to claim 7, it is characterised in that：The material of substrate layer is polyamide, gathers
Ester, polyimides it is one or more, the material of the first adhesive linkage is adhesive for polyurethane, epoxy resin adhesive, acrylic acid
Resin adhesive, polyester adhesive it is one or more, aluminium foil layer 3 is soft single side optical aluminum foil, and the material of the second adhesive linkage is
One kind or more of adhesive for polyurethane, epoxy resin adhesive, acrylic resin adhesive, polyester adhesive, acid modified resin
Kind, the material of hot sealing layer be polyolefin, cyclic polyolefin it is one or more.
9. a kind of preparation method of lithium battery flexible packaging material, which is characterized in that it includes the following steps：
(1) first, organic coating and inorganic oxide layer are deposited on aluminium foil layer, obtain aluminium foil layer/corrosion-resistant finishes composition
Laminated body；
(2) with adhesive that substrate layer and aluminium foil layer pressure roller is compound, it obtains by substrate layer/first adhesive linkage/aluminium foil layer/corrosion-resistant
Coat composed laminated body；
(3) with adhesive that the corrosion-resistant finishes pressure roller of hot sealing layer and laminated body is compound, obtain lithium battery flexible packaging material.
10. the preparation method of lithium battery flexible packaging material according to claim 9, which is characterized in that two in step (1)
Layer sequence interchangeable is repeated as many times.
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