CN110391359A - Battery housing material, battery external package casing, preparation method and battery - Google Patents
Battery housing material, battery external package casing, preparation method and battery Download PDFInfo
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- CN110391359A CN110391359A CN201810356935.1A CN201810356935A CN110391359A CN 110391359 A CN110391359 A CN 110391359A CN 201810356935 A CN201810356935 A CN 201810356935A CN 110391359 A CN110391359 A CN 110391359A
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- plastic layer
- composite plastic
- battery
- impervious barrier
- housing material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to technical field of secondary batteries, it is related to a kind of battery housing material, battery external package casing, preparation method and battery.Battery housing material provided by the invention, the composite plastic layer including impervious barrier and comprising the first composite plastic layer and the second composite plastic layer, first composite plastic layer, impervious barrier and the second composite plastic layer are cascading；The composite plastic layer includes following component: SAN, CPE, MBS and optional auxiliary agent.Packaging material of the invention has certain intensity and impact resistance, preferable heat resistance, lower water imbibition, preferable electrical insulating property and corrosion resistance, it can effectively prevent the generation of electrolyte leakage phenomenon, the safety for guaranteeing integral battery, reduces the production cost of battery.
Description
Technical field
The invention belongs to technical field of secondary batteriess, are related to the packaging material of secondary cell, and in particular to a kind of battery use
Housing material, battery external package casing, preparation method and battery.
Background technique
In recent years, while with people's raising to the consciousness of environmental protection, using natural resources such as sunlight and wind-force,
It is even more to attract attention as secondary cells or double layer capacitor etc. such as battery, lithium ions for storing electric energy.And in institute
Have in battery, the packaging material for cell devices such as encapsulated electrode and electrolyte becomes integral component.Current electricity
Pond generally uses aluminium as the shell of battery, and usually this kind of batteries are called aluminum-shell battery by we, in aluminum-shell battery, metal
Particle has detrimental effects to battery security, after the lamination thickness of battery battery core reaches certain thickness, due to using
Aluminum hull is so just need to consider the safety of battery.In order to allow battery to have higher safety, while in view of reduction
Cost, existing battery start slowly using case material of the plastics as battery.Case material due to plastics as battery
It is than aluminium lower as the case material cost of battery, at the same various shapes can also be met, slimming, lighting are wanted
It asks, people are more prone to the case material for using plastics as battery, so that plastics be used to start into as the case material of battery
For a kind of development trend.
But the battery of the existing case material as battery that uses plastics there is a problem of it is very much, such as: plastic housing electricity
Pond is by the problem of being easy to appear leakage after a period of use, general electric battery with plastic case is in the electrolyte after use in 2 years
5~15% can be lost, electric battery with plastic case service life is seriously affected.
Since battery has very high requirement to battery case materials, it is desirable that battery case should have certain intensity and impact resistance
Property, while battery case should have preferable heat resistance and lower water imbibition, and battery case should also have preferable electricity absolutely
Edge and corrosion resistance.Wherein, impact strength is to measure a kind of index of toughness of material, is normally defined sample in shock loading
Under the action of fracture or when jackknifing, the energy that unit cross-sectional area is absorbed.Impact strength is used to evaluate the impact resistance of material
Or the brittleness and toughness degree of judgement material.
However, common plastics are ABS plastic and PP plastics in the packaging material of current battery, ABS plastic has very
Good impact strength, but that there are hot-air aging resistances is very poor because it haves the defects that double bond to make it.PP plastics have centainly
Intensity, but its barrier property is poor, not can effectively solve the leakage problem of electrolyte.
Therefore, a kind of novel battery plastics shell material that overall performance is excellent is researched and developed to be very necessary.
In consideration of it, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of battery housing material, which has certain intensity and resistance to
Impact, preferable heat resistance, lower water imbibition, preferable electrical insulating property and corrosion resistance, can effectively prevent electrolyte
The generation of leakage phenomenon guarantees the safety of integral battery, helps to improve the performance of the secondary cells such as lithium battery and extends use
Service life.
The second object of the present invention is to provide a kind of battery external package casing, and the shell is mainly by above-mentioned battery with outer
Packaging material is made, thus at least has the advantages that identical as above-mentioned battery housing material.
The third object of the present invention is to provide a kind of preparation method of battery external package casing, and this method has operation
Simply, high production efficiency, feature at low cost, low for equipment requirements, it is easy to accomplish industrialization large-scale production.
The fourth object of the present invention is to provide a kind of battery, which has above-mentioned battery external package casing, can promote
There is high barrier property, excellent electrolyte resistance stability, heat resistance and electrical insulating property etc. into battery, ensure that the peace of battery
Quan Xing extends the service life of battery.
To achieve the above object, the technical solution adopted by the present invention are as follows:
According to an aspect of the present invention, the present invention provides a kind of battery housing material, including impervious barrier and comprising
The composite plastic layer of first composite plastic layer and the second composite plastic layer, first composite plastic layer, impervious barrier and second are multiple
Plastic layer is closed to be cascading；
The composite plastic layer includes following component: SAN, CPE, MBS and optional auxiliary agent.
As further preferred technical solution, the composite plastic layer includes following component according to parts by weight:
SAN60~100 part, CPE0.1~20 part, MBS0.1~20 part and 0~1 part of auxiliary agent；
Preferably, the composite plastic layer includes following component according to parts by weight:
SAN60~90 part, CPE5~20 part, MBS5~20 part and 0.05~0.3 part of auxiliary agent；
Preferably, the composite plastic layer includes following component according to parts by weight:
SAN70~80 part, CPE10~15 part, MBS10~15 part and 0.1~0.2 part of auxiliary agent.
As further preferred technical solution, the impervious barrier include in plastics, metal, alloy or metal composite extremely
Few one kind；
Preferably, the impervious barrier by aluminizing, stainless steel, in EVOH, PVDC, PLA, PA, HDPE, PE-RT or PE-X
At least one formed；Or,
The impervious barrier is by the alloy including at least any one in tin, aluminium, copper, iron, zinc, nickel, titanium, zirconium, chromium, manganese or magnesium
It is formed；Or,
The impervious barrier is the metal including at least any one in tin, aluminium, copper, iron, zinc, nickel, titanium, zirconium, chromium, manganese or magnesium
Compound is formed.
As further preferred technical solution, chemical conversion processing is implemented at least one face of the impervious barrier.
As further preferred technical solution, the auxiliary agent includes antioxidant.
As further preferred technical solution, the number of plies of first composite plastic layer and the second composite plastic layer is respectively only
It is on the spot 1~20 layer, preferably 1~12 layer.
As further preferred technical solution, there is adhesive layer between first composite plastic layer and impervious barrier；With/
Or,
There is adhesive layer between second composite plastic layer and the impervious barrier；
Preferably, first composite plastic layer with a thickness of 10~150 μm；
Preferably, the impervious barrier with a thickness of 5~100 μm；
Preferably, second composite plastic layer with a thickness of 10~150 μm.
According to another aspect of the present invention, the present invention provides a kind of battery external package casing, has storage battery
Inner space is prepared using above-mentioned battery with housing material.
According to another aspect of the present invention, the present invention also provides a kind of preparation sides of above-mentioned battery external package casing
Method is prepared by the method for extrusion molding or injection molding；Or,
The method that the first composite plastic layer and the second composite plastic layer is respectively coated by two faces in the impervious barrier
It is prepared；
Preferably, the preparation method of the composite plastic layer includes:
It will be mixed after SAN, CPE, MBS and optional auxiliary agent drying with high-speed mixer, squeeze out, make through double screw extruder
Grain, then the injection molding after cooling, pelletizing and drying, obtains composite plastic layer.
According to another aspect of the present invention, the present invention also provides a kind of batteries, have above-mentioned battery outer packing shell
Body, anode, cathode and electrolyte.
Compared with prior art, the beneficial effects of the present invention are:
Battery housing material provided by the invention, including the first composite plastic being mainly made of SAN, CPE and MBS
Layer, impervious barrier and the second composite plastic layer being mainly made of SAN, CPE and MBS, i.e., by using high-intensitive, high performance plastics
+ high obstructing performance material+high intensity, the mode of high performance plastics form battery housing material, have various excellent mechanicals
Property and thermal property etc. can satisfy electric battery with plastic case (using plastics as the case material of battery) and its shell material wanted
It asks, the leakage problem of electrolyte can be effectively relieved.
Above-mentioned battery, due to using the modified plastics being mainly made of SAN, CPE and MBS, makes its tool with housing material
There are certain intensity and impact resistance, preferable heat resistance, lower water imbibition, preferable electrical insulating property and preferable corrosion-resistant
Property, the leakage of electrolyte can be prevented, guarantees the safety of battery, extends the service life of battery, can be effectively relieved existing
The performances such as application plastic material heat resistance, resistance to ag(e)ing, intensity and/or barrier property in the cell housing it is poor, easily there is electricity
The problem of solving liquid leakage.
Battery external package casing of the invention is mainly made of above-mentioned battery of housing material, thus is at least had
The advantage identical as above-mentioned battery housing material.The preparation method of the battery external package casing, have cleaning, efficiently,
The feature of low cost, and it is easy to operate, productivity effect is high, and it is low for equipment requirements without complicated device systems, it is easy
Realize industrialization large-scale production, it is industrially applicable.
Battery of the invention has above-mentioned battery external package casing, can promote battery with high barrier property, excellent
Electrolyte resistance stability, heat resistance and electrical insulating property etc., ensure that the safety of battery, extend the service life of battery.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiments and examples, but this field skill
Art personnel will be understood that following embodiments and embodiment are merely to illustrate the present invention, and are not construed as limiting model of the invention
It encloses.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.The person that is not specified actual conditions, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
In a first aspect, provide a kind of battery housing material at least one embodiment, including impervious barrier and comprising
The composite plastic layer of first composite plastic layer and the second composite plastic layer, first composite plastic layer, impervious barrier and second are multiple
Plastic layer is closed to be cascading；
The composite plastic layer includes following component: SAN, CPE, MBS and optional auxiliary agent.
Present invention is generally directed to use plastics as battery case materials there is also leakage is easy to appear at present, especially
It is the performance of the electric battery with plastic case product in China, and only only a few even can reach day almost without several technical indicators of enterprise
The level of this enterprise, main is exactly the technical problem unqualified there are electrolyte resistance and scouring depth.So that domestic lithium battery producer
Significant cost pressure is faced, hence it is imperative that the cost of the lithium battery cost of raw material, especially battery packaging material is reduced, because
The packaging material of this electric battery with plastic case realizes that import substitution, the demand of production domesticization are also just increasingly prominent.To alleviate above-mentioned technical problem,
The present invention develops a kind of composite plastic layer applied in electric battery with plastic case.
In above-mentioned composite plastic layer, SAN (Styrene Acrylonitrile) is that styrene-acrylonitrile is styrene-acrylonitrile copolymer
The copolymer of nitrile, it has good mechanical strength, heat resistance and chemical stability, at present the notch impact strength of SAN resin
For 1.26KJ/m2, tensile strength 50.53MPa, vicat softening temperature is 105.6 DEG C, melt index 14.21g/10min,
If directly being applied the requirement for being not met by battery to battery case materials in battery case materials, thus need to SAN
Resin carries out toughening modifying to meet battery to the performance requirement of battery case materials.
CPE (Chlorinated Polyethylene) is the part hydrogen atom that haloflex is on polyethylene molecular chain
Product after being substituted by a chlorine atom both.Its appearance is white powder, non-toxic and tasteless, has excellent weatherability, resistance to ozone, chemically-resistant
Drug and ageing-resistant performance have good oil resistivity, anti-flammability and tinctorial property.Toughness well (still has flexible at -30 DEG C
Property), there is good compatibility with other high molecular materials, decomposition temperature is higher.
MBS (Methyl methacrylate-Butadiene-Styrene) is methyl methacrylate (M), fourth two
The terpolymer object of alkene (B) and styrene (S).It has very high impact strength under room temperature and low temperature；In addition, MBS
Also there is preferable cold resistance, processing performance etc..
Based on this, the present invention provides a kind of composite plastic layers, mainly by SAN, CPE, MBS and optional auxiliary agent group
At CPE has certain toughening effect for SAN/CPE binary polymer blend, but toughening effect is undesirable, thus the application
It also added MBS, the compatibility of CPE and SAN can be increased by the addition of MBS, and then help to improve SAN/CPE blending polymerization
The modified effect of object.Therefore, under the mating reaction of SAN, CPE and MBS three, greatly enhance composite plastic toughness,
The performances such as heat resistance, resistance to ag(e)ing, so that the packaging shell material has good impact strength and excellent barrier property.
Further, the present invention combines composite plastic layer with impervious barrier, i.e. the first composite plastic layer, impervious barrier and
Two composite plastic layers are cascading, and the number of plies of the first composite plastic layer, the second composite plastic layer, impervious barrier can not
It is restricted.In this way, by using high-intensitive, high performance plastics+high obstructing performance material+high intensity, the mode of high performance plastics
Formed battery housing material, have certain intensity, good impact resistance, preferable heat resistance, lower water imbibition,
Preferable electrical insulating property and preferable corrosion resistance, can effectively prevent the leakage of electrolyte, guarantee the safety of battery, extend
The service life of battery, while greatly reducing the production cost of battery.
It is understood that above-mentioned " optional auxiliary agent " indicates: auxiliary agent can be added in the composite plastic layer,
Do not add auxiliary agent.
In a preferred embodiment, the composite plastic layer includes following component according to parts by weight:
SAN60~100 part, CPE0.1~20 part, MBS0.1~20 part and 0~1 part of auxiliary agent.
Help to mention under the coordinated effect of above-mentioned raw materials using suitable and suitable SAN, CPE, MBS and auxiliary agent
Impact resistance, intensity, processing performance, heat resistance, weatherability, corrosion resistance and ageing-resistant performance of high composite plastic layer etc.；Together
The additive amount of the modification agent aid MBS of Shi Shiyi is also more conducive to improve compatibility of the CPE in SAN, makes it have excellent
Comprehensive performance；And above-mentioned raw materials source is wide, is easy to get, low in cost, safety and environmental protection.
In the present invention, according to parts by weight, the typical but non-limiting content of SAN is 60 parts, 65 parts, 70 parts, 75 parts, 80
Part, 85 parts, 90 parts, 95 parts or 100 parts；The typical but non-limiting content of CPE is 0.1 part, 1 part, 2 parts, 4 parts, 5 parts, 6 parts, 8
Part, 10 parts, 12 parts, 14 parts, 15 parts, 16 parts, 18 parts or 20 parts；The typical but non-limiting content of MBS is 0.1 part, 1 part, 2
Part, 4 parts, 5 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 15 parts, 16 parts, 18 parts or 20 parts；Auxiliary agent is typical but non-limiting to be contained
Amount is 0 part, 0.05 part, 0.1 part, 0.15 part, 0.2 part, 0.25 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.8 part or 1 part.
It should be noted that the present invention does not have the source of SAN, CPE, MBS and auxiliary agent special limitation, using ability
Each raw material known to field technique personnel；Its commercial goods can be such as used, it can also be ripe using those skilled in the art
The preparation method known voluntarily is prepared.
Preferably, the composite plastic layer includes following component according to parts by weight:
SAN60~90 part, CPE5~20 part, MBS5~20 part and 0.05~0.3 part of auxiliary agent；
Preferably, the composite plastic layer includes following component according to parts by weight:
SAN70~80 part, CPE10~15 part, MBS10~15 part and 0.1~0.2 part of auxiliary agent.
Typical but unrestricted, composite plastic layer includes following component according to parts by weight: SAN90 parts, CPE5 parts,
MBS5 parts and 0.1 part of auxiliary agent；Alternatively, SAN80 parts, CPE10 parts, MBS10 parts and 0.1 part of auxiliary agent；Alternatively, SAN70 parts, CPE15
Part, MBS15 parts and 0.1 part of auxiliary agent；Alternatively, SAN60 parts, CPE20 parts, MBS20 parts and 0.1 part of auxiliary agent.
By advanced optimizing the content proportion relation of each material component, the heat resistance of composite plastic layer can further improve
The performances such as energy, corrosion resistance, electrical insulating property and impact resistance, stability and intensity, the balance between each performance is more preferable,
Comprehensive performance is more excellent, can more be effectively prevented the leakage of electrolyte, and practical application effect is more preferable, securely and reliably, uses the longevity
Life length.
In a preferred embodiment, the impervious barrier include in plastics, metal, alloy or metal composite extremely
Few one kind；
Preferably, the impervious barrier by aluminizing, stainless steel, in EVOH, PVDC, PLA, PA, HDPE, PE-RT or PE-X
At least one formed；Or,
The impervious barrier is by the alloy including at least any one in tin, aluminium, copper, iron, zinc, nickel, titanium, zirconium, chromium, manganese or magnesium
It is formed；Or,
The impervious barrier is the metal including at least any one in tin, aluminium, copper, iron, zinc, nickel, titanium, zirconium, chromium, manganese or magnesium
Compound is formed.
Impervious barrier of the invention primarily serves the effect of barrier, can use currently used aluminium, however with it is existing
Using aluminium as unlike core layer in technology, impervious barrier aluminium of the invention only plays the role of auxiliary.Thus, this hair
The bright specific material for impervious barrier does not do excessive limitation, can also use plastics, alloy using metals such as aluminiums
Or metal composite, it can also be using other materials.
As long as plastics, metal, alloy, metal composite here to electrolyte stabilization and has certain vapor barrier
Property, it appropriate can be chosen without special limitation.
Typical but unrestricted plastics are EVOH, PVDC, PLA, PA, HDPE, PE-RT or PE-X etc..
Typical but unrestricted metal is aluminium, magnesium, zinc, iron, nickel etc..
Alloy refers to the alloy that metal and other one or more of metals are formed；And metal composite refers to metal and other
Nonmetallic materials combine and are formed by metal-base composites.
Typical but non-limiting alloy is including at least any in tin, aluminium, copper, iron, zinc, nickel, titanium, zirconium, chromium, manganese or magnesium
A kind of alloy, as ferro-tin alloy, magnesium alloy, magnalium manganese alloy, chromium nickel system stainless steel, chrome stainless steel, 301 stainless steels,
304 stainless steels etc..
Typical but non-limiting metal composite is including at least tin, aluminium, copper, iron, zinc, nickel, titanium, zirconium, chromium, manganese or magnesium
In any one metal composite, such as tin/graphene complex, nickel/Polyaniline etc..
From the angle of processability, the easness started with, price, intensity, corrosion resistance etc., above-mentioned impervious barrier is preferably adopted
Be aluminize, stainless steel, EVOH or PVDC.Wherein EVOH is ethylene/vinyl alcohol copolymer, is a kind of high barrier material,
Excellent blocking effect is showed to gas, smell, fragrance, solvent etc.；PVDC be polyvinylidene chloride be a kind of barrier property it is high,
Toughness is strong and low-temperature heat-sealing, heat-shrinkable and the good material of chemical stability, have hinder wet, resistance oxygen, moisture-proof, acid and alkali-resistance,
The performances such as resistance to oil immersion and resistant to many chemical solvent.
In a preferred embodiment, chemical conversion processing is implemented at least one face of the impervious barrier.
The impervious barrier has two opposite surfaces, and the first composite plastic layer and the second composite plastic layer are respectively arranged at
On two opposite surfaces of impervious barrier.
For stabilisation of the impervious barrier in conjunction with composite plastic layer, prevent from dissolving and further preventing corrosion etc., it is preferably right
Face, the further preferred two sides of at least side of impervious barrier are subjected to chemical conversion processing.Wherein chemical conversion processing packet
It includes and forms the processing of acid resistance overlay film or corrosion resistance overlay film on the surface of impervious barrier, so that at least one side of impervious barrier has chemistry
Conversion processing layer, such as corrosion-proof layer etc..
Optionally, the surface of impervious barrier is equipped with the corrosion-proof layer constituted with conductive coating through hot setting.
It optionally, can be with are as follows: by being coated in as the chemical conversion processing method for assigning anticorrosive property to impervious barrier
Film obtained from the particle of the metal oxides such as dispersed alumina, titanium oxide, tin oxide, barium sulfate in phosphoric acid, and through excessively high
Temperature sintering, in the method that the surface of impervious barrier forms corrosion-proof layer.
Chemical conversion processing can be carried out by the methods of stick coating method, rolling method, gravure coating method, infusion process.
In a preferred embodiment, the auxiliary agent includes antioxidant.
What the auxiliary agent in composite plastic of the invention preferably added is antioxidant, and the antioxidant includes but is not limited to antioxygen
Agent 1010, irgasfos 168, antioxidant 619F, antioxidant 1076, antioxidant 626, antioxidant 702, antioxidant 1171, antioxidant
One or more kinds of mixture in BHT or anti-oxidant DLTP.Certainly, the auxiliary agent can also include its commonly used in the art
Auxiliary agent of his type, such as antistatic agent, stabilizer, fire retardant, pigment, filler, reinforcing agent and subtle inorganic compound etc..
The assistant types of addition are not particularly limited in the present invention, and above-mentioned auxiliary agent can be used alone, can also be with
It is used in combination of two or more, the additive amount of auxiliary agent is micro (0.1phr or so).
In a preferred embodiment, the number of plies of first composite plastic layer and the second composite plastic layer is respectively only
It is on the spot 1~20 layer, preferably 1~12 layer.For example, the number of plies of the first composite plastic layer it is typical but it is unrestricted for 1,2,3,4,
5,6,7,8,9,10,11,12,14,15,16,18 or 20；The number of plies of second composite plastic layer it is typical but it is unrestricted for 1,2,3,
4,5,6,7,8,9,10,11,12,14,15,16,18 or 20.
In currently used battery packaging material, the number of plies of each material is usually 1-5 layers, and packaging shell material of the invention
Material can be set to the composite plastic layer and impervious barrier of more layers, and the number of plies can reach 10 layers or more even more multilayers, and when total
The number of plies entirely packs that shell material is still with good performance at 10 layers or more, can guarantee the whole electrochemistry of battery
Energy；Application flexibility is more preferable, and practicability is stronger.
In a preferred embodiment, there is adhesive layer between first composite plastic layer and impervious barrier；With/
Or,
There is adhesive layer between second composite plastic layer and the impervious barrier.
It, can also be to improve between the first composite plastic layer and impervious barrier in battery housing material of the invention
Adhesive layer is set as needed for the purpose of cementability between them；In addition, between the second composite plastic layer and impervious barrier,
Adhesive layer can also be set as needed for the purpose of improving the cementability between them.For the thickness of adhesive layer, such as
It can be for 2 μm or more 40 μm hereinafter, preferably 3 μm or more 20 μm or less.
It is understood that above-mentioned adhesive layer can be set or be not provided with, it is for composite plastic layer and impervious barrier
In conjunction with and the layer that is set as needed.Bonding mechanism for being used to form the bonding agent of adhesive layer is also not particularly limited, and is changed
Learn any ways such as response type, solvent volatile-type, hot-melt type, hot pressing type.
In a preferred embodiment, first composite plastic layer with a thickness of 10~150 μm, preferably 20~
100 μm, further preferably 30~60 μm；
Preferably, the impervious barrier with a thickness of 5~100 μm, preferably 10~80 μm, further preferably 20~40 μ
m；
Preferably, second composite plastic layer with a thickness of 10~150 μm, preferably 20~100 μm, further preferably
It is 30~60 μm.
Preferably, the overall thickness of composite plastic layer and impervious barrier be 100~200 μm, preferably 120~190 μm, further
Preferably 150~180 μm.
It is sufficient can to assign the battery housing material for composite plastic layer and impervious barrier in above-mentioned thickness range
Mechanical strength can mention the durability of battery when using batteries such as secondary cells；Furthermore it is also possible to assign it adequately
Stretch process.
The first composite plastic layer, impervious barrier and the second composite plastic layer in the present invention can be one or more material shapes
At single or multi-layer structure, thickness can according to practical application request be adapted setting.
Preferably, the battery packages shell material is the packaging material of secondary cell.
In optional embodiment of the invention, which can also include sealant layer, peeling agent layer
And protective layer, peeling agent layer therein are successively from top to bottom mutually posted with protective layer, and are located at the first composite plastic layer or second
The outside of composite plastic layer.By the setting of these above-mentioned auxiliary layers, appearance, the sealing of battery housing material can be improved
Property, insulation shielding etc..
Second aspect provides a kind of battery external package casing at least one embodiment, has the interior of storage battery
Portion space is prepared using above-mentioned battery with housing material.
The form of battery provided by the present invention external package casing is not particularly limited, it is commonly used in the art,
Such as the forms such as button, tabular, cylindric.
Optionally, which has shell and the interposer for accommodating each battery.
Battery external package casing and aforementioned battery are thus the electricity based on the same inventive concept with housing material
Pond shell at least has the institute of aforementioned battery housing material effective, and details are not described herein.
The third aspect provides a kind of preparation method of above-mentioned battery external package casing at least one embodiment,
It is prepared by the method for extrusion molding or injection molding；Or,
The method that the first composite plastic layer and the second composite plastic layer is respectively coated by two faces in the impervious barrier
It is prepared.
Excessive restriction is not done for the preparation method of battery external package casing, using extrusion commonly used in the art
The modes such as molding or injection molding.
The preparation method is simple, and productivity effect is high, without complicated device systems, low for equipment requirements, work easy to accomplish
Industryization large-scale production, it is industrially applicable.
The mode of above-mentioned " coating " includes but is not limited to dip-coating, spraying, showering, roller coating or spin coating.
Preferably, the preparation method of the composite plastic layer includes:
It will be mixed after SAN, CPE, MBS and optional auxiliary agent drying with high-speed mixer, squeeze out, make through double screw extruder
Grain, then the injection molding after cooling, pelletizing and drying, obtains composite plastic layer.
Further, it will be mixed after SAN, CPE, MBS of formula ratio and optional auxiliary agent drying with high-speed mixer, then
It squeezes out, be granulated through double screw extruder, be added to NG120-A plastic injection molding machine after traction, pelletizing and drying after cooling
In, obtain composite plastic layer.
Fourth aspect provides a kind of battery at least one embodiment, with above-mentioned battery external package casing, just
Pole, cathode and electrolyte.
It is understood that anode, cathode and the electrolyte in the battery are not particularly limited, this field can be used
The common anode of battery, cathode and electrolyte.The assembling mode of battery is not particularly limited, using conventional battery pack
Dress technique is assembled.
Due to the battery have above-mentioned battery external package casing, and then promote battery with high barrier property, compared with
Low water imbibition, excellent electrolyte resistance stability, heat resistance, electrical insulating property and corrosivity etc., ensure that the safety of battery,
Extend the service life of battery.
Combined with specific embodiments below and comparative example, the invention will be further described.
Embodiment 1
A kind of battery housing material, including impervious barrier and comprising the first composite plastic layer and the second composite plastic layer
Composite plastic layer, the first composite plastic layer, impervious barrier and the second composite plastic layer are cascading, and the thickness of each layer is followed successively by
40 μm, 20 μm and 40 μm, the number of plies of each layer is 1 layer；
Wherein, composite plastic layer includes following component according to parts by weight: SAN90 parts, CPE5 parts, MBS5 parts and antioxygen
0.1 part of agent；
Impervious barrier is to aluminize.
Embodiment 2
A kind of battery housing material, including impervious barrier and comprising the first composite plastic layer and the second composite plastic layer
Composite plastic layer, the first composite plastic layer, impervious barrier and the second composite plastic layer are cascading, and the thickness of each layer is followed successively by
50 μm, 15 μm and 50 μm, the number of plies of each layer is 1 layer；
Wherein, composite plastic layer includes following component according to parts by weight: SAN80 parts, CPE10 parts, MBS10 parts and anti-
0.1 part of oxygen agent；
Impervious barrier is to aluminize.
Embodiment 3
A kind of battery housing material, including impervious barrier and comprising the first composite plastic layer and the second composite plastic layer
Composite plastic layer, the first composite plastic layer, impervious barrier and the second composite plastic layer are cascading, and the thickness of each layer is followed successively by
40 μm, 20 μm and 40 μm, the number of plies of each layer is 1 layer；
Wherein, composite plastic layer includes following component according to parts by weight: SAN70 parts, CPE15 parts, MBS15 parts and anti-
0.1 part of oxygen agent；
Impervious barrier is stainless steel.
Embodiment 4
A kind of battery housing material, including impervious barrier and comprising the first composite plastic layer and the second composite plastic layer
Composite plastic layer, the first composite plastic layer, impervious barrier and the second composite plastic layer are cascading, and the thickness of each layer is followed successively by
45 μm, 16 μm and 45 μm, the number of plies of each layer is 1 layer；
Wherein, composite plastic layer includes following component according to parts by weight: SAN60 parts, CPE20 parts, MBS20 parts and anti-
0.1 part of oxygen agent；
Impervious barrier is stainless steel.
Embodiment 5
A kind of battery housing material, including impervious barrier and comprising the first composite plastic layer and the second composite plastic layer
Composite plastic layer, impervious barrier is between the first composite plastic layer and the second composite plastic layer, the first composite plastic layer, impervious barrier
50 μm, 10 μm and 30 μm are followed successively by with the thickness of the second composite plastic layer, the number of plies of each layer is respectively 1 layer, 2 layers and 2 layers；
Remaining is same as Example 1.
Embodiment 6
A kind of battery housing material, including impervious barrier and comprising the first composite plastic layer and the second composite plastic layer
Composite plastic layer, impervious barrier is between the first composite plastic layer and the second composite plastic layer, the first composite plastic layer, impervious barrier
30 μm, 8 μm and 22 μm are followed successively by with the thickness of the second composite plastic layer, the number of plies of each layer is respectively 2 layers, 4 layers and 3 layers；
Remaining is same as Example 2.
Embodiment 7
A kind of battery housing material, including impervious barrier and comprising the first composite plastic layer and the second composite plastic layer
Composite plastic layer, the first composite plastic layer, impervious barrier and the second composite plastic layer are cascading, and the thickness of each layer is followed successively by
20 μm, 15 μm and 20 μm, the number of plies of each layer is respectively 5 layers, 1 layer and 5 layers；
Remaining is same as Example 3.
Embodiment 8
A kind of battery housing material, the difference with embodiment 1 are only that:
Corrosion-protected surface processing is applied with for the surface that impervious barrier is aluminized.
Embodiment 9-10
A kind of battery housing material, the difference with embodiment 1 are only that:
Impervious barrier is respectively EVOH and PVDC.
Embodiment 11
A kind of battery housing material, the difference with embodiment 1 are only that:
There is adhesive layer between first composite plastic layer and impervious barrier, have between the second composite plastic layer and impervious barrier viscous
Connect layer.
Embodiment 12
A kind of battery housing material, the difference with embodiment 1 are only that:
Composite plastic layer includes following component according to parts by weight: SAN100 parts, CPE18 parts, MBS12 parts, antioxidant
0.05 part, 0.05 part of antistatic agent and 0.1 part of stabilizer.
The battery external package casing being prepared using the battery in embodiment 1-12 with housing material, can pass through
The method of extrusion molding or injection molding is prepared.
Wherein, the preparation method of composite plastic layer includes: that will use high speed after SAN, CPE, MBS of formula ratio and auxiliary agent drying
Then mixing machine mixing is squeezed out through double screw extruder, is granulated, be added to NG120- after traction, pelletizing and drying after cooling
In A plastic injection molding machine, composite plastic layer is obtained.
Comparative example 1
A kind of battery housing material, the difference from embodiment 1 is that composite plastic layer；
Composite plastic layer includes following component according to parts by weight: SAN55 parts, CPE25 parts, MBS25 parts and antioxidant
0.1 part；
Main matter content in this comparative example in composite plastic layer is not in range provided by the present invention.
Comparative example 2
A kind of battery housing material, the difference from embodiment 1 is that composite plastic layer；
Composite plastic layer includes following component according to parts by weight: SAN80 parts, CPE20 parts and 0.1 part of antioxidant；
MBS is omitted in the composite plastic layer of this comparative example.
Comparative example 3
A kind of battery housing material, the difference from embodiment 1 is that composite plastic layer；
Composite plastic layer in this comparative example is using ABS plastic in the prior art.
Comparative example 4
A kind of battery housing material, the difference from embodiment 1 is that composite plastic layer；
Composite plastic layer in this comparative example is using PP plastics in the prior art.
Performance test
The battery in embodiment 1-12 and comparative example 1-4 is carried out with housing material respectively relevant physical
Energy, Mechanics Performance Testing, the performance test results are as shown in table 1.
1 the performance test results of table
Heat seal strength test method therein are as follows: by the composite plastic layer of sample to impervious barrier according to encapsulation 180 DEG C of * of condition
4sec*0.6MP is sealed, and then tests Bonding strength (N/15mm) with tensile testing machine, this item test assessment sample heat-sealing
Intensity, heat seal strength is higher, and electrolyte more will not leak outside.The test method of peel strength are as follows: sample is cut into 15mm wide small pieces and is put
Enter in electrolyte, electrolyte composition is (EC:DEC=1:1,1MLiPF6), it is closed at 85 DEG C to impregnate 4 hours, assess composite plastic
Peel strength between layer and impervious barrier.
In addition, also having carried out vapor water barriers performance, oxygen with housing material to the battery of each embodiment and comparative example
The correlated performance test of barrier property and anti-electrolyte property etc., test result are as shown in table 2.
2 the performance test results of table
The test method of electrolyte resistance therein are as follows: soak 85 DEG C electrolyte 7 days according to the sample that GB8808-88 is measured
Electrolyte resistance afterwards.The appraisal procedure of package are as follows: inject a sample into electrolyte (EC:DEC=1:1,1MLiPF6), heat-sealing
It saves one month afterwards, whether there is or not electrolyte leakages for confirmation.
Battery of the invention has certain intensity, good resistance to punching with housing material it can be seen from Tables 1 and 2
Hitting property, vapor water barriers performance with higher and oxygen barrier property, and can effectively electrolyte leakage, guarantee the peace of battery
Quan Xing, excellent combination property.And pass through the comparative analysis of embodiment and comparative example part it can also be seen that changing each in composite plastic layer
The content of component keeps it not within the scope of the present invention, perhaps omits any component therein or uses existing skill
Common ABS plastic, PP plastic or other material in art can be such that the performance of battery housing material declines, intensity, electrolyte resistance
Performance etc. is poor, influences the service life of battery.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of battery housing material, which is characterized in that answered including impervious barrier and comprising the first composite plastic layer and second
The composite plastic layer of plastic layer is closed, first composite plastic layer, impervious barrier and the second composite plastic layer are cascading；
The composite plastic layer includes following component: SAN, CPE, MBS and optional auxiliary agent.
2. battery housing material according to claim 1, which is characterized in that the composite plastic layer includes by weight
The following component of number meter:
SAN60~100 part, CPE0.1~20 part, MBS0.1~20 part and 0~1 part of auxiliary agent；
Preferably, the composite plastic layer includes following component according to parts by weight:
SAN60~90 part, CPE5~20 part, MBS5~20 part and 0.05~0.3 part of auxiliary agent；
Preferably, the composite plastic layer includes following component according to parts by weight:
SAN70~80 part, CPE10~15 part, MBS10~15 part and 0.1~0.2 part of auxiliary agent.
3. battery housing material according to claim 1 or 2, which is characterized in that the impervious barrier includes plastics, gold
At least one of category, alloy or metal composite；
Preferably, the impervious barrier by aluminizing, stainless steel, in EVOH, PVDC, PLA, PA, HDPE, PE-RT or PE-X extremely
A kind of few formation；Or,
The impervious barrier is by the alloy shape including at least any one in tin, aluminium, copper, iron, zinc, nickel, titanium, zirconium, chromium, manganese or magnesium
At；Or,
The impervious barrier is the metal composite including at least any one in tin, aluminium, copper, iron, zinc, nickel, titanium, zirconium, chromium, manganese or magnesium
Object is formed.
4. battery housing material according to claim 3, which is characterized in that at least one face of the impervious barrier
Implement chemical conversion processing.
5. battery housing material according to claim 1 or 2, which is characterized in that the auxiliary agent includes antioxidant.
6. battery housing material according to claim 1 or 2, which is characterized in that first composite plastic layer and
The number of plies of second composite plastic layer is each independently 1~20 layer, preferably 1~12 layer.
7. battery housing material according to claim 1 or 2, which is characterized in that first composite plastic layer and
There is adhesive layer between impervious barrier；And/or
There is adhesive layer between second composite plastic layer and the impervious barrier；
Preferably, first composite plastic layer with a thickness of 10~150 μm；
Preferably, the impervious barrier with a thickness of 5~100 μm；
Preferably, second composite plastic layer with a thickness of 10~150 μm.
8. a kind of battery external package casing has the inner space of storage battery, which is characterized in that use claim 1~7
Described in any item batteries are prepared with housing material.
9. the preparation method of battery external package casing as claimed in claim 8, which is characterized in that pass through extrusion molding or note
Molding method is moulded to be prepared；Or,
The method preparation of the first composite plastic layer and the second composite plastic layer is respectively coated by two faces in the impervious barrier
It obtains；
Preferably, the preparation method of the composite plastic layer includes:
Will SAN, CPE, MBS and optional auxiliary agent it is dry after mix, through extrusion, granulation, cooling, pelletizing and it is dry after be molded into
Type obtains composite plastic layer.
10. a kind of battery, which is characterized in that have battery external package casing, anode, cathode and electricity according to any one of claims 8
Xie Zhi.
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Cited By (1)
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| WO2022212454A1 (en) * | 2021-03-31 | 2022-10-06 | Xerox Corporation | Biodegradable electrochemical device with barrier layer |
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