WO2017148444A1 - 电池包装材料、软包电池及电池热控制装置 - Google Patents

电池包装材料、软包电池及电池热控制装置 Download PDF

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Publication number
WO2017148444A1
WO2017148444A1 PCT/CN2017/075659 CN2017075659W WO2017148444A1 WO 2017148444 A1 WO2017148444 A1 WO 2017148444A1 CN 2017075659 W CN2017075659 W CN 2017075659W WO 2017148444 A1 WO2017148444 A1 WO 2017148444A1
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Prior art keywords
aluminum
layer
battery
aluminum foil
corrosion
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PCT/CN2017/075659
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English (en)
French (fr)
Inventor
谢彦君
Original Assignee
谢彦君
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Application filed by 谢彦君 filed Critical 谢彦君
Priority to US16/082,232 priority Critical patent/US20190386260A1/en
Priority to CN201790000606.2U priority patent/CN213845356U/zh
Priority to DE112017001136.1T priority patent/DE112017001136T5/de
Publication of WO2017148444A1 publication Critical patent/WO2017148444A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/61—Types of temperature control
    • H01M10/613—Cooling or keeping cold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/10—Alloys based on aluminium with zinc as the next major constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/62—Heating or cooling; Temperature control specially adapted for specific applications
    • H01M10/625—Vehicles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/64—Heating or cooling; Temperature control characterised by the shape of the cells
    • H01M10/647—Prismatic or flat cells, e.g. pouch cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/655—Solid structures for heat exchange or heat conduction
    • H01M10/6554—Rods or plates
    • H01M10/6555—Rods or plates arranged between the cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/655—Solid structures for heat exchange or heat conduction
    • H01M10/6556—Solid parts with flow channel passages or pipes for heat exchange
    • H01M10/6557—Solid parts with flow channel passages or pipes for heat exchange arranged between the cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/656—Means for temperature control structurally associated with the cells characterised by the type of heat-exchange fluid
    • H01M10/6567—Liquids
    • 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
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags
    • 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
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/117—Inorganic material
    • H01M50/119—Metals
    • 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
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/121—Organic material
    • 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
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • 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
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
    • H01M50/128—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers with two or more layers of only inorganic material
    • 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
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/204—Racks, modules or packs for multiple batteries or multiple cells
    • H01M50/207—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape
    • H01M50/211—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape adapted for pouch cells
    • 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
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/289—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by spacing elements or positioning means within frames, racks or packs
    • H01M50/291—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by spacing elements or positioning means within frames, racks or packs characterised by their shape
    • 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
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/289—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by spacing elements or positioning means within frames, racks or packs
    • H01M50/293—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by spacing elements or positioning means within frames, racks or packs characterised by the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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

Definitions

  • the invention relates to a packaging material for a battery and a soft pack battery, in particular to a packaging material for a soft pack battery and a soft pack battery which can be used for immersing in a cooling water, for example, a water cooling system applicable to the field of a vehicle power battery and an energy storage battery. medium.
  • a cooling water for example, a water cooling system applicable to the field of a vehicle power battery and an energy storage battery. medium.
  • the thermal management of the power battery is one of the core technologies of the power battery.
  • the existing soft pack battery cooling method is more air-cooled. Even if it is water-cooled, the water-cooled plate is used to contact the battery for heat exchange. The corresponding contact thermal resistance is high and the heat exchange efficiency is low.
  • the aluminum plastic film used for packaging the soft pack battery is usually made of 8 series aluminum alloy aluminum foil, and the aluminum foil is annealed to a soft aluminum foil, and the deep molding property is good.
  • the battery packaging material is mainly considered to be resistant to electrolyte corrosion.
  • the main technical solution is to physically or chemically modify the corrosion-resistant layer on the side of the packaging material facing the electrolyte, which is to prevent the electrolyte from corroding the inner surface of the aluminum foil and causing aluminum plastic. Peeling between layers.
  • the outermost layer of the existing aluminum plastic film contains a protective plastic film such as polyamide. These plastic protective films have poor hydrolysis resistance, and if they are in contact with water for a long time, they are easily hydrolyzed.
  • the existing aluminum-plastic film aluminum foil has a high iron content and is poor in water corrosion resistance, and is likely to cause corrosion and perforation when exposed to water.
  • the thickness of the aluminum foil aluminum foil layer in the existing power soft pack battery is usually only 40 micrometers, and the existing aluminum plastic film does not meet the long-term water corrosion resistance requirements regardless of its composition and/or thickness. . Since the water-resistant corrosion resistance is insufficient, the battery packaged by the aluminum plastic film is immersed in water for a long time, and there is a risk of corrosion perforation.
  • the conventional means of the prior art is to improve the hydrolysis resistance of the outer protective film, for example, a PET film which is more water resistant than the nylon film is used as the outermost protective film.
  • PET film improves the corrosion resistance of water vapor or water droplets in the air, but it is still not suitable for long-term immersion in water.
  • the present invention boldly adopts a cooling scheme of directly immersing a soft pack battery in cooling water in order to obtain higher battery cooling performance.
  • the outermost nylon protective layer of the existing soft plastic battery packaging has poor corrosion resistance against the antifreeze coolant.
  • the aluminum foil used as the water blocking layer is aluminum-iron alloy, and its mechanical strength and anti-freezing coolant Corrosion performance is also poor, so the existing aluminum plastic film can not meet the requirements of long-term immersion water cooling system.
  • the present invention creatively provides the following new battery packaging material solutions and battery cooling system solutions to meet the thermal management needs of large capacity battery systems such as new energy vehicles or energy storage.
  • the main The invention is characterized in that the composition is ethylene glycol and water) or the anti-corrosion performance of the cooling water is insufficient, that is, the defect that is easily corroded and perforated.
  • the invention provides an aluminum-plastic composite film for packaging lithium ion secondary batteries (hereinafter referred to as Aluminum plastic film), which has higher resistance to coolant corrosion.
  • a first aspect of the present invention provides a battery formed of a metal plastic composite film, preferably a packaging material for a soft pack battery (preferably an aluminum plastic film), comprising a metal foil layer (preferably an aluminum foil layer) and a composite metal foil A plastic layer on the inner surface of the layer, preferably an aluminum foil layer.
  • a second aspect of the present invention provides a soft pack battery comprising an electrode material and an electrolyte and the above-mentioned metal foil layer (preferably an aluminum plastic film) for outer wrapping, the metal foil layer (preferably an aluminum foil layer)
  • the metal foil layer preferably an aluminum foil layer
  • the plastic layer of the surface isolates the electrolyte from the metal foil layer, preferably the aluminum plastic film.
  • a third aspect of the present invention provides a battery thermal control device, preferably a soft pack battery thermal control device, comprising the above-described soft pack battery.
  • the soft pack battery may be packaged in a cooling liquid (such as an antifreeze coolant) after being packaged by the above-mentioned aluminum plastic film which is resistant to the immersion corrosion of the coolant, preferably, the metal plastic composite film is formed.
  • the battery packaging material is immersed in the cooling liquid, and more preferably, the metal foil layer (preferably an aluminum foil layer) is immersed in the cooling liquid so that heat can be directly exchanged with the cooling liquid. In this way, the heat exchange effect of the battery is better, and the temperature of the battery is more uniform around the top, bottom, left and right.
  • the battery packaging material preferably an aluminum plastic film, formed of the metal plastic composite film.
  • the aluminum foil layer is a single layer, and more preferably, the aluminum foil layer is formed of a corrosion resistant aluminum alloy.
  • corrosion resistance means resistance to cooling water or antifreeze corrosion.
  • corrosion resistance as used in the present invention means resistance to cooling water or antifreeze, and does not mean resistance to electrolyte corrosion.
  • the aluminum foil layer is a composite layer, and the aluminum foil layer comprises a core material and a skin material located outside the core material, and the corrosion potential of the skin material of the aluminum foil layer is lower than the corrosion potential of the core material. More preferably, the core material is located between the plastic layer and the skin material inside the aluminum foil layer. More preferably, in the battery thermal control device, the skin material of the aluminum plastic film encapsulating the soft pack battery is immersed in the cooling liquid.
  • the aluminum plastic film of the present invention is a film composite material formed of a plastic film and an aluminum foil film, and is used as a packaging material for a polymer lithium battery.
  • the aluminum foil layer is composited with a plastic layer on one side, or a plastic layer is composited on both sides of the aluminum foil layer. If the plastic layer is only composited on one side of the aluminum foil layer, it is preferably laminated only to the inner side of the aluminum foil layer.
  • the plastic layer compounded on one side surface of the aluminum foil layer may be a single layer plastic or a multilayer plastic.
  • the inner plastic layer is preferably a thermoplastic resin film.
  • a thermoplastic resin film for example, polypropylene (PP) film or polyethylene (PE) film.
  • the thickness of the inner plastic layer may be selected from 50 to 300 micrometers, preferably from greater than 60 to less than 100 micrometers, and more preferably from 70 to 90 micrometers.
  • the inner plastic layer may also be referred to as a heat seal layer or a seal layer.
  • the inner plastic layer is a polyolefin resin or an acid-modified polyolefin resin.
  • the inner plastic layer may also be blended with various additives such as one or more of a flame retardant, a lubricant, an anti-blocking agent, an antioxidant, a light stabilizer, and an adhesion-imparting agent.
  • the inner plastic layer has better electrical insulation properties and thus has a higher withstand voltage value, such as a withstand voltage preferably greater than 1000V, more preferably greater than 2000V.
  • the outer plastic layer is preferably a heat resistant resin film.
  • a polyamide (PA) or nylon (Ny or ON) film or a polyester (PET) film, or a polyimide (PI) film.
  • the composite layer aluminum alloy preferably includes at least a core material and a skin material composited on the outer side of the core material.
  • the composite layer aluminum alloy may be a two-layer aluminum alloy or a multilayer aluminum alloy.
  • the above aluminum plastic film of the present invention may be of any one of the structures A) to B):
  • the aluminum plastic film has a laminate composed of an inner plastic heat seal layer, an intermediate aluminum foil layer, and an outer plastic protective layer, wherein the intermediate aluminum foil layer is formed of a composite layer aluminum foil having a sacrificial anode protection function.
  • the composite layer aluminum foil is formed of a core material and a skin material having a corrosion potential lower than that of the core material.
  • the aluminum plastic film has a laminate composed of an inner plastic heat seal layer and an outer aluminum foil layer, wherein the outer aluminum foil layer is formed of a composite layer aluminum foil having a sacrificial anode protection function.
  • the aluminum plastic film does not contain an outer plastic protective layer.
  • the inner plastic heat seal layer may also be referred to as a thermoplastic resin film layer
  • the outer plastic protective layer may also be referred to as a heat resistant resin film layer.
  • the corrosion potential of the sheath material in the composite aluminum foil is 5 mV-500 mV lower than the corrosion potential of the core material. Further, the corrosion potential of the skin material is 50 mV-500 mV lower than the corrosion potential of the core material. Preferably, the corrosion potential of the sheath material is 70 mV-200 mV lower than the corrosion potential of the core material. More preferably, the corrosion potential of the sheath material is from 100 mV to 170 mV lower than the corrosion potential of the core material.
  • the corrosion potential is referred to as a corrosion potential in a water-based coolant environment.
  • the cooling liquid is a water-based coolant.
  • the water-based coolant refers to a coolant containing water as a basic component.
  • the water-based coolant may also contain various antifreeze agents (such as ethanol, ethylene glycol, propylene glycol, etc.) to form an antifreeze solution having an antifreeze function. Therefore, the cooling liquid of the present invention contains the following types: pure water, a mixed liquid of ethylene glycol and water, and the like.
  • the aluminum plastic film comprises an aluminum foil layer and a plastic layer composited on the surface of the aluminum foil layer; wherein the aluminum foil layer is further covered with a metal zinc layer.
  • the core material of the above composite aluminum foil layer is formed of a corrosion-resistant aluminum alloy or pure aluminum.
  • the pure aluminum includes industrial pure aluminum and high purity aluminum.
  • the purity of aluminum in the pure aluminum is preferably ⁇ 99.0%, more preferably 99.0%-99.99%.
  • the corrosion-resistant aluminum alloy according to the present invention means that the aluminum alloy and the aluminum plastic film can maintain a normal function for a long period of time without failure in an environment in direct contact with the cooling liquid, for example, the aluminum alloy is not corroded and perforated by the cooling liquid.
  • the "non-failure” includes that the electrical insulation function of the aluminum plastic film does not fail and the barrier function does not fail. Although its performance is attenuated, it can still meet the basic requirements.
  • the term "long-term” refers to the normal life cycle duration of a product (such as a car or an automobile power battery), such as a life of more than 5 years, preferably more than 10 years, more preferably more than 15 years.
  • the corrosion-resistant aluminum alloy according to the present invention may be selected from the following rust-proof aluminum or an aluminum alloy having good corrosion resistance: a 1 series aluminum alloy, a 3 series aluminum alloy, a 5 series aluminum alloy, and a 6 series aluminum alloy. Since the corrosion-resistant aluminum alloy (such as aluminum-manganese alloy AA3003, etc., omitted AA below) or pure aluminum has good resistance to coolant corrosion, it can be used as an aluminum foil layer of aluminum plastic film, which can be applied to direct contact with coolant. Application.
  • the core material and the leather material are compositely formed, the core material is located on the inner side, the leather material is located on the outer side, and the corrosion potential of the leather material is lower (or negative) than the corrosion potential of the core material.
  • electrochemical corrosion is formed, and the skin material acts as a sacrificed anode to protect the core material as a cathode, thereby ensuring that the aluminum foil layer in the aluminum plastic film can corrode with water-based coolant for a long period of time, thereby ensuring the battery. Service life.
  • the leather material may be a single layer material or a multilayer material.
  • the multilayer skin material is sequentially lowered from the inside to the outside.
  • the thickness of the skin material preferably accounts for 8 to 20%, more preferably 10 ⁇ 2%, of the entire aluminum foil layer.
  • the inner side of the present invention refers to the side close to the electrolyte inside the battery when applied to the soft pack battery; the outer side refers to the side away from the electrolyte inside the battery when applied to the soft pack battery.
  • the core material may also be referred to as an aluminum substrate.
  • the plastic layer may be a plastic layer of various mature applications in the prior art, such as a cast polypropylene film (CPP) for the inner layer, a nylon film (ON) or/and a polyester film (PET) for the outer layer, and a plastic layer. Adhesive bonding or thermal lamination can be used between the aluminum foil layer and the prior art.
  • the corrosion-resistant aluminum alloy is selected from the group consisting of aluminum manganese aluminum alloy, or aluminum magnesium aluminum alloy, or aluminum magnesium silicon aluminum alloy, or aluminum silicon aluminum alloy.
  • the corrosion-resistant aluminum alloy is more preferably an aluminum manganese aluminum alloy or an aluminum magnesium aluminum alloy.
  • the corrosion-resistant aluminum alloy is selected from the group consisting of a 3 series aluminum alloy, or a 1 series aluminum alloy, or a 5 series aluminum alloy, or a 6 series aluminum alloy, or a 4 series aluminum alloy. Or these aluminum alloys have good corrosion resistance.
  • the corrosion-resistant aluminum alloy is more preferably a 3 series aluminum alloy, or a 1 series aluminum alloy, or a 5 series aluminum alloy, or a 6 series aluminum alloy.
  • the aluminum alloy of the present invention is named using the corresponding standards of the American Aluminum Association.
  • the skin material of the aluminum foil layer is selected from the group consisting of aluminum zinc aluminum alloy, or aluminum copper aluminum alloy.
  • the leather material of the aluminum foil layer is more preferably an aluminum zinc aluminum alloy.
  • the zinc element content in the aluminum-zinc alloy is preferably from 1% to 10%, more preferably from 4% to 7%.
  • the skin material of the aluminum foil layer is selected from a 7-series aluminum alloy or a 2-series aluminum alloy. That is, the leather material is selected from the aluminum alloy of the 7-series or 2-series aluminum alloy whose corrosion potential is lower than the corrosion potential of the core material, such as the 7072 aluminum alloy or the Al clad 2024 aluminum alloy.
  • the skin material of the aluminum foil layer is more preferably a 7-series aluminum alloy.
  • the corrosion potential of 3003 aluminum alloy is about -0.72V
  • the corrosion potential of 7072 aluminum alloy is about -0.88V
  • the corrosion potential of 2024 aluminum alloy is about -0.83V.
  • other improvements to the 7072 can be used for the leather.
  • the skin material of the aluminum foil layer is selected from the group consisting of a modified aluminum alloy to which zinc is added.
  • the sheath material is preferably a zinc-based 1 series aluminum alloy or a zinc-added 3 series aluminum alloy, such as a 3003 aluminum alloy modified type in which a mass percentage of 1.0% to 2.5% zinc is added.
  • the 3003 potential drop of zinc added is about -0.82 to -0.88V, so it is lower than the potential of the 3003 core material.
  • the sheath material is preferably an aluminum alloy formed by adding zinc to a 1 series aluminum alloy (pure aluminum), such as a 1050 aluminum alloy modified type having a mass percentage of 4% to 7% zinc.
  • the corrosion-resistant aluminum alloy is preferably 3003 aluminum alloy, or 3004 aluminum alloy, or 3005 aluminum alloy, or 3105 aluminum alloy, or 3A21 aluminum alloy.
  • the pure aluminum is 1050 aluminum alloy, or 1060 aluminum alloy, or 1070 aluminum alloy, or 1100 aluminum alloy.
  • the skin material of the aluminum foil layer is a 7072 aluminum alloy or a 7075 aluminum alloy.
  • the aluminum foil of the present invention generally refers to a film-like (or flaky) pure aluminum or aluminum alloy, so the aluminum foil of the present invention can also be said to be an aluminum film, and the thickness can be selected as an aluminum film within 200 micrometers, or alternatively 200. - 300 micron or 300-500 micron thick aluminum film.
  • the thickness of the aluminum foil layer in the aluminum plastic film is preferably from 80 to 500 ⁇ m.
  • the thickness is more preferably from 100 to 300 ⁇ m.
  • the thickness is still more preferably from 200 to 300 ⁇ m.
  • the thickness of the aluminum foil layer in the aluminum plastic film is 80-100 microns, or 100-150 microns, or 150-200 microns, or 200-300 microns, or 300-500 microns.
  • the outer portion of the aluminum foil layer is covered with a metallic zinc layer.
  • the zinc layer is preferably formed by a zinc spray process.
  • the aluminum foil layer is a composite layer
  • the aluminum foil layer comprises a core material and a leather material
  • the core material is an aluminum alloy
  • the leather material is a metal zinc layer.
  • the exterior of the aluminum foil layer is bonded to the plastic protective layer by a release agent.
  • the plastic protective layer on the outside of the aluminum foil layer is thus easily separated.
  • the heat seal layer material may be a polypropylene (PP) film or a polyethylene (PE) film.
  • the material of the plastic protective layer may be a nylon (ON) film or a polyester (PET) film.
  • the aluminum foil layer of the aluminum plastic film is a single layer (non-composite layer)
  • the aluminum foil layer may be a 3 series aluminum alloy, or a 1 series aluminum alloy, or a 5 series aluminum alloy, or 6 series aluminum alloy.
  • the core material of the aluminum foil layer may be a 3 series aluminum alloy, or a 1 series aluminum alloy, or a 5 series aluminum alloy, or a 6 series aluminum alloy, or an 8 series aluminum alloy;
  • the skin material of the aluminum foil layer may be a 7-series aluminum alloy or a 2-series aluminum alloy.
  • the aluminum foil layer of the aluminum plastic film provided by the present invention has good corrosion resistance, and the aluminum foil layer and the aluminum plastic film containing the aluminum foil layer have long-term resistance to coolant corrosion.
  • the aluminum foil layer adopts a 3 series aluminum alloy (such as 3003), and more preferably a 3 series aluminum alloy and a 7 series aluminum alloy composite aluminum alloy composite layer (such as 3003/7072). Therefore, it has excellent resistance to coolant corrosion, and can be applied to a power pack battery system for a vehicle, and allows the aluminum plastic film of the soft pack battery to directly contact with the coolant for heat exchange.
  • a 3 series aluminum alloy such as 3003
  • a 7 series aluminum alloy composite aluminum alloy composite layer such as 3003/7072
  • the above-mentioned aluminum plastic film of the present invention can also be used for an aluminum plastic film for battery packaging, and the aluminum foil layer functions as a water blocking layer.
  • the inner side of the aluminum foil layer may further have an anti-corrosion treatment layer formed by chromate treatment or formed by rare earth oxide treatment, but is not essential.
  • the aluminum plastic film containing only the inner plastic layer is immersed in the conductive coolant, and the aluminum foil layer is in electrical communication with the conductive coolant.
  • the electrolyte passes through the inner plastic layer to reach the aluminum foil layer, the electrolyte is in electrical communication with the aluminum foil layer, the conductive coolant and the external ground line, which can trigger the insulation resistance alarm and detect the hydrofluoric acid on the aluminum foil in time. Corrosion and prevention of electrolyte leakage and other hazards. Therefore, in the thermal management system of the present invention, the inner side of the aluminum-plastic film aluminum foil is not subjected to conventional anti-corrosion treatment, and the safety performance of the battery and the entire system can still be guaranteed.
  • the present invention provides an aluminum plastic film which has the following resistance to coolant corrosion: the corrosion resistance test method is an OY water solution corrosion test; the aluminum plastic film or its aluminum foil layer The corrosion life in the above test was greater than 500 hours. Further, the aluminum plastic film or the aluminum foil layer has a corrosion resistance life of more than 1000 hours. Further, the aluminum plastic film or its aluminum foil layer has a corrosion resistance life of more than 2000 hours.
  • the thickness of the aluminum foil of the above-mentioned aluminum plastic film which satisfies the requirements for the corrosion resistance of the aqueous solution of OY in the present invention is preferably more than 80 ⁇ m, further preferably more than 100 ⁇ m, still more preferably from 120 ⁇ m to 300 ⁇ m.
  • the aluminum plastic film or its aluminum foil layer has the following resistance to coolant corrosion: OY aqueous solution corrosion test, or internal corrosion resistance test in ASTM D2570 standard; resistance of the aluminum plastic film or its aluminum foil layer in the above test The corrosion life is greater than 150 hours, or greater than 200 hours, or greater than 336 hours. Further, the aluminum plastic film or the aluminum foil layer has a corrosion resistance life of more than 500 hours. Still further, the aluminum plastic film or its aluminum foil layer has a corrosion resistance life of more than 1000 hours. Further, the aluminum plastic film or the aluminum foil layer thereof has a corrosion resistance life of more than 2000 hours; further, the aluminum plastic film or the aluminum foil layer has a corrosion resistance life of more than 2,500 hours.
  • the 8-line (such as 8021 or 8079) aluminum foil with a thickness of 40 microns has a service life of about 98 hours in the OY aqueous solution corrosion test, and cannot meet the design life requirement of the vehicle at all, so it cannot meet the requirements of the antifreeze immersion cooling method. . Therefore, in order to have the above corrosion resistance, the aluminum foil in the aluminum plastic film needs to have a suitable aluminum alloy material composition and/or a suitable thickness.
  • the aluminum foil material satisfying the above requirements for resistance to coolant corrosion can be selected from a single layer of a 1 series aluminum alloy (pure aluminum), a single layer of a 3 series aluminum alloy, or a composite layer aluminum alloy having a sacrificial anode protection function.
  • the thickness of the aluminum foil which satisfies the above requirements for resistance to coolant corrosion can be selected from the following thicknesses: 80-120 micrometers, or 120-150 micrometers, or 150-200 micrometers, or 200-300 micrometers.
  • pure aluminum AA1050 with a thickness greater than 150 microns or a composite aluminum alloy formed by a combination of AA1050 with a thickness of 100 microns and AA7072 with a thickness of 20 microns (ie, a total thickness of the composite aluminum alloy of 120 microns), the above two aluminum foils are used to manufacture aluminum.
  • the plastic film can meet the above-mentioned anti-freeze corrosion life requirements, so as to meet the automotive life requirements.
  • the present invention can also improve the water-resistant corrosion life of the aluminum-plastic film from the outer plastic layer.
  • the outer plastic layer is a hydrolysis resistant plastic layer.
  • the outer plastic layer is a Teflon layer, or a PE layer, or a composite material of a PE layer and a PA layer, or a water resistant improvement layer of PA.
  • an anticorrosive coating such as chromizing treatment or rare earth oxide treatment may be applied on the outer surface of the aluminum foil layer.
  • the aluminum plastic film or its aluminum foil resistant to coolant (such as an antifreeze mainly composed of ethylene glycol and water) has a corrosion life of more than 5 years, preferably more than 10 years, more preferably more than 15 years.
  • the term "life” refers to the defect that the aluminum plastic film and the aluminum foil cannot be corroded and perforated during the life span.
  • the aluminum foil in the aluminum plastic film needs to be selected from the above-mentioned suitable aluminum alloy material and has sufficient thickness.
  • the aluminum plastic film is composed of an aluminum foil layer and a thermoplastic resin film laminated on the aluminum foil, wherein the aluminum foil is a composite foil having a sacrificial anode function, and the thickness is preferably 100 to 300 ⁇ m.
  • the existing aluminum plastic film product does not take into consideration the application of immersion in the antifreeze solution, nor does it have the function of immersing in the antifreeze solution for a long period of time without failing; and the aluminum plastic film product of the invention has the above special characteristics.
  • the aluminum plastic film or the aluminum foil thereof also has deep drawability or moldability.
  • the aluminum plastic film or its aluminum foil also has good deep drawability or moldability.
  • the aluminum plastic film also has good deep drawability.
  • the aluminum plastic film or its aluminum foil also has a good cupping value. Because of its deep drawability, it can be measured by the cupping value.
  • the stamping depth value or cupping value of the aluminum foil in the aluminum plastic film or aluminum plastic film is more than 5 mm, preferably Greater than 10 mm, more preferably greater than 12 mm.
  • the so-called stamping depth value or cupping value means that the aluminum plastic film or its aluminum foil cannot be perforated after the stamping or cupping test within this value.
  • the present invention further provides an aluminum plastic film comprising an aluminum foil layer and a plastic layer composited on the surface of the aluminum foil layer;
  • the aluminum foil layer is a composite layer aluminum foil, the aluminum foil layer comprises a core material and is located outside the core material
  • the corrosion potential of the leather material of the aluminum foil layer is lower than the corrosion potential of the core material; wherein the leather material located outside the core material is formed by two layers of leather material or more than two layers of multilayer leather material, and the corrosion potential is from inward direction. The outside is lowered in turn. This forms a surface corrosion gradient that is more conducive to preventing pitting corrosion.
  • the composite layer aluminum foil can be heated at a high temperature to gradually expand the zinc element in the leather material to the core material. Disperse, so that the aluminum foil layer from the outside to the inside process, the content of zinc elements changes continuously and gradually, the corrosion potential also changes continuously, avoiding the zinc content and corrosion potential cliff-type changes or mutations, which is more conducive to corrosion morphology transformation For uniform lamellar corrosion.
  • the anti-corrosion mechanism of the composite aluminum foil is different from the traditional anti-corrosion coating treatment method such as chromization on the surface of the aluminum foil.
  • the composite aluminum foil itself is aluminum, which improves the corrosion state by adjusting the corrosion potential of different layers inside the aluminum foil, that is, guided by pitting corrosion.
  • Layered corrosion prevents aluminum foil perforation and battery failure. If the outer surface of the aluminum foil is chromed and immersed in the cooling water, although the corrosion rate of the aluminum foil can be reduced, the corrosion state of the aluminum foil cannot be improved, and the pitting corrosion is not greatly inhibited.
  • the composite layer aluminum foil according to the present invention includes not only the composite between the plurality of different aluminum alloys before the high temperature treatment, but also the element content gradation or corrosion potential in the aluminum foil in the direction perpendicular to the surface of the aluminum foil after the high temperature treatment. Gradient composite layer.
  • the soft pack battery thermal control device as described above further includes a cooling liquid, and the outer package of the soft pack battery is in direct contact with the cooling liquid.
  • the battery thermal control device includes a coolant, which is water, or a mixture of ethanol and water, or a mixture of ethylene glycol and water, or a mixture containing propylene glycol and water, or other antifreeze. Coolant. These coolants are currently used in automotive and industrial coolants. They are not insulating cooling media, but conductive coolants with electrical conductivity (including weak electrical conductivity); however, compared to silicone oil or transformer oil. The insulating cooling medium has the advantages of high thermal conductivity, good fluidity, high heat conduction efficiency, and relatively low cost.
  • the present invention provides a soft pack battery thermal control device comprising a soft pack battery and a cooling liquid, the outer package of the soft pack battery being in direct contact with the coolant, and the soft pack battery is used.
  • the coolant is a conductive coolant.
  • the thermal control device further includes a main board and an outer casing.
  • the main board and the outer casing form a sealed cavity.
  • the electrodes of the soft pack battery protrude above the main board, and the body of the soft pack battery is placed in the sealed cavity.
  • the thermal control device further includes a partition; at least part of a surface of the partition is in direct contact with at least a portion of an outer surface of the soft pack battery, and a fluid passage is disposed in the partition; and a plurality of soft pack batteries form a battery
  • the unit, the battery unit and the partition are spaced apart.
  • the plurality of soft pack batteries may be one, or two, or a plurality of battery cells.
  • the battery packaging material is preferably an aluminum plastic film.
  • the separator is made of a metal material; the corrosion potential of the separator is equal to or less than the corrosion potential of the aluminum foil in the aluminum plastic film.
  • the separator is made of a metal material; the corrosion potential of the separator is lower than the corrosion potential of the aluminum foil in the aluminum plastic film, or the corrosion potential of the separator is equal to or lower than the corrosion potential of the aluminum material of the aluminum foil in the aluminum plastic film.
  • the baffle serves to support the function of the soft pack battery and the tissue flow field, and the baffle may be an extruded flat tube or a flat fin or a staggered serrated fin.
  • the above fin is a type of separator, or a fin-shaped separator having a fluid passage.
  • the fin spacer of the present invention does not include fins such as pin fins that cannot support the battery cells.
  • the battery unit is closely spaced from the fin spacers to form a unitary body, and the unit can be fastened together by straps or through bolts, so that the thermal control system and the battery unit have reliable vibration resistance.
  • the battery thermal control device further includes a main board, and the main board has a socket The portion of the battery that protrudes from the aluminum plastic film is inserted into the main board through the socket.
  • the battery thermal control device further includes an outer casing, the outer casing is provided with a receiving chamber, and the battery unit and the partition are disposed in the receiving chamber of the outer casing, and the outer casing further includes Fluid inlet and fluid outlet.
  • the main board is located in the accommodating chamber of the outer casing, and divides the accommodating chamber into two parts, the first part accommodating the battery unit main body and the partition, and the second part is accommodated from the aluminum plastic film
  • the extended electrode and/or electrode is connected to the port portion, the first portion and the second portion being physically isolated.
  • the battery thermal control device of the present invention may further comprise a cooling pump, a coolant heat exchanger and a corresponding water pipe; or the invention provides a battery cooling system using the above battery thermal control device, further comprising a cooling pump and a cooling liquid Heat exchanger and corresponding water pipes.
  • the coolant heat exchanger is a gas-liquid heat exchanger that directly exchanges heat between the coolant and the ambient air.
  • the heat exchange efficiency of the battery is very high, the heat transfer resistance between the battery body and the coolant is very low, and the heat transfer temperature difference is very small; therefore, the material in the battery body (such as electrolyte, The separator and the solid electrolyte interface film SEI) can allow the coolant to have a higher temperature without over-temperature, that is, reduce the external requirements of the battery cooling, and reduce the cooling cost, so that the above-mentioned gas-liquid heat exchanger can be used.
  • the above cooling system may further include an electric heater for heating the battery.
  • the aluminum foil layer is initially contacted as a contact layer with the cooling liquid, or is peeled off from the outer protective layer (such as a nylon film). After that, it is in contact with the coolant as a water contact layer.
  • the present invention provides another battery packaging material which is formed by compounding a metal foil and a thermoplastic resin film located inside the metal foil; or a composite of a thermoplastic resin film and a metal foil and a heat resistant resin film, the metal foil being located in the thermoplastic resin Between the film and the heat resistant resin film; wherein the metal foil is a single layer metal having corrosion resistance, or the metal foil comprises a core material and a skin material located outside the core material, and the corrosion potential of the metal material of the metal foil is lower than The corrosion potential of the core material.
  • the metal foil is preferably an aluminum foil and/or a copper foil and/or a stainless steel foil.
  • the thickness of the metal foil is preferably 20 to 50 microns, or 50 to 80 microns, or 80 to 150 microns, or 150 to 200 microns, or 200 to 300 microns.
  • the outer side of the metal foil does not contain a plastic film, that is, the plastic film is only composited on the inner side of the metal foil.
  • the inner side of the metal foil layer may further have an anti-corrosion treatment layer, and the anti-corrosion treatment layer is chromate.
  • the treatment is formed or formed by treatment with a rare earth oxide.
  • the present invention also provides a soft pack battery solution, that is, a soft pack battery, which is packaged in an aluminum plastic film having the following resistance to coolant corrosion:
  • the corrosion resistance test method is: OY aqueous solution corrosion test
  • the body of the soft pack battery was immersed in a cooling liquid having a corrosion resistance life of more than 500 hours in the above test.
  • the corrosion-resistant life of the flexible battery body is greater than 1000 hours. Further, the soft pack battery body has a corrosion resistance life of more than 2000 hours.
  • the above corrosion resistance test method is an internal corrosion resistance test in the ASTM D2570 standard, or an outer package aluminum foil is evaluated using a method similar to the "internal corrosion performance test" in Section 5.14 of the QC/T 468-2010 standard.
  • the OY water solution corrosion test referred to in the present invention is a general OY aqueous solution corrosion test in the heat exchanger aluminum heat transfer industry.
  • the method for manufacturing an aluminum plastic film according to the present invention comprises: first selecting a corresponding aluminum foil by the following aqueous solution corrosion test: the corrosion resistance test adopts an OY aqueous solution corrosion test method, and the corrosion resistance life of the aluminum foil under the corrosion test method is greater than 500 Hours; then the aluminum foil and the plastic film are composited to form an aluminum plastic film.
  • the corrosion-resistant life is preferably greater than 1000 hours. More preferably, it is more than 2000 hours.
  • the aluminum foil may be selected from the above pure aluminum or aluminum alloy.
  • the aluminum foil of the aluminum plastic film is only composited with a thermoplastic film on the inner side, that is, the outer side of the aluminum foil does not contain a heat resistant plastic film or a protective film.
  • the invention improves the corrosion resistance and mechanical strength of the aluminum foil in the aluminum plastic film, and the aluminum plastic film without the plastic film on the outer side is not only durable and reliable, but also has a simpler process and lower cost.
  • the aluminum plastic film of the invention has a new function, that is, has the function of long-term resistance to cooling water corrosion, so it can be soaked for a long time. In the cooling water without failure, to meet the thermal management requirements of the immersed water-cooled soft-pack battery cooling system, providing a reliable guarantee for the performance improvement of the battery system.
  • the aluminum foil in the aluminum plastic film is made of a composite layer aluminum foil with different corrosion potential matching between the inner layers, so that the corrosion state of the aluminum foil tends to be layered and corroded. It is good to avoid corrosion failure of aluminum foil in aluminum plastic film.
  • one of the more preferable schemes for the aluminum foil for packaging soft pack batteries of the present invention is to use a pure aluminum core material and a pure aluminum-based zinc-coated leather material composite, which not only has excellent resistance to cooling water pitting corrosion. At the same time, it also has good formability and packageability.
  • the aluminum plastic film provided by the invention can also be a technical solution formed by the combination of the above technical features, which can be used for the packaging of the soft pack battery which is directly in contact with the cooling water, and has the advantages of resistance to cooling water corrosion and long service life.
  • Figure 1 is a schematic view showing the structure of a first aluminum plastic film
  • FIG. 2 is a schematic view showing the structure of a second aluminum plastic film
  • FIG. 3 is a schematic view showing the application of a battery using the aluminum plastic film of the present invention.
  • Figure 4 is a schematic diagram of a soft pack battery
  • Figure 5 is a schematic diagram of a thermal control device for a soft pack battery
  • Figure 6 is a schematic view showing the structure of a third type of aluminum plastic film
  • Figure 7 is a comparison diagram of the corrosion resistance of a single-layer aluminum alloy (left) and a composite aluminum alloy (right);
  • the fin spacer shown in FIG. 8 is a staggered serrated fin, and includes a plurality of tooth-shaped units.
  • the inner rows of the same-toothed unit are connected to form a fluid passage, and adjacent tooth-shaped units are alternately arranged in a front-back direction, and the tooth-shaped unit is The top and bottom planes are in direct contact with the battery;
  • the fin spacer shown in FIG. 9 is a flat fin, and includes upper and lower flat plates connected to the parallel vertical plate and the both ends of the vertical plate.
  • the flat plate is in direct contact with the battery, and a fluid passage is formed between the vertical plates.
  • the aluminum plastic film comprising an aluminum foil layer 1 and plastic layers 2, 3 laminated on both sides of the aluminum foil layer, wherein the aluminum foil layer 1 is composed of a 3 series aluminum alloy aluminum foil layer 7 (core The material is combined with a 7-series aluminum alloy aluminum foil layer 6 (skin material). If the 3003 aluminum alloy is combined with the 7072 aluminum alloy, the 7072 aluminum alloy layer 6 is composited on the outer side of the 3003 aluminum alloy layer 7.
  • the aluminum plastic film is formed by laminating a heat seal layer, a 3003 aluminum foil layer, a 7072 aluminum foil layer, and a nylon layer, wherein the aluminum foil layer and the plastic layer are bonded by a conventional adhesive.
  • the aluminum plastic film from the inside to the outside is: heat seal layer, adhesive layer, 3003 aluminum foil core layer, 7072 aluminum foil skin layer, adhesive layer, nylon protective layer.
  • the corrosion potential of 3003 aluminum alloy is about -0.72V, and the corrosion potential of 7072 aluminum alloy is about -0.88V. Since the corrosion potential of the 7072 aluminum alloy is lower than the corrosion potential of the 3003 aluminum alloy, when contacted with the coolant, the 7072 aluminum alloy acts as a sacrificial anode, protecting the core material from corrosion.
  • the thickness of the heat seal layer is preferably 80-100 ⁇ m, the thickness of the nylon protective layer is preferably 20-30 ⁇ m, and the thickness of the composite aluminum foil layer is preferably 200-300 ⁇ m; wherein the thickness of the 7-series aluminum alloy layer 6 preferably accounts for the entire aluminum foil layer. 10% of 1%.
  • the inner and outer plastic layers 2, 3 and the aluminum foil layer 1 are bonded and bonded by the adhesives 4, 5, respectively.
  • the heat treatment state of the aluminum foil layer may be an O state, an H14 state, or an H16 state, and among them, an O state is preferable.
  • the aluminum foil layer of the embodiment is thicker than the aluminum foil layer in the conventional aluminum plastic film, which is beneficial to the long-term anti-freezing liquid corrosion resistance and the water vapor barrier property of the aluminum plastic film, thereby ensuring the long-term reliability of the soft-pack battery packaging. .
  • This embodiment is substantially similar to the structure of Embodiment 1, and the aluminum alloy layer 1 is also formed by the composite of the core material 7 and the skin material 6, and the skin material 6 is an anode protective layer.
  • the 7072 aluminum alloy was replaced with zinc Zn-added 3003 aluminum alloy (3003 + 1% Zn or 3003 + 1.5% Zn as shown below) as the sacrificial anode layer.
  • the potential of 3003+1% Zn is approximately -0.83V to -0.89V, and its potential is lower than the potential of the 3003 core material.
  • the aluminum foil layer 2 is a second aluminum plastic film comprising an aluminum foil layer 1 and a thermoplastic resin film layer 3 laminated on the inner side of the aluminum foil layer, wherein the aluminum foil layer is a composite layer aluminum foil, the aluminum foil layer comprises a core material and The skin material located on the outer side of the core material has a corrosion potential lower than that of the core material.
  • the core material of the aluminum foil layer is formed of a corrosion-resistant aluminum alloy or pure aluminum.
  • the composite aluminum foil layer 1 is formed by a composite of a 3 series aluminum foil layer 7 (such as 3003) and a 7 series aluminum foil layer 6 (such as 7072).
  • the aluminum foil layer 1 is only internally laminated with a thermoplastic resin film layer 3 (also referred to as a heat seal layer 3, such as CPP), without the need for an outer nylon protective layer.
  • the thickness of the heat seal layer 3 is preferably 30 to 50 ⁇ m, and the thickness of the entire composite aluminum foil layer 1 is preferably 200 ⁇ m.
  • the 7-series aluminum alloy layer 6 is composited on the outer side as a sacrificial anode; the thickness of the 7-series aluminum alloy preferably accounts for 10% of the entire aluminum foil layer 1.
  • the 7-series aluminum alloy acts as a water-repellent layer.
  • the inner thermoplastic resin film layer 3 and the aluminum foil layer 1 are bonded and bonded by an adhesive 5 which is commonly used for an aluminum plastic film.
  • the soft pack battery made of the aluminum plastic film provided above can be immersed in the coolant for a long time, and has long-term resistance to coolant corrosion.
  • the core material layer is also made of 3003 aluminum alloy, except that the skin material 6 is replaced by a metal zinc (Zn) layer instead of the 7-type aluminum foil layer, and the thickness of the metal zinc layer may preferably be 10 -20 microns can be formed by a zinc spray process.
  • the potential of the metal zinc is lower than the potential of the aluminum alloy core material, so that the core material can be used as a sacrificial anode to prevent corrosion.
  • Metallic zinc can also effectively prevent pitting of aluminum alloy core materials.
  • This embodiment describes a battery using the above aluminum plastic film and an application form of the battery.
  • the composite layer aluminum alloy aluminum foil in 3 that is, the aluminum foil is made of 3003 aluminum alloy core material and is externally compounded with 7072 aluminum alloy leather material.
  • the body of the soft pack battery 11 is immersed in the antifreeze coolant. In this way, the heat exchange effect of the battery is better, and the temperature of the battery is more uniform around the upper and lower sides.
  • This embodiment employs an aluminum plastic film structure similar to that of Embodiment 1, except that the adhesive for bonding the nylon protective layer is a release agent which is easy to separate. That is, the nylon protective layer is similar to the release film.
  • the nylon layer can protect the aluminum foil layer; after the deep drawing is completed, the nylon layer can be easily separated from the aluminum foil layer to form an aluminum plastic film similar to that in the embodiment 3.
  • the aluminum plastic film described in this embodiment is formed by a composite of a thermoplastic resin film (i.e., a heat seal layer such as polypropylene) and a composite layer aluminum alloy aluminum foil.
  • the core layer 7 of the aluminum foil layer is made of pure aluminum having a grade of 1050, and the skin material 6 is formed of an aluminum alloy containing 4% to 7% of zinc element based on pure aluminum 1050 (simplified as AA1050 + 4-7% Zn).
  • the corrosion potential of the leather material is negative to the core material, and the leather material is used as the sacrificial anode protection core material, and the skin material recombination ratio is preferably 10 ⁇ 2%.
  • the heat-treated state of the composite aluminum alloy aluminum foil layer is an annealed state (O state), and the thickness is preferably from 100 to 300 ⁇ m, more preferably from 200 to 300 ⁇ m.
  • the composite aluminum foil layer has excellent resistance to coolant corrosion and good ductility and deep drawability.
  • the aluminum plastic film or the aluminum foil thereof is required to have good ductility and deep drawing properties, for example, the GB/T 4156-2007 "metal material sheet and thin strip Eriksson cupping test" standard test, the aluminum plastic film or The cup diameter of the aluminum foil is preferably greater than 5 mm, more preferably greater than 10 mm.
  • the aluminum plastic film or its aluminum foil is required to have good resistance to coolant corrosion.
  • the corrosion resistance test method uses the OY water solution corrosion test commonly used in the heat exchanger aluminum heat transfer industry.
  • the specific test method can also refer to the OY aqueous solution corrosion test in Example 1 of CN201080021209.6.
  • the OY aqueous solution corrosion test is roughly as follows:
  • OY aqueous solution components chloride ion (Cl - ): 195 ⁇ 1 mg / liter, sulfate ion (SO 4 2- ): 60 ⁇ 0.2 mg / liter, iron ion (Fe 3 + ): 30 ⁇ 0.1 mg / liter , copper ion (Cu 2+ ): 1 ⁇ 0.01 mg / liter.
  • the pH of the aqueous OY solution was about 3 (the pH of the aqueous solution in the OY test described in the present invention was about 3 unless otherwise specified).
  • OY aqueous solution temperature 88 ° C, stirred at a rate of 0.6-0.9 m / s (200 rpm) for 8 hours, and then allowed to stand for 16 hours; the above cycle was repeated.
  • the corrosion-resistant life of the aluminum plastic film or its aluminum foil can also be evaluated by the corrosion-resistant service life of the aluminum plastic film or the aluminum foil immersed in the antifreeze on the actual vehicle, for example, the aluminum plastic film having a service life of more than 5 years on the actual vehicle is selected. It is preferably greater than 10 years, more preferably greater than 15 years.
  • the battery thermal control device introduced in this embodiment adopts the above soft pack battery which can be directly immersed in a coolant (such as a coolant mainly composed of ethylene glycol and water).
  • the soft pack battery thermal control device comprises a soft pack battery 11 and a water-based coolant, and the outer package of the soft pack battery 11 is in direct contact with the cooling liquid, and the soft pack battery 11 is made of any one of the above-mentioned anti-cooling liquids. Corroded packaging materials (such as aluminum-plastic films that are resistant to water-based coolants) are formed.
  • the thermal control device further includes a spacer 12, which is preferably a staggered serrated fin spacer as shown in FIG. 8 or a straight fin spacer as shown in FIG.
  • the soft pack battery 11 constitutes a battery unit (of course, two soft pack batteries can also be used to form one battery unit), and the battery unit is spaced apart from the partition plate 12.
  • the baffle serves to support the soft pack battery on the one hand and to organize the flow field of the coolant on the other hand.
  • the aluminum plastic film seals the battery core, and only the battery electrode or the electrode connection port protrudes from the aluminum plastic film;
  • the battery thermal control device further includes a main board 13, and the main board 13 is provided with a socket.
  • the portion of the battery that protrudes from the aluminum plastic film i.e., the positive and negative electrode tabs 111 is inserted into the main board 13 through the socket.
  • a portion of the top edge 112 of the battery is also inserted into the main board 13 through the socket.
  • the battery thermal control device further includes an outer casing 14 having a receiving chamber therein, and a plurality of the battery cells and the partition 12 are tightly integrated into the receiving chamber of the outer casing 14, the outer casing Body 14 also includes a fluid inlet and a fluid outlet (not shown).
  • the main board 13 is located in the accommodating chamber of the outer casing 14, and divides the accommodating chamber into two parts, the first part accommodating the battery unit main body and the partition 12, and the second part is accommodated from the aluminum plastic film
  • the extended electrode and/or electrode is connected to the port portion, the first portion and the second portion being physically isolated.
  • the battery thermal control device further includes a coolant, which is water, or a mixture containing ethylene glycol and water, or a mixture containing propylene glycol and water, or an antifreeze coolant.
  • a coolant which is water, or a mixture containing ethylene glycol and water, or a mixture containing propylene glycol and water, or an antifreeze coolant.
  • the separator 12 is made of a metal material, and the corrosion potential of the separator 12 is lower than the corrosion potential of the aluminum foil in the aluminum plastic film.
  • the metal foil of the packaging material is selected from AA1050 aluminum alloy, and the separator 12 is selected from AA1050+5% Zn.
  • the corrosion potential of the separator 12 is negative to the corrosion potential of the aluminum foil of the aluminum plastic film.
  • the metal foil of the packaging material is selected from the composite material AA1050/AA1050+5% Zn aluminum alloy, and the separator 12 is selected from AA1050+7% Zn.
  • Such a separator can also serve as an anodic protection to further prevent battery corrosion failure.
  • This example is the same as the aluminum foil used in Example 7, except that the aluminum foil material and the aluminum plastic film excellent in molding properties (or deep drawability) were evaluated and selected in the following manner.
  • the CPP surface of the film is directed toward the core and placed in a stamping tester. Ensure that the film is smooth and wrinkle-free, and the amount of side pressure film is sufficient.
  • the heat sealing condition is: heat sealing temperature 190 ° C (upper and lower Uniform heating), heat sealing pressure is 0.2 MPa, heat sealing time is 6 seconds.
  • the aluminum plastic film of the present invention has a molding depth of more than 5.0 mm; more preferably, an aluminum plastic film or aluminum foil having a molding depth of more than 10.0 mm is selected.
  • This embodiment is the same as the aluminum foil used in Example 7, except that it is not evaluated by the OY test, but an aluminum foil of an aluminum plastic film similar to the "internal corrosion performance test" in Section 5.14 of the QC/T 468-2010 standard. The corrosion life of the corrosion is evaluated.
  • Antifreeze model 45% ethylene glycol antifreeze, freezing temperature: -30 ° C
  • ASTM water 1 L (liter) of distilled water contains 148 mg (mg) of sodium sulfide, 165 mg of sodium chloride, and 138 mg of sodium bicarbonate.
  • the experimental results show that the corrosion resistance life of the aluminum foil of the present invention is more than 1000 hours.
  • the core material and the skin material of the composite layer aluminum alloy may be selected from the following items 1 to 4 of Table 2:
  • the corrosion resistance life of the aluminum foil of this embodiment is greater than 1000 hours, even greater than 1500 or 2000 hours.
  • the embodiment provides an aluminum plastic film comprising an aluminum foil layer and a plastic layer composited on the surface of the aluminum foil layer; the aluminum foil layer is a composite layer aluminum foil, and the aluminum foil layer comprises a core material and a leather material located outside the core material.
  • the corrosion potential of the aluminum foil layer is lower than the corrosion potential of the core material; wherein the leather material located outside the core material is formed by two layers of leather material or more than two layers of multilayer leather material, and the corrosion potential is sequentially decreased from the inside to the outside. .
  • the aluminum foil layer in the aluminum plastic film is the core material, the first layer of the skin material, and the second layer of the skin material from the inside to the outside, the core material is AA1050 aluminum alloy, and the first layer of the skin material is AA1050 plus 2% Zn.
  • Aluminum alloy, the second layer of leather is AA1050 based on 4% Zn aluminum alloy. Therefore, the corrosion potential is: core material > first layer of skin material > second layer of skin material. This can further ensure that the corrosion is layered corrosion of layer-by-layer corrosion, thereby further avoiding spot corrosion and ensuring battery safety.
  • This embodiment provides a corrosion resistance test of another soft-package battery outer package aluminum-plastic film aluminum foil, that is, a test method for anti-freeze liquid corrosion of a soft-pack battery. This test method is used to evaluate and determine the anti-freeze corrosion life of the product.
  • Mixing solution components consisting of a 40% by volume antifreeze solution and a 60% ASTM solution.
  • the antifreeze model is 45% ethylene glycol antifreeze, the freezing temperature is minus 30 degrees Celsius;
  • the ASTM solution is configured by 1 liter of distilled water and 148 mg of sodium sulfate, 165 mg of sodium chloride and 138 mg of sodium hydrogencarbonate.
  • Mixed solution temperature 90 ⁇ 2 degrees Celsius.
  • the mixed solution flowed in a horizontal direction parallel to the largest surface of the battery body, and the flow rate through the surface of the battery body was 0.5 m/s.
  • the test was run for 76 hours at the above temperature and flow rate, and was stopped for 8 hours for one cycle.
  • the pH value of the solution was checked and replenished during the shutdown.
  • the solution was divided into pH value and visual inspection. No pH above ⁇ 1 was allowed during the test. The value changes, the appearance of the solution does not allow turbidity and precipitation.
  • the corrosion depth of the aluminum foil of the battery pack can be checked at any time during the test. If the maximum value of the corrosion depth values of all corrosion points is greater than 10% of the original thickness value of the aluminum foil, the test time accumulated at the time when the maximum corrosion depth value reaches 10% of the original thickness value of the aluminum foil is defined as the battery outer packaging aluminum plastic.
  • the corrosion-resistant life of the film aluminum foil is also the anti-freeze corrosion life of the soft-pack battery. Therefore, the so-called life in the test method of this embodiment is the test time accumulated to achieve the above corrosion depth value.
  • the aluminum-plastic film of the soft pack battery package of the present invention is preferably an aluminum plastic film composed of an aluminum foil and a thermoplastic resin film laminated on the inner side of the aluminum foil.
  • the outer side of the aluminum foil has no other plastic layer, so the aluminum foil starts with the antifreeze solution. direct contact.
  • the soft plastic battery outer packaging aluminum plastic film of the present invention may be, although not preferred, an aluminum plastic film composed of an aluminum foil and a thermoplastic resin film laminated on the inner side of the aluminum foil and a heat resistant resin film laminated on the outer side of the aluminum foil.
  • the present invention defines the corrosion resistance test of the above-mentioned soft-package battery outer packaging aluminum-plastic film aluminum foil as "the anti-freeze corrosion life test of a specific soft-package battery ".
  • soft pack batteries having a lifetime value greater than 336 hours in the antifreeze corrosion life test of the particular soft pack battery were selected. Since the power battery is very demanding for safety, it is preferably a soft pack battery of more than 500 hours, more preferably a soft pack battery of more than 1000 hours; further preferably a soft pack battery of preferably more than 2000 hours. Still further, a soft pack battery of preferably more than 5000 hours is preferred.
  • Another assessment method is provided as follows.
  • the test time is fixed at 14 days (ie, 336 hours), and the pitting depth is examined everywhere, and the maximum pitting depth is included.
  • the step is preferably less than 5%.
  • the maximum pitting depth is 20% to 50% of the original thickness value of the aluminum foil, or is greater than 10% and less than 20%, or greater than 0% and less than 10%.
  • the aluminum foil in the aluminum plastic film needs to have a suitable aluminum alloy material composition and a suitable thickness.
  • the aluminum foil material satisfying the above requirements for resistance to coolant corrosion can be selected from a single layer of a 1 series aluminum alloy (pure aluminum) or a composite layer aluminum alloy having a sacrificial anode protection function.
  • the thickness of the aluminum foil that satisfies the above requirements for resistance to coolant corrosion can be selected from the following thicknesses: 120-300 microns.
  • pure aluminum AA1050 with a thickness greater than 150 microns or a composite aluminum alloy formed by a combination of AA1050 with a thickness of 100 microns and AA7072 with a thickness of 20 microns (ie, a total thickness of the composite aluminum alloy of 120 microns), the above two aluminum foils are used to manufacture aluminum.
  • Plastic film and soft pack batteries can meet the above-mentioned anti-freeze corrosion life requirements, thus meeting the automotive life requirements.
  • This embodiment describes an aluminum plastic film whose aluminum foil is formed by compounding a core material and an outer skin material, wherein the core material is formed of an 8-series aluminum alloy (such as 8079 or 8021) of 100 micrometers to 300 micrometers, and the outer skin material is made of 8 series aluminum.
  • the alloy is formed by adding 2%-6% by mass of zinc element (as described in Table 3 below), and the recombination rate is 10%-20%.
  • the aluminum plastic film containing such a composite aluminum alloy has good corrosion resistance and deep drawability, and is tested according to the method of Example 7, and has a corrosion resistance life of more than 1300 hours.
  • This embodiment describes an aluminum plastic film in which an aluminum foil is formed by compounding a core material and an outer skin material, wherein the core material is formed of a 1 series aluminum alloy (such as 1050) of 100 micrometers to 300 micrometers, and the outer skin material is composed of a 1 series aluminum alloy foundation.
  • a 1 series aluminum alloy such as 1050
  • the outer skin material is composed of a 1 series aluminum alloy foundation.
  • the addition of 2% to 6% by mass of zinc element was formed (as described in Table 4), and the recombination rate was 10% to 20%.
  • the core material is formed by a 1 series aluminum alloy (such as 1050) of 100 micrometers to 300 micrometers, and the outer skin material is formed by adding 2% to 6% by mass of zinc element on the basis of the 1 series aluminum alloy (as shown in Table 4). ).
  • the aluminum plastic film containing the composite aluminum alloy has good electrolyte corrosion resistance and good resistance to cooling water corrosion; and the corrosion resistance life is more than 1800 hours according to the method of Example 7.
  • an aluminum plastic film comprising an aluminum foil layer and a plastic layer composited on a surface of the aluminum foil layer, wherein the aluminum foil layer
  • the material is 3003 aluminum alloy.
  • the aluminum plastic film is composed of an outer layer protective layer 2, an aluminum foil layer 1, and an inner layer heat sealing layer 3 from the outside to the inside, and the outer layer protective layer 2 is made of nylon (ON) and the inner layer heat sealing layer 3 is used for flow.
  • the polypropylene film (CPP) which also acts as an insulating layer, also maintains electrical insulation between the aluminum foil layer 1 and the internal electrolyte.
  • the outer protective layer 2, the inner layer heat seal layer 3 and the aluminum foil layer 1 are bonded and bonded by an adhesive (or an adhesive) 4, 5, respectively.
  • the outer protective layer 2 serves to protect the aluminum foil layer 1 during the deep drawing process.
  • the adhesive layer is composed of any one of the following resins: a polyester-urethane resin, a polyether-urethane resin, an isocyanate resin, and an unsaturated carboxylic acid graft polyolefin resin.
  • the aluminum foil layer 1 can also be replaced by other rust-proof aluminum, such as 5 series rust-proof aluminum or other 3 series rust-proof aluminum, more specifically, such as: 3004, 3005, 3105, 5052, 5086, etc.; aluminum foil layer 1 can also Replace with 6 series aluminum alloy, such as 6063.
  • the aluminum foil layer may also be pure aluminum, pure aluminum is 1050 aluminum alloy, or 1060 aluminum alloy, or 1100 aluminum alloy, or a modified type based on the above pure aluminum basic type. These pure aluminum also have good corrosion resistance.
  • the soft pack battery formed by the aluminum plastic film can be directly immersed in the cooling liquid and has a long-term resistance to coolant corrosion, wherein the coolant is preferably a water-based coolant containing ethylene glycol or/and propylene glycol.
  • the coolant is preferably a water-based coolant containing ethylene glycol or/and propylene glycol.
  • the outer protective layer 2 provides protection for the aluminum foil layer 1 in this deep drawing process.
  • the nylon layer 2 may swell and dissolve, but this does not affect the insulation, sealing properties and long-term resistance to coolant corrosion of the aluminum plastic film.
  • the soft pack battery can be directly immersed in the coolant for cooling.
  • the beneficial effect of this is that the heat exchange efficiency of the soft pack battery is very high, and it does not overheat even when working at a high current, which can improve the power density and reliability of the entire battery system.
  • the 3 or 5 series rust-proof aluminum Compared with the 8 series aluminum alloy, the 3 or 5 series rust-proof aluminum has better anti-freeze corrosion resistance, and its corrosion resistance life is longer and more reliable.
  • This embodiment describes a soft-package polymer lithium ion battery coated with the aluminum plastic film described in Embodiment 17, and this embodiment is substantially the same as Embodiment 5 except that the aluminum plastic used for packaging the soft pack battery is used.
  • the aluminum foil in the film is formed of a single-layer aluminum alloy which is formed of a rust-proof aluminum foil, such as a 3003 aluminum foil.
  • This embodiment describes a soft-package polymer lithium ion battery coated with the aluminum plastic film described in Embodiment 17, and this embodiment is substantially the same as Embodiment 5 except that the aluminum plastic used for packaging the soft pack battery is used.
  • the aluminum foil in the film is formed from a single layer of aluminum alloy formed of a 1 series aluminum alloy foil, such as an O-state 1050 aluminum alloy aluminum foil or other pure aluminum.
  • This embodiment describes an aluminum plastic film whose aluminum foil is formed by compounding a core material and an outer skin material, wherein the core material is 150 micrometers to 300 Micron 8-series aluminum alloy (such as 8079 or 8021) is formed, and the outer skin material is made of 7-series aluminum alloy (such as 7072), and the recombination rate is 20%-50%. Further, after the 8 series and the 7 series are combined, heating or annealing treatment is performed to form a step potential change by appropriate diffusion of the Zn element.
  • the aluminum plastic film containing such a composite aluminum alloy has good corrosion resistance and deep drawability, and is tested according to the method of Example 7, and has a corrosion resistance life of more than 1500 hours.
  • This embodiment describes an aluminum plastic film which is bonded from the inside to the outside by a thermoplastic film (e.g., CPP), an aluminum foil layer, and a Teflon film. Since the Teflon film has good water and corrosion resistance, the soft pack battery made of the aluminum plastic film can be immersed in water or antifreeze for a long time.
  • a thermoplastic film e.g., CPP
  • an aluminum foil layer e.g., aluminum foil layer
  • Teflon film e.g., Teflon film
  • Example 7 Reference can be made to Example 7, but the pH of the aqueous OY solution selected in this example is about 11. This example is the same as Example 7 except that the pH of the OY aqueous solution is different from that of Example 7.
  • an aluminum foil with a corrosion resistance of more than 1000 hours is used for the aluminum plastic film for the battery packaging material.
  • a single layer of 1050 aluminum alloy and a composite layer of aluminum alloy (the core material is 1050 aluminum alloy, and the skin material is a sacrificial layer with a negative potential) is subjected to a corrosion resistance comparison test in the OY experiment.
  • the antifreeze system was selected for the OY experiment.
  • the experiment time was 4 weeks.
  • the surface of the material was immersed in nitric acid to remove the corrosion products. The details are as follows:
  • the left figure shows that the AA1050 single-layer aluminum alloy has obvious pitting corrosion, and the pitting corrosion is more serious; while the right figure shows the aluminum of the composite sacrificial layer. No significant pitting occurred on the alloy surface. From this, it is understood that the occurrence of pitting corrosion can be effectively suppressed by compounding a skin material having a relatively negative corrosion potential on the surface of the aluminum alloy core material.
  • the time of corrosion resistance of the aluminum foil against the cooling water can meet the requirements of the automobile; and since the inner core of the aluminum foil is pure aluminum, the electrolyte corrosion resistance is superior to the conventional one.
  • the iron aluminum alloy thus protects the battery's life and safe use.

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Abstract

用于包装电池的电池用包装材料，特别涉及应用于车用的软包电池用包装材料和软包电池热管理系统。针对现有技术中电池用包装材料的抗腐蚀性能不足的缺陷，特提供如下电池包装用铝塑复合膜解决方案：即电池用包装材料，所述电池用包装材料包括铝箔层（1）和复合于铝箔层（1）表面的塑料层（2）；其中，铝箔层（1）由耐冷却水腐蚀的铝合金形成。

Description

电池包装材料、软包电池及电池热控制装置 技术领域
本发明涉及电池用包装材料及软包电池，特别涉及可应用于浸泡于冷却水中的软包电池用包装材料及软包电池，比如可应用于车用动力电池领域和储能电池领域的水冷系统中等。
背景技术
动力电池的热管理是动力电池的核心技术之一，现有的软包电池冷却方式中更多的是风冷，即使是水冷，也是采用水冷板与电池接触换热，而这种换热方式中相应的接触热阻高，换热效率低。纵观现有技术中没有将软包电池直接浸泡在水或防冻液中的应用，更没有与之相适应的专用铝塑膜。
现有技术中软包电池包装用的铝塑膜通常采用8系铝合金铝箔，这种铝箔退火后为软质铝箔，冲深成型性好。目前电池包装材料主要考虑的是耐电解质腐蚀性，主要技术方案是在包装材料朝向电解质的一侧通过物理或化学方式改性形成耐腐蚀层，其作用是防止电解质腐蚀铝箔内表面而导致铝塑膜层间剥离。现有铝塑膜最外层都含有聚酰胺等保护用塑料膜，这些塑料保护膜耐水解能力差，若长期与水接触则很容易水解失效。现有铝塑膜铝箔中铁含量较高，抗水腐蚀能力差，遇水则容易造成腐蚀穿孔。另外，从节约成本和提高电池容量出发，现有动力软包电池中铝塑膜铝箔层的厚度通常仅为40微米，现有铝塑膜无论其成分和/或厚度都不符合长期耐水腐蚀要求。由于耐水腐蚀性能不足，由该种铝塑膜包装的电池长时间浸泡在水中，则存在腐蚀穿孔的风险。
为了提高铝塑膜的耐水解能力，现有技术通常的手段是改善外层保护膜的耐水解能力，比如采用比尼龙膜更耐水的PET膜作为最外侧保护膜。采用PET膜后对耐空气中的水汽或水滴腐蚀性能有所提高，但还是不适合于长期浸泡于水中。
发明内容
本发明从软包电池冷却的需求出发，为了获得更高的电池冷却性能，本发明大胆采用将软包电池直接浸泡于冷却水中的冷却方案。然而，进过深入研究后发现现有软包电池包装用铝塑膜中最外侧尼龙保护层抗防冻冷却液腐蚀性能差，作为阻水层的铝箔为铝铁合金，其机械强度和抗防冻冷却液腐蚀性能也较差，故现有铝塑膜不能满足长期的浸泡式水冷系统要求。为了克服上述缺陷，本发明创造性地提供如下新的电池包装材料方案和电池冷却系统方案，以满足新能源车用或储能用等大容量电池系统的热管理需求。
针对现有技术中用于包装电池(battery)的铝塑膜耐车用防冻冷却液(简称防冻液，其主 要成分为乙二醇和水)或耐冷却水的抗腐蚀性能不足的缺陷，即容易被腐蚀穿孔的缺陷，本发明特提供一种可用于锂离子二次电池包装用铝塑复合膜(以下简称铝塑膜)，其具有更高的耐冷却液腐蚀能力。
本发明第一个方面是提供一种由金属塑料复合薄膜形成的电池、优选为软包电池用包装材料(优选为铝塑膜)，包括金属箔层(优选为铝箔层)和复合于金属箔层(优选为铝箔层)内表面的塑料层。
本发明第二个方面是提供一种软包电池，包含有电极材料和电解质以及外部包裹用的上述的金属箔层(优选为铝塑膜)，所述金属箔层(优选为铝箔层)内表面的塑料层将电解质与金属箔层(优选为铝塑膜)隔离。
本发明第三个方面是提供一种电池热控制装置，优选为软包电池热控制装置，包含有上述的软包电池。该软包电池可采用耐冷却液浸泡腐蚀的上述的铝塑膜包装之后，可以将该软包电池浸泡在冷却液(如防冻冷却液)中，优选地，所述由金属塑料复合薄膜形成的电池用包装材料浸泡在所述冷却液中，更优选地，所述金属箔层(优选为铝箔层)浸泡在所述冷却液中，从而可以直接与冷却液进行热交换。这样电池的换热效果更好，且电池上下左右各处的温度更均匀。
本发明第四个方面是提供一种制造所述由金属塑料复合薄膜形成的电池用包装材料、优选为铝塑膜的方法。
在本发明一种优选实施例中，铝箔层为单层，更优选地，铝箔层由耐腐蚀的铝合金形成。其中，所谓耐腐蚀是指耐冷却水或防冻液腐蚀。若未特别说明，本发明中所谓耐腐蚀均是指耐冷却水或防冻液腐蚀，而不是指耐电解液腐蚀。
在本发明一种优选实施例中，铝箔层为复合层，铝箔层包含有芯材和位于芯材外侧的皮材，铝箔层的皮材的腐蚀电位低于芯材的腐蚀电位。更优选地，所述芯材位于铝箔层内侧的塑料层与皮材之间。更优选的，所述电池热控制装置中，包装软包电池的铝塑膜的皮材浸泡在所述冷却液中。
本发明的铝塑膜是一种塑料膜和铝箔膜形成的薄膜复合材料，是作为聚合物锂电池用包装材料。
其中，铝箔层的单面复合有塑料层，或者铝箔层的两面均复合有塑料层。若塑料层仅复合于铝箔层的单面，优选为仅复合于铝箔层的内侧。其中，上述方案中包括如下情况：复合于铝箔层某一侧表面的塑料层，既可以是单层塑料，也可以是多层塑料。
进一步的，所述内侧塑料层优选为热塑性树脂薄膜。比如，聚丙烯(PP)薄膜或聚乙烯 (PE)薄膜。其中，内侧塑料层的厚度可选为50-300微米，优选为大于60小于100微米，更为优选为70-90微米。该内侧塑料层也可称为热封层或密封层。优选地，所述内侧塑料层为聚烯烃树脂或酸改性聚烯烃树脂。该内侧塑料层中也可以配合各种添加剂，如阻燃剂、润滑剂、防粘连剂、抗氧化剂、光稳定剂、粘着赋予剂中的一种或几种。
优选地内侧塑料层具有更好的电绝缘特性，从而耐电压值更高，比如耐电压优选大于1000V，更为优选大于2000V。
进一步的，所述外侧塑料层优选为耐热性树脂薄膜。比如聚酰胺(PA)或尼龙(Ny或ON)膜、或聚酯(PET)薄膜、或聚酰亚胺(PI)薄膜。
另外，上述复合层铝合金，优选为至少包括芯材和复合于芯材外侧的皮材。复合层铝合金可以是两层铝合金、也可以是多层铝合金。
本发明上述铝塑膜，可以是包括A)-B)中的任意一种结构：
A)所述铝塑膜具有由内侧塑料热封层、中间铝箔层、外侧塑料保护层构成的叠层体，其中中间铝箔层为具有牺牲阳极保护功能的复合层铝箔形成。比如，该复合层铝箔由芯材和腐蚀电位低于芯材的皮材形成。
B)所述铝塑膜具有由内侧塑料热封层、外侧铝箔层构成的叠层体，其中外侧铝箔层为具有牺牲阳极保护功能的复合层铝箔形成。该铝塑膜不含有外侧塑料保护层。
其中，内侧的塑料热封层也可称热塑性树脂薄膜层，外侧的塑料保护层也可称耐热性树脂薄膜层。
复合层铝箔中皮材的腐蚀电位比芯材的腐蚀电位低5mV-500mV。进一步的，皮材的腐蚀电位比芯材的腐蚀电位低50mV-500mV。优选地，皮材的腐蚀电位比芯材的腐蚀电位低70mV-200mV。更为优选地，皮材的腐蚀电位比芯材的腐蚀电位低100mV-170mV。
本发明中，若未特别说明的，腐蚀电位均指为在水基冷却液环境下的腐蚀电位。通过这种复合铝箔中皮材与芯材的合理电位匹配，有利于避免铝箔(特别是芯材)的点腐蚀。
本发明中若未特别说明，所述冷却液为水基冷却液。所谓水基冷却液，是指以水作为基本成分的冷却液。水基冷却液还可以是包含有各种防冻剂(比如乙醇、乙二醇、丙二醇等)以形成具有防冻功能的防冻液。所以，本发明的冷却液包含有如下种类：纯水、乙二醇与水的混合液等。
或者，所述铝塑膜包括铝箔层和复合于铝箔层表面的塑料层；其中，铝箔层外部还覆盖有金属锌层。
进一步的，上述复合铝箔层的芯材由耐腐蚀的铝合金或纯铝形成。所述纯铝包括工业纯铝和高纯铝。所述纯铝中铝的纯度优选≥99.0％，更为优选为99.0％-99.99％。
本发明所述的耐腐蚀的铝合金，是指在与冷却液直接接触的环境下，铝合金和铝塑膜能长期保持正常的功能而不失效，比如铝合金不被冷却液腐蚀穿孔。其中所述“不失效”包括铝塑膜的电绝缘功能不失效且阻隔功能也不失效。其性能虽然有量上的衰减，但仍能满足基本要求。其中所谓的“长期”，是指产品(如汽车或汽车动力蓄电池)正常的寿命周期时长，比如寿命大于5年，优选大于10年，更为优选大于15年。本发明所述耐腐蚀的铝合金，可选自如下防锈铝或者说具有良好耐蚀性的铝合金：1系铝合金、3系铝合金、5系铝合金、6系铝合金。由于耐腐蚀的铝合金(如铝锰合金AA3003等，以下省略AA)或纯铝具有很好的耐冷却液腐蚀功能，故将其作为铝塑膜的铝箔层，可以应用于与冷却液直接接触的应用场合。
若铝箔层为复合层，由芯材和皮材复合形成，芯材位于内侧，皮材位于外侧，且皮材的腐蚀电位低于(或称负于)芯材的腐蚀电位。在与有腐蚀性介质接触时，形成电化学腐蚀，皮材作为被牺牲的阳极，保护作为阴极的芯材，从而确保铝塑膜中的铝箔层能够长期耐水基冷却液腐蚀，进而确保电池的使用寿命。其中，皮材可以是单层材料，也可以是多层材料。若皮材为多层，则优选地多层皮材由内到外腐蚀电位依次降低。皮材厚度优选占整个铝箔层的8～20％，更为优选为10±2％。本发明所谓内侧是指应用于软包电池时，靠近电芯内部电解质的那侧；所谓外侧是指应用于软包电池时，远离电芯内部电解质的那侧。
其中，芯材也可称为铝基材。塑料层可以是现有技术中各种成熟应用的塑料层，如内层采用流延聚丙烯薄膜(CPP)，外层采用尼龙薄膜(ON)或/和聚酯薄膜(PET)，且塑料层与铝箔层之间可以采用现有工艺中粘合剂粘接复合或热法复合。
进一步的，耐腐蚀的铝合金选自铝锰铝合金，或者铝镁铝合金，或者铝镁硅铝合金，或者铝硅铝合金。耐腐蚀的铝合金更为优选为铝锰铝合金，或者铝镁铝合金。
或者，进一步的，耐腐蚀的铝合金选自3系铝合金，或者1系铝合金，或者5系铝合金，或者6系铝合金，或者4系铝合金。或者说这些铝合金具有良好的抗蚀性。耐腐蚀的铝合金更为优选为3系铝合金，或者1系铝合金，或者5系铝合金，或者6系铝合金。
本发明铝合金命名采用美国铝业协会相应标准。
进一步的，若铝箔层为复合层，铝箔层的皮材选自铝锌铝合金，或者铝铜铝合金。铝箔层的皮材更为优选为铝锌铝合金。铝锌合金中锌元素含量优选为1％-10％，更为优选为4％-7％。
或者，进一步的，若铝箔层为复合层，铝箔层的皮材选自7系铝合金，或者2系铝合金。即该皮材选自7系或2系铝合金中腐蚀电位低于芯材腐蚀电位的铝合金，如选用7072铝合金、或Al clad 2024铝合金。铝箔层的皮材更为优选为7系铝合金。比如，3003铝合金腐蚀电位约为-0.72V，7072铝合金腐蚀电位约为-0.88V，2024铝合金腐蚀电位约为-0.83V。另外，除 了7072的基本型之外，皮材也可选用7072的其他改进型。
或者，进一步的，若铝箔层为复合层，铝箔层的皮材选自添加锌的改进型铝合金。其中，皮材优选为添加锌的1系铝合金或添加锌的3系铝合金，比如添加质量百分比为1.0％-2.5％锌的3003铝合金改进型。添加了锌的3003电位降低，大约为-0.82至-0.88V，故低于3003芯材的电位。或者，皮材优选为在1系铝合金(纯铝)基础上添加锌形成的铝合金，比如添加质量百分比为4％-7％锌的1050铝合金改进型。
进一步的，耐腐蚀的铝合金优选为3003铝合金，或3004铝合金，或3005铝合金，或3105铝合金，或3A21铝合金。
进一步的，纯铝为1050铝合金，或者1060铝合金，或者1070铝合金，或者1100铝合金。
进一步的，若铝箔层为复合层，铝箔层的皮材为7072铝合金、或者7075铝合金。
本发明所述的铝箔泛指为薄膜状(或薄片状)的纯铝或铝合金，故本发明铝箔也可以说是铝膜，厚度可选为200微米以内的铝膜，也可选为200-300微米或300-500微米厚的铝膜。或者，进一步的，铝塑膜中铝箔层的厚度优选为80-500微米。该厚度更为优选为100-300微米。该厚度再更为优选为200-300微米。
或者，进一步的，铝塑膜中铝箔层的厚度为80-100微米，或者100-150微米，或者150-200微米，或者200-300微米，或者300-500微米。
进一步的，铝箔层的外部覆盖有金属锌层。所述锌层优选采用喷锌工艺形成。
或者，进一步的，铝箔层为复合层，铝箔层包含有芯材和皮材，芯材为铝合金，皮材为金属锌层。
进一步的，铝箔层的外部通过离型剂粘合塑料保护层。这样铝箔层外部的塑料保护层便于被分离。
进一步的，所述热封层材料可以是聚丙烯(PP)薄膜、也可以是聚乙烯(PE)薄膜。
进一步的，所述塑料保护层的材料可以是尼龙(ON)薄膜，也可以是聚酯(PET)薄膜。
以上技术方案中，包含如下技术方案：若铝塑膜的铝箔层为单层(非复合层)，则该铝箔层可以是3系铝合金，或者1系铝合金，或者5系铝合金，或者6系铝合金。若铝塑膜的铝箔层为复合层，则该铝箔层的芯材可以是3系铝合金，或者1系铝合金，或者5系铝合金，或者6系铝合金，或者8系铝合金；其铝箔层的皮材可以是7系铝合金，或者2系铝合金。
本发明以上提供的铝塑膜的铝箔层抗蚀性良好，铝箔层和含有该铝箔层的铝塑膜具有长期耐冷却液腐蚀性能。
本发明以上提供的铝塑膜，比如铝箔层采用了3系铝合金(如3003)，更为优选地采用了3系铝合金和7系铝合金复合的铝合金复合层(如3003/7072)，故其具有优良的耐冷却液腐蚀性能，可应用于车用软包动力电池系统中，并可让软包电池的铝塑膜与冷却液直接接触换热。
本发明上述的铝塑膜，也可以用于电池包装用铝塑膜，所述铝箔层具有阻水层的作用。
作为可选方案，上述铝箔层内侧还可以具有防腐蚀处理层，该防腐蚀处理层为铬酸盐处理形成、或者由稀土氧化物处理形成，但并不是必需的。本发明中仅包含内侧塑料层的铝塑膜浸泡在导电冷却液中，铝箔层与导电冷却液电连通。在极少数情况下，当电池电解质穿过内侧塑料层达到铝箔层时，电解质与铝箔层、导电冷却液以及外部接地线形成电连通，进而可触发绝缘电阻报警，及时探测到氢氟酸对铝箔的腐蚀，并防止电解液泄漏等危险发生。所以，本发明热管理系统中铝塑膜铝箔内侧不做传统的防腐蚀处理，电池及整个系统的安全性能仍能得到保障。
本发明提供还如下铝塑膜，所述铝塑膜或其铝箔层具有如下耐冷却液腐蚀性能：耐腐蚀测试方法为OY水溶液(Oyama Water Solution)腐蚀试验；该铝塑膜或其铝箔层的在上述试验中的耐腐蚀寿命大于500小时。进一步的，所述铝塑膜或其铝箔层的耐腐蚀寿命大于1000小时。更进一步的，所述铝塑膜或其铝箔层的耐腐蚀寿命大于2000小时。
本发明中上述满足OY水溶液耐腐蚀性能要求的铝塑膜的铝箔厚度优选为大于80微米，进一步优选大于100微米，更进一步优选为120微米-300微米。
或者，所述铝塑膜或其铝箔层具有如下耐冷却液腐蚀性能：OY水溶液腐蚀试验、或者ASTM D2570标准中内部耐腐蚀性能试验；该铝塑膜或其铝箔层的在上述试验中的耐腐蚀寿命大于150小时，或大于200小时，或大于336小时。进一步的，所述铝塑膜或其铝箔层的耐腐蚀寿命大于500小时。再进一步的，所述铝塑膜或其铝箔层的耐腐蚀寿命大于1000小时。更进一步的，所述铝塑膜或其铝箔层的耐腐蚀寿命大于2000小时；再更进一步的，所述铝塑膜或其铝箔层的耐腐蚀寿命大于2500小时。
现有技术中厚度为40微米的8系(如8021或8079)铝箔在OY水溶液腐蚀试验中的寿命约为98小时，根本不能满足车辆设计寿命要求，故不能满足防冻液浸泡式冷却方式的要求。因此，若需具有上述耐腐蚀性能，铝塑膜中铝箔需要具有合适的铝合金材料组成和/或合适的厚度。
满足上述耐冷却液腐蚀性能要求的铝箔材料可从如下材料中选取：单层的1系铝合金(纯铝)、单层的3系铝合金、或具有牺牲阳极保护功能的复合层铝合金。
满足上述耐冷却液腐蚀性能要求的铝箔厚度可从如下厚度中选取：80-120微米、或120-150微米、或150-200微米、或200-300微米。
比如厚度大于150微米的纯铝AA1050，或者厚度为100微米的AA1050与20微米的AA7072复合形成的复合层铝合金(即复合层铝合金总厚度120微米)，选用以上两种铝箔用于制造铝塑膜可满足上述耐防冻液腐蚀寿命要求，从而可满足汽车寿命要求。
除了从铝箔角度解决上述耐腐蚀寿命问题之外，本发明还可以从外侧塑料层改善铝塑膜的耐水腐蚀寿命问题。优选地，该外侧塑料层为耐水解的塑料层。进一步的，该外侧塑料层为特氟龙层、或者PE层、或者PE层与PA层的复合材料、或者PA的耐水改进层。或者，若外侧无塑料层，即铝箔为外层材料，则可在铝箔层外表面做防腐涂层，如铬化处理、或稀土氧化物处理。
或者，从整车应用角度进行描述，优选铝塑膜或其铝箔耐冷却液(如主要由乙二醇和水组成的防冻液)腐蚀的寿命为大于5年，优选大于10年，更为优选大于15年。
本发明若未特别说明，所谓寿命，是指铝塑膜和其铝箔在寿命期限内不能出现腐蚀穿孔的缺陷。本发明为了得到上述耐冷却液腐蚀性能，铝塑膜中铝箔需要选用上述合适的铝合金材料和足够的厚度。比如优选地，该铝塑膜由铝箔层和复合于铝箔上的热塑性树脂薄膜构成，其中铝箔为具有牺牲阳极功能复合层铝箔，厚度优选为100至300微米。现有的铝塑膜产品没有考虑到浸泡于防冻液中的应用，也不具备长期浸泡于防冻液中而不失效的功能；而本发明的铝塑膜产品具备上述特殊特征。
进一步的，该铝塑膜或其铝箔还同时具有深冲性或成型性。或者说，该铝塑膜或其铝箔还同时具有良好的深冲性或成型性。或者说该铝塑膜还同时具有良好的深冲成型性。或者该铝塑膜或其铝箔还同时具有良好的杯突值。因其深冲性可以以杯突值来衡量。比如，以GB/T4156-2007《金属材料薄板和薄带埃里克森杯突试验》标准测试，该铝塑膜或铝塑膜中的铝箔的冲压深度值或杯突值大于5毫米，优选大于10毫米，更优选为大于12毫米。其中所谓冲压深度值或杯突值，是指铝塑膜或其铝箔在该值以内的冲压后或杯突测试后不能出现穿孔现象。
进一步的，本发明还提供一种铝塑膜，所述铝塑膜包括铝箔层和复合于铝箔层表面的塑料层；铝箔层为复合层铝箔，铝箔层包含有芯材和位于芯材外侧的皮材，铝箔层的皮材的腐蚀电位低于芯材的腐蚀电位；其中，位于芯材外侧的皮材由两层皮材或多于两层的多层皮材复合形成，腐蚀电位由内向外依次降低。由此形成面腐蚀梯度，更有利于防止点状腐蚀。
为了形成电位梯度，还可以让复合层铝箔进行高温加热，让皮材中锌元素向芯材逐步扩 散，从而铝箔层由外到内的过程中，锌元素的含量连续逐步的变化，腐蚀电位也连续逐步变化，避免了锌元素含量和腐蚀电位断崖式变化或突变，从而更有利于腐蚀形态转化为均匀的层状腐蚀。复合层铝箔的防腐机理不同于铝箔表面铬化等传统的防腐涂层处理方式，复合层铝箔本身都是铝材，其通过调整铝箔内部不同层的腐蚀电位改善腐蚀形态，即由点腐蚀引导为层状腐蚀，防止铝箔穿孔和电池失效。若采用铝箔外表面铬化处理后浸泡在冷却水中，虽然可以降低铝箔的腐蚀速率，但不能改善铝箔的腐蚀形态，对点腐蚀的抑制作用不大。
值得说明的是，通过高温扩散过程后，上述复合层各层之间的界限已不是十分明确，各层之间成分及电位不是阶梯式的突变，而是一个渐变的过程。所以本发明所述的复合层铝箔，既包括未高温处理前的多层不同铝合金之间的复合；也包括高温处理后，在垂直于铝箔表面的方向上，铝箔中元素含量渐变或腐蚀电位渐变的复合层。
如上所述的软包电池热控制装置，还包括冷却液，所述软包电池的外包装与冷却液直接接触。进一步的，所述的电池热控制装置所包括的冷却液为水、或者包含乙醇与水的混合液、或者包含乙二醇与水的混合液、或者包含丙二醇与水的混合液、或者其他防冻冷却液。这些冷却液为目前汽车上和工业上常用的冷却液，它们不是绝缘型冷却介质，而是具有导电性能(包括微弱的导电性能)的导电冷却液；但是，相比于硅油或变压器油之类的绝缘型冷却介质，上述导电冷却液具有导热系数高、流动性好、导热效率高以及成本相对廉价等优点。
在以上基础上，本发明提供如下软包电池热控制装置，该软包电池热控制装置包含有软包电池和冷却液，所述软包电池的外包装与冷却液直接接触，软包电池采用以上所述的软包电池中的一种或几种。其中，冷却液为导电冷却液。
进一步的，该热控制装置还包括主板和外壳体，主板和外壳体形成密封腔，软包电池的电极伸出于主板之上，软包电池的本体置于密封腔中。
进一步的，该热控制装置还包括隔板；所述隔板的至少部分表面与所述软包电池至少部分外表面直接接触，并且隔板内设有流体通道；若干个软包电池组成一个电池单元，电池单元与隔板间隔设置。所述若干个软包电池可以是1个、或2个、或多个组成一个电池单元。其中，电池用包装材料优选为铝塑膜。所述隔板采用金属材料；隔板的腐蚀电位等于或负于铝塑膜中铝箔腐蚀电位。进一步的，所述隔板采用金属材料；隔板的腐蚀电位负于铝塑膜中铝箔腐蚀电位，或者隔板的腐蚀电位等于或负于铝塑膜中铝箔的皮材的腐蚀电位。所述隔板起支撑软包电池作用和组织流场作用，隔板可以是挤压扁管，也可以是平直翅片、错列锯齿翅片形式的。本发明中上述翅片是隔板的一种，或者说是具有流体通道的翅片式隔板。这些翅片隔板主要发挥分隔相邻的电池单元以便形成流道的作用，并对电池单元进行支撑和固定； 所以，本发明所述翅片隔板不包括不能支撑电池单元的针形翅片之类的翅片。电池单元与翅片隔板紧密地间隔设置，组成一个整体，并可以采用绑带或贯穿螺栓将该整体紧固在一起，这样，该热控制系统和电池单元就具有可靠的抗振动强度。
进一步的，所述铝塑膜将所述电池芯体四周密封，仅电池电极、或电极连接端口从所述铝塑膜中伸出；电池热控制装置还包括主板，所述主板上设有插口，所述电池从铝塑膜内伸出的部分通过所述插口插入到主板上。
进一步的，所述电池热控制装置还包括外壳体，所述外壳体内部设有容纳腔室，所述电池单元与隔板均置于所述外壳体的容纳腔室内，所述外壳体还包括流体入口和流体出口。
进一步的，所述主板位于所述外壳体的容纳腔室内，并将所述容纳腔室隔开成为两个部分，第一部分容纳电池单元主体以及隔板，第二部分容纳从所述铝塑膜伸出的电极和/或电极连接端口部分，所述第一部分和第二部分之间物理隔绝。
本发明所述电池热控制装置，还可以包括冷却泵、冷却液换热器和相应的水管；或者本发明提供一种电池冷却系统，其采用上述电池热控制装置，还包括冷却泵、冷却液换热器和相应的水管。其中，冷却液换热器为冷却液与环境空气进行直接热交换的气液热交换器。
由于采用上述电池热控制装置，电池的换热效率非常高，电池本体与冷却液之间的传热热阻非常低、换热温差非常小；所以，在保证电池本体内物质(如电解液、隔膜和固体电解质界面膜SEI)不超温的前提下，可以允许冷却液有更高的温度，即降低了电池冷却对外界的要求，降低了冷却成本，从而可以使用上述气液热交换器。进一步的，上述冷却系统还可以包括电加热器，以用于给电池加热。
本发明以上耐冷却液腐蚀的铝塑膜和由此铝塑膜包裹的软包电池中，铝箔层或者一开始便作为触水层与冷却液接触，或者待外侧保护层(如尼龙膜)剥离后作为触水层与冷却液接触。
本发明提供另一种电池用包装材料，其由金属箔和位于金属箔内侧的热塑性树脂薄膜复合形成；或者其由热塑性树脂薄膜和金属箔以及耐热性树脂薄膜复合形成，金属箔位于热塑性树脂薄膜和耐热性树脂薄膜之间；其中，金属箔为具有抗蚀性的单层金属，或者金属箔包含有芯材和位于芯材外侧的皮材，金属箔的皮材的腐蚀电位低于芯材的腐蚀电位。所述金属箔优选为铝箔和/或铜箔和/或不锈钢箔。金属箔的厚度优选为20到50微米、或50到80微米、或80到150微米、或150到200微米、或200到300微米。优选地，金属箔外侧不含有塑料膜，即塑料膜仅复合于金属箔的内侧。
作为可选方案，上述金属箔层内侧还可以具有防腐蚀处理层，该防腐蚀处理层为铬酸盐 处理形成、或者由稀土氧化物处理形成。
从另一个角度，本发明还提供如下软包电池解决方案，即一种软包电池，其采用铝塑膜包装，该软包电池本体具有如下耐冷却液腐蚀性能：
耐腐蚀测试方法为：OY水溶液腐蚀试验；
将该软包电池的本体浸泡于冷却液中，该软包电池的在上述试验中的耐腐蚀寿命大于500小时。
进一步的，所述软包电池本体的耐腐蚀寿命大于1000小时。更进一步的，所述软包电池本体的耐腐蚀寿命大于2000小时。
或者，上述耐腐蚀试验方法为ASTM D2570标准中内部耐腐蚀性能试验，或者采用类似QC/T 468-2010标准中的5.14节“内部腐蚀性能试验”方法对其外包装铝箔进行评估。
本发明中所指的OY水溶液(Oyama Water Solution)腐蚀试验为热交换器铝热传输行业通用的OY水溶液腐蚀试验。
本发明所述的铝塑膜制造方法，包括：首先通过如下耐水溶液腐蚀试验选择相应的铝箔：耐腐蚀测试采用OY水溶液腐蚀试验方法，该铝箔的在该腐蚀试验方法下的耐腐蚀寿命大于500小时；然后再将该铝箔和塑料薄膜进行复合形成铝塑膜。
其中耐腐蚀寿命优选为大于1000小时。更优选为大于2000小时。所述铝箔可从上述纯铝或铝合金中选取。
本发明提供的多个技术方案中更优选的方案之一是，铝塑膜的铝箔仅内侧复合有热塑性塑料薄膜，即铝箔外侧不含有耐热性塑料膜或保护膜。相比于传统铝塑膜，本发明通过改善铝塑膜中铝箔的耐冷却水腐蚀性和机械强度，外侧不含塑料膜的铝塑膜不仅耐久可靠，而且工艺更简便和成本更低，当该铝塑膜与冷却水接触换热时，其换热效率更高；更重要的是，本发明上述铝塑膜还具有新的功能，即具有能够长期耐冷却水腐蚀功能，故可以长期浸泡在冷却水中而不失效，从而满足浸泡式水冷的软包电池冷却系统的热管理需求，为电池系统的性能提升提供了可靠的保障。
本发明提供的多个技术方案中另一更优选的方案之一是，铝塑膜中铝箔通过采用内部层间不同腐蚀电位匹配的复合层铝箔，使得铝箔腐蚀形态更趋于层状腐蚀，更好地避免铝塑膜中铝箔腐蚀穿孔失效。
不同于其他复合层铝箔，本发明软包电池包装用铝箔的更优选方案之一是采用纯铝芯材和纯铝基础上加锌的皮材复合，其不仅具有优良的抗冷却水点蚀性能，同时还具有较好的成型性和可包装性。
本发明提供的铝塑膜还可以是上述技术特征的组合形成的技术方案，其可用于直接与冷却水接触的软包电池的包装，具有耐冷却水腐蚀、使用寿命长的优点。
附图说明
图1为第一种铝塑膜结构示意图；
图2为第二种铝塑膜结构示意图；
图3为采用本发明铝塑膜的电池的应用示意图；
图4为软包电池示意图；
图5为软包电池热控制装置示意图；
图6为第三种铝塑膜结构示意图；
图7为单层铝合金(左图)与复合层铝合金(右图)耐蚀性对比测试效果图；
图8所示的翅片隔板为错列锯齿翅片，包括多个齿形单元，同一列齿形单元内部连通形成流体通道，相邻齿形单元之间前后交错排布，齿形单元的顶部和底部平面与电池直接接触；
图9所示的翅片隔板为平直翅片，包括平行的竖板和竖板两端连接的上下平板，平板与电池之间直接接触，竖板之间形成流体通道。
具体实施方式
下面结合具体实例对本发明进行进一步描述，本发明的保护范围包括但不限于此。
实施例1
如附图1提供一种铝塑膜，所述铝塑膜包括铝箔层1和复合于铝箔层两侧表面的塑料层2、3，其中，铝箔层1由3系铝合金铝箔层7(芯材)和7系铝合金铝箔层6(皮材)复合形成。如采用3003铝合金与7072铝合金复合，7072铝合金层6复合于3003铝合金层7的外侧。或者说，该铝塑膜由热封层、3003铝箔层、7072铝箔层和尼龙层依次叠层形成，其中铝箔层与塑料层以传统的粘合剂粘合。或者说，该铝塑膜由内到外各层为：热封层、粘合层、3003铝箔芯层、7072铝箔皮层、粘合层、尼龙保护层。
3003铝合金的腐蚀电位约为-0.72V，7072铝合金的腐蚀电位约为-0.88V。由于7072铝合金的腐蚀电位低于3003铝合金的腐蚀电位，当与冷却液接触时，7072铝合金作为被牺牲的阳极，保护芯材不被腐蚀。热封层厚度优选为80-100微米，尼龙保护层厚度优选为20-30微米，该复合铝箔层的厚度优选为200-300微米；其中，7系铝合金层6的厚度优选占整个铝箔层1的10％。同样内外塑料层2、3与铝箔层1之间分别通过粘合剂4、5粘接复合。
另外，铝箔层的热处理状态可采用O状态、或H14状态、或H16状态，其中优选为O状态。
本实施例的铝箔层比传统铝塑膜中的铝箔层更厚，这样既有利于长期耐防冻液腐蚀性能，又有利于铝塑膜的水汽阻隔性，从而保障软包电池包装的长期可靠性。
实施例2
本实施例与实施例1的结构大致类似，铝合金层1也由芯材7和皮材6复合形成，皮材6为阳极保护层。所不同的是，用添加锌Zn的3003铝合金(如下表3003+1％Zn或3003+1.5％Zn)代替7072铝合金作为牺牲阳极层。3003+1％Zn的电位大约在-0.83V至-0.89V，其电位低于3003芯材的电位。
表1合金化学成分
Figure PCTCN2017075659-appb-000001
实施例3
如附图2提供第二种铝塑膜，所述铝塑膜包括铝箔层1和复合于铝箔层内侧的热塑性树脂薄膜层3，其中，铝箔层为复合层铝箔，铝箔层包含有芯材和位于芯材外侧的皮材，铝箔层的皮材的腐蚀电位低于芯材的腐蚀电位。进一步的，铝箔层的芯材由耐腐蚀的铝合金或纯铝形成。比如，复合铝箔层1由3系列铝箔层7(如3003)和7系列铝箔层6(如7072)复合形成。铝箔层1上仅内侧复合了热塑性树脂薄膜层3(也可称热封层3，比如采用CPP)，而无需外部尼龙防护层。
热封层3(CPP)厚度优选为30-50微米，整个复合铝箔层1厚度优选为200微米。其中，7系铝合金层6复合于外侧，作为牺牲阳极；7系铝合金的厚度优选占整个铝箔层1的10％。当用作软包电池包装且电池浸泡在冷却水中时，该7系铝合金即作为触水层。同样内侧热塑性树脂薄膜层3与铝箔层1之间通过铝塑膜常用的粘合剂5粘接复合。由以上提供的铝塑膜制成的软包电池可长期浸泡在冷却液中，具备长期耐冷却液腐蚀功能。
实施例4
本实施例与实施例3的结构大致类似，芯材层也采用3003铝合金，所不同的是，皮材6由金属锌(Zn)层代替7系铝箔层，金属锌层厚度可以优选为10-20微米，可通过喷锌工艺形成。该金属锌的电位比铝合金芯材的电位低，故可以作为牺牲阳极保护芯材不被腐蚀。且 金属锌还能有效地防止铝合金芯材点蚀。
实施例5
本实施例介绍采用了上述铝塑膜的电池以及该电池的应用方式。提供一种软包电池，包含有电极材料和聚合物电解质以及外部包裹用的铝塑膜，其中，软包电池采用包含有牺牲阳极功能的复合层铝箔的铝塑膜包裹，如实施例1或3中的复合层铝合金铝箔，即铝箔采用3003铝合金芯材外部复合有7072铝合金皮材。软包电池采用以上耐防冻冷却液浸泡腐蚀的铝塑膜包装之后，可以将该软包电池浸泡在防冻冷却液中，从而可以直接与防冻冷却液进行热交换。如图3所示，软包电池11通过顶边112与主板13密封后，软包电池11的本体浸泡在防冻冷却液中。这样电池的换热效果更好，电池上下左右各处的温度更均匀。
实施例6
本实施例采用与实施例1类似的铝塑膜结构，所不同的是，粘合尼龙保护层的粘合剂采用便于分离的离型剂。即尼龙保护层类似于离型膜。这样，在铝塑膜深冲成型过程中，尼龙层可以保护铝箔层；在深冲成型完成后，尼龙层能够方便地与铝箔层分离，从而形成类似实施例3中的铝塑膜。
实施例7
本实施例所介绍的铝塑膜为由热塑性树脂薄膜(即热封层，如聚丙烯)和复合层铝合金铝箔复合形成。铝箔层的芯材层7采用牌号为1050的纯铝，皮材6由在纯铝1050基础上添加4％-7％锌元素的铝合金形成(简化表示为AA1050+4-7％Zn)，皮材的腐蚀电位负于芯材，皮材作为牺牲阳极保护芯材，皮材复合率优选为10±2％。复合铝合金铝箔层的热处理状态为退火状态(O态)，厚度优选为100-300微米,更为优选为200-300微米。该复合铝箔层既具有优良的耐冷却液腐蚀性能，又具有很好的延展性和深冲性能。
该铝塑膜或其铝箔要求具有较好的延展性和深冲性能，比如以GB/T 4156-2007《金属材料薄板和薄带埃里克森杯突试验》标准测试，该铝塑膜或其铝箔的杯突值优选大于5毫米，更为优选大于10毫米。
该铝塑膜或其铝箔要求具有较好的耐冷却液腐蚀性能。耐腐蚀性能试验方法采用热交换器铝热传输行业常用的OY水溶液(Oyama Water Solution)腐蚀试验，具体试验方法介绍也可参考CN201080021209.6中实施例1中关于OY水溶液腐蚀试验。该OY水溶液腐蚀试验大致如下：
OY水溶液组分：氯离子(Cl-):195±1毫克/升，硫酸根离子(SO4 2-):60±0.2毫克/升，铁离子(Fe3+):30±0.1毫克/升，铜离子(Cu2+):1±0.01毫克/升。OY水溶液的pH约为3(在未 特别说明的情况下，本发明所述的OY试验中水溶液pH取值均约为3)。
OY水溶液温度：88℃，以0.6-0.9m/s(200rpm)的速度搅拌8小时，然后静置16小时；重复上述循环。
在上述OY水溶液腐蚀试验中，忽略接近铝箔边缘5mm的任何穿孔。当铝箔中除边缘5mm之外的任一点发生腐蚀穿孔时，所累积的腐蚀试验时间即为该铝塑膜铝箔在该OY水溶液中的耐腐蚀寿命。实验显示，本发明实施例铝箔耐腐蚀寿命大于1000小时。
以上，铝塑膜或其铝箔的耐腐蚀寿命也可以以它在实车上浸泡于防冻液中的耐腐蚀使用寿命进行评估，如选用在实车上的使用寿命大于5年的铝塑膜，优选大于10年，更为优选大于15年。
实施例8
如图4和图5所示，本实施例介绍的电池热控制装置采用以上可长期直接浸泡于冷却液(如主要由乙二醇与水组成的冷却液)中的软包电池。该软包电池热控制装置，包含有软包电池11和水基冷却液，所述软包电池11的外包装与冷却液直接接触，所述软包电池11为由上述任一种抗冷却液腐蚀的包装材料(如抗水基冷却液腐蚀的铝塑膜)形成。该热控制装置还包括隔板12，该隔板12优选为图8所示的错列锯齿翅片隔板或如图9所示的平直翅片隔板；隔板12的至少部分表面与所述软包电池11至少部分外表面直接接触，并且隔板12内设有流体通道121，流体通道121与电池11直接接触，同时流体通道121内的冷却水与电池11直接接触换热；一个软包电池11组成一个电池单元(当然也可以采用两个软包电池组成一个电池单元)，电池单元与隔板12间隔设置。隔板一方面起支撑软包电池的作用，另一方面起组织冷却液流场的作用。
所述铝塑膜将所述电池芯体四周密封，仅电池电极、或电极连接端口从所述铝塑膜中伸出；电池热控制装置还包括主板13，所述主板13上设有插口，所述电池从铝塑膜内伸出的部分(即正负电极极耳111)通过所述插口插入到主板13上。优选地，电池的部分顶边112也通过所述插口插入到主板13上。
所述电池热控制装置还包括外壳体14，所述外壳体14内部设有容纳腔室，多个所述电池单元与隔板12组成的紧密整体嵌入外壳体14的容纳腔室内，所述外壳体14还包括流体入口和流体出口(图中未示出)。
所述主板13位于所述外壳体14的容纳腔室内，并将所述容纳腔室隔开成为两个部分，第一部分容纳电池单元主体以及隔板12，第二部分容纳从所述铝塑膜伸出的电极和/或电极连接端口部分，所述第一部分和第二部分之间物理隔绝。
所述的电池热控制装置还包括冷却液，所述冷却液为水、或者包含乙二醇与水的混合液、或者包含丙二醇与水的混合液、或者防冻冷却液。
优选地，所述隔板12采用金属材料，隔板12的腐蚀电位负于铝塑膜中铝箔腐蚀电位，比如包装材料金属箔选用AA1050铝合金，隔板12选用AA1050+5％Zn。或者，隔板12的腐蚀电位负于铝塑膜的铝箔的皮材的腐蚀电位，比如包装材料金属箔选用复合材料AA1050/AA1050+5％Zn铝合金，隔板12选用AA1050+7％Zn。这样隔板还可以起阳极保护作用，进一步防止电池腐蚀失效。
实施例9
本实施例与实施例7所用铝箔相同，所不同的是，以如下方法评估和选择成型性能(或深冲性能)优良的铝箔材料和铝塑膜。
依照如下A-F进行成型性能测试和评估：
A、模芯采用特氟龙材质，模具尺寸为34mm×44mm，圆角R＝0.6mm。根据测试要求调整冲压成型测试仪成型深度为5.0mm-15.0mm之间某一数值，调节压缩空气压力使模具侧压大于等于3.0MPa。
B、取表面平整、洁净、无皱折样品膜，裁取宽度不小于100mm、长度不小于200mm的膜供测试。
C、将膜的CPP面朝向模芯，放入冲压成型测试仪内。保证膜平整无皱褶，侧压膜余量充足。
D、按压按钮，进行冲压成型，冲压成型完成后小心取出样品待用。
E、将冲压成型后样品的CPP面与未冲压成型样品的CPP面相结合，保证样品平整无变形，沿冲压成型边缘不大于2mm处进行热封，热封条件为：热封温度190℃(上下均匀加热)，热封压力为0.2MPa，热封时间为6秒。
F、对热封好后的冲压成型样品进行目测，检查样品有无破裂、分层现象。
通过以上方法可以看出，本发明铝塑膜成型深度大于5.0mm；更优选地筛选出成型深度大于10.0mm的铝塑膜或铝箔。
实施例10
本实施例与实施例7所用铝箔相同，所不同的是，不是采用OY试验来评估，而是采用类似QC/T 468-2010标准中的5.14节“内部腐蚀性能试验”对铝塑膜的铝箔的耐腐蚀寿命进行评估。
其中，QC/T 468标准中的5.14节中耐腐蚀试验检测大致如下：
试验温度：88℃
混合溶液流量：1.3-1.6L/s(升每秒)
混合溶液：
防冻液型号：45％的乙二醇防冻液，冻结温度：-30℃
ASTM水：1L(升)的蒸馏水中含有148mg(毫克)的硫化钠，165mg的氯化钠，138mg的碳酸氢钠。
混合比：40％防冻液+60％ASTM水。
实验结果显示，本发明铝箔耐腐蚀寿命大于1000小时。
实施例11
复合层铝合金的芯材和皮材可从如下表2选项1至选项4中选择任一种：
表2
Figure PCTCN2017075659-appb-000002
采用实施例7的方法，本实施例铝箔耐腐蚀寿命大于1000小时，甚至大于1500或2000小时。
实施例12
本实施例提供一种铝塑膜，所述铝塑膜包括铝箔层和复合于铝箔层表面的塑料层；铝箔层为复合层铝箔，铝箔层包含有芯材和位于芯材外侧的皮材，铝箔层的皮材的腐蚀电位低于芯材的腐蚀电位；其中，位于芯材外侧的皮材由两层皮材或多于两层的多层皮材复合形成，腐蚀电位由内向外依次降低。
比如，铝塑膜中铝箔层由内到外依次为芯材、第一层皮材、第二层皮材，芯材为AA1050铝合金，第一层皮材为AA1050基础上加2％Zn的铝合金，第二层皮材为AA1050基础上加4％Zn的铝合金。所以，腐蚀电位为：芯材>第一层皮材>第二层皮材。这样能够进一步保障腐蚀是逐层腐蚀的层状腐蚀，从而进一步避免点状腐蚀，保障电池安全。
实施例13
本实施例提供另一种软包电池外包装铝塑膜铝箔的耐腐蚀性能试验，也即软包电池的耐防冻液腐蚀试验方法。该试验方法用于评估和测定产品的耐防冻液腐蚀寿命。
将若干个相同软包电池的本体浸泡于如下混合溶液中，软包电池正负极耳竖直朝上，混 合溶液浸没高度为与软包电池顶边下沿齐平。
混合溶液成分：由体积比为40％防冻液和60％ASTM溶液组成。其中防冻液型号为45％的乙二醇防冻液，冻结温度为零下30摄氏度；ASTM溶液为由1升蒸馏水与148毫克硫酸钠、165毫克氯化钠和138毫克碳酸氢钠配置。
混合溶液温度：90±2摄氏度。混合溶液流向为与电池本体最大表面平行的水平方向，流经电池本体表面的流速为0.5m/s。
试验以上述温度和流速运行76小时，停机静置8小时为一个循环，停机期间进行溶液pH值检查和补液，溶液检查分为pH值和外观检查，试验过程中不允许出现±1以上的pH值变化，溶液外观不允许出现混浊和沉淀。
试验过程中可随时检查电池外包装铝塑膜铝箔的腐蚀深度。若所有腐蚀点的腐蚀深度值中的最大值大于铝箔原始厚度值的10％，则将该最大腐蚀深度值达到铝箔原始厚度值的10％的时刻所累计的试验时间定义为电池外包装铝塑膜铝箔的耐腐蚀寿命，也即为软包电池的耐防冻液腐蚀寿命。故本实施例试验方法中所谓的寿命，即为达到上述腐蚀深度值所累计的试验时间。
上述试验中，不同的地方以本发明上述说明为准，其他地方可参照中国汽车行业标准QC/T468-2010。值得说明的是：本发明软包电池外包装铝塑膜优选为由铝箔和复合于铝箔内侧的热塑性树脂薄膜组成的铝塑膜，铝箔的外侧无其他塑料层，故铝箔一开始即与防冻液直接接触。但本发明软包电池外包装铝塑膜也可以是(虽非优选)由铝箔和复合于铝箔内侧的热塑性树脂薄膜以及复合于铝箔外侧的耐热性树脂薄膜组成的铝塑膜。由于通常的耐热性树脂薄膜(如PA或PET)很容易被防冻液溶胀剥离，故为了统一测试标准，在进行上述耐腐蚀寿命试验前，先将铝塑膜外的耐热性树脂薄膜剥离，然后再进行上述腐蚀试验测试。
为了便于简要表述，本发明将上述软包电池外包装铝塑膜铝箔的耐腐蚀性能试验定义为“特定的软包电池的耐防冻液腐蚀寿命试验”。
为了满足汽车对零件耐久性的要求，选择那些在该特定的软包电池的耐防冻液腐蚀寿命试验中的寿命值大于336小时的软包电池。由于动力电池对安全性要求非常苛刻，故优选大于500小时的软包电池，更优选大于1000小时的软包电池；进一步为优选大于2000小时的软包电池。再进一步为优选大于5000小时的软包电池。
如下提供另一种考核方式，在上述“特定的软包电池的耐防冻液腐蚀寿命试验”中，试验时间固定为14天(即336小时)，检查各处点蚀深度，其中最大点蚀深度要求小于铝箔原始厚度值的50％；优选为小于20％，更为优选为小于10％；进一步优选为小于8％；再进一 步优选为小于5％。或者说，最大点蚀深度为铝箔原始厚度值的20％～50％，或者为大于10％且小于20％，或者为大于0％且小于10％。
若需具有上述耐腐蚀性能，铝塑膜中铝箔需要具有合适的铝合金材料组分和合适的厚度。
满足上述耐冷却液腐蚀性能要求的铝箔材料可从如下材料中选取：单层的1系铝合金(纯铝)、或具有牺牲阳极保护功能的复合层铝合金。
满足上述耐冷却液腐蚀性能要求的铝箔厚度可从如下厚度中选取：120-300微米。
比如厚度大于150微米的纯铝AA1050，或者厚度为100微米的AA1050与20微米的AA7072复合形成的复合层铝合金(即复合层铝合金总厚度120微米)，选用以上两种铝箔用于制造铝塑膜和软包电池可满足上述耐防冻液腐蚀寿命要求，从而可满足汽车寿命要求。
实施例14
本实施例介绍如下铝塑膜，其铝箔由芯材和外侧皮材复合形成，其中芯材为100微米-300微米的8系铝合金(如8079或8021)形成，外侧皮材由8系铝合金基础上添加2％-6％质量百分比的锌元素形成(如下表3所述)，复合率取10％-20％。含有这种复合铝合金的铝塑膜，其耐蚀性和深冲性都较良好，根据实施例7方法测试，其耐腐蚀寿命大于1300小时。
表3
元素 硅 铁 铜 锌 铝 其他
质量百分比 0.05-0.30 0.70-1.3 ≤0.05 2.0-6.0 余量 ≤0.15
实施例15
本实施例介绍如下铝塑膜，其铝箔由芯材和外侧皮材复合形成，其中芯材为100微米-300微米的1系铝合金(如1050)形成，外侧皮材由1系铝合金基础上添加2％-6％质量百分比的锌元素形成(如表4所述)，复合率取10％-20％。
实施例16
其中芯材为100微米-300微米的1系铝合金(如1050)形成，外侧皮材由1系铝合金基础上添加2％-6％质量百分比的锌元素形成(如表4所示铝合金)。含有这种复合铝合金的铝塑膜，其具有良好的耐电解液腐蚀功能和良好的耐冷却水腐蚀功能；根据实施例7方法测试，其耐腐蚀寿命大于1800小时。
表4
Figure PCTCN2017075659-appb-000003
实施例17
提供一种铝塑膜，所述铝塑膜包括铝箔层和复合于铝箔层表面的塑料层，其中，铝箔层 材料为3003铝合金。
参照图6，铝塑膜由外向内依次由外层防护层2、铝箔层1、和内层热封层3组成，外层防护层2采用尼龙(ON)、内层热封层3采用流延聚丙烯薄膜(CPP)，该内层热封层3同时也发挥绝缘作用，保持铝箔层1与内部电解质之间的电绝缘。外层防护层2、内层热封层3与铝箔层1之间分别通过粘合剂(或接着剂)4、5粘接复合。其中外层防护层2用于在深冲过程中保护铝箔层1的作用。粘合剂层是由以下树脂中的任何一种构成的，这些树脂是聚酯-氨酯树脂、聚醚-氨酯树脂、异氰酸酯树脂和不饱和羧酸接枝聚烯烃树脂。
以上，铝箔层1也可采用其他防锈铝进行替代，如5系防锈铝或其他3系防锈铝，更具体的比如：3004、3005、3105、5052、5086等；铝箔层1也可以采用6系铝合金替代，如6063等。当然，铝箔层也可以是纯铝，纯铝为1050铝合金，或者1060铝合金，或者1100铝合金，或者基于上述纯铝基本型的改进型。这些纯铝也有很好的耐腐蚀性。
由此铝塑膜形成的软包电池可直接浸泡在冷却液中，且具有长期耐冷却液腐蚀功能，其中冷却液优选为含有乙二醇或/和丙二醇的水基冷却液。在形成软包电池的过程中，需要进行深冲工艺，外层防护层2在此深冲工艺中提供对铝箔层1的保护作用。软包电池浸泡在冷却液中一段时间之后，尼龙层2可能会溶胀溶解剥离，但这不会影响铝塑膜的绝缘性、密封性和长期耐冷却液腐蚀性。由于该软包电池的铝塑膜具备长期耐冷却液腐蚀功能，故可将软包电池直接浸泡在冷却液中进行冷却。这样带来的有益效果是软包电池的换热效率非常高，即使在大电流做功时也不会过热，这样可提高整个电池系统的功率密度和可靠性。
相对于8系铝合金，3系或5系的防锈铝具有更好的耐防冻液腐蚀性能，其耐蚀性寿命更长更可靠。
实施例18
本实施例介绍采用了实施例17中所述的铝塑膜包裹的软包聚合物锂离子电池，本实施例与实施例5大致相同，所不同的是，用于包装软包电池的铝塑膜中的铝箔是由单层铝合金形成，该单层铝合金由防锈铝箔形成，如采用3003铝箔形成。
实施例19
本实施例介绍采用了实施例17中所述的铝塑膜包裹的软包聚合物锂离子电池，本实施例与实施例5大致相同，所不同的是，用于包装软包电池的铝塑膜中的铝箔是由单层铝合金形成，该单层铝合金由1系铝合金箔形成，如采用O态1050铝合金铝箔或其他纯铝形成。
实施例20
本实施例介绍如下铝塑膜，其铝箔由芯材和外侧皮材复合形成，其中芯材为150微米-300 微米的8系铝合金(如8079或8021)形成，外侧皮材由7系铝合金(如7072)，复合率取20％-50％。进一步的，8系与7系复合后再进行加热或退火处理，以便Zn元素的适当扩散形成梯次电位变化。含有这种复合铝合金的铝塑膜，其耐蚀性和深冲性都较良好，根据实施例7方法测试，其耐腐蚀寿命大于1500小时。
实施例21
本实施例介绍如下铝塑膜，该铝塑膜从内到外由热塑性薄膜(如CPP)、铝箔层和特氟龙薄膜粘合而成。由于特氟龙薄膜具有很好的耐水耐腐蚀性，所以由该铝塑膜制得的软包电池可以长期浸泡在水或防冻液中。
实施例22
可参考实施例7，但本实施例选用的OY水溶液的pH约为11。本实施例除了OY水溶液的pH值不同于实施例7之外，其余条件与实施例7相同。本发明实施例选用耐腐蚀寿命大于1000小时的铝箔用于电池包装材料用的铝塑膜。
实施例23
本实施例对单层1050铝合金和复合层铝合金(芯材为1050铝合金、皮材为电位较负的牺牲层)在OY实验中进行耐蚀性对比试验。
选择防冻液体系进行OY实验，实验时间为4周，实验后对材料表面进行硝酸浸泡去除腐蚀产物，具体情况如下：
如图7中所示，防冻液体系OY试验4周后，左图所示为AA1050单层铝合金发生了较为明显的点蚀，点蚀较为严重；而右图所示为复合牺牲层的铝合金表面未发生明显的点蚀。由此可知，通过在铝合金芯材表面复合腐蚀电位较负的皮材，可以有效地抑制点腐蚀的发生。由上述复合层铝箔形成的铝塑膜内表面塑料层热封后，铝箔耐冷却水腐蚀的时间能够满足汽车要求；同时由于铝箔内侧芯材的为纯铝，其耐电解质腐蚀能力也优于传统的铁铝合金，从而保障电池的寿命和安全使用。
以上对本发明的具体实施例进行了详细描述，但其只是作为范例，本发明并不限制于以上描述的具体实施例。对于本领域技术人员而言，任何对本发明进行的等同修改和替代也都在本发明的范畴之中。因此，在不脱离本发明的精神和范围下所作的均等变换和修改，都应涵盖在本发明的范围内。

Claims (16)

  1. 一种由金属塑料复合薄膜形成的电池用包装材料，包括金属箔层和复合于金属箔层内表面的塑料层。
  2. 如权利要求1所述的电池用包装材料，其为铝塑膜，包括铝箔层和复合于铝箔层内表面的塑料层；其中，铝箔层为单层铝箔，铝箔层由耐冷却水或防冻液腐蚀的铝合金或纯铝形成；所述耐冷却水或防冻液腐蚀的铝合金选自3系铝合金或者1系铝合金；塑料层仅复合于铝箔层的内侧，内侧塑料层为热塑性树脂薄膜。
  3. 如权利要求1所述的电池用包装材料，其为铝塑膜，包括铝箔层和复合于铝箔层内表面的塑料层；其中，铝箔层为复合层铝箔，铝箔层包含有芯材和位于芯材外侧的皮材，铝箔层的皮材的腐蚀电位低于芯材的腐蚀电位。
  4. 如权利要求3所述的电池用包装材料，其特征在于，
    所述芯材包括含有如下组分的铝合金：
    Si≤0.25wt％；Cu≤0.05wt％；Mg≤0.05wt％；Zn≤0.05wt％；Mn≤0.05wt％；Ti≤0.03wt％；V≤0.05wt％；Fe≤0.4wt％；其余为铝；
    所述皮材至少包括含有如下组分的铝锌合金：
    Zn 4-7wt％；Si 0.5-1.0wt％；Ti 0.1-0.2wt％；Fe 0.5-1.5wt％；
    或者；
    所述芯材包括含有如下组分的铝合金：
    Si≤0.25wt％；Cu≤0.05wt％；Mg≤0.05wt％；Zn≤0.05wt％；Mn≤0.05wt％；Ti≤0.03wt％；V≤0.05wt％；Fe≤0.4wt％；Sm 0.1-0.3wt％；其余为铝；
    所述皮材至少包括含有如下组分的铝锌合金：
    Zn 4-7wt％；Si 0.5-1.0wt％；Ti 0.1-0.2wt％；Fe 0.5-1.5wt％；Sm 0.1-0.3wt％。
  5. 如权利要求3所述的电池用包装材料，复合层铝箔中皮材的腐蚀电位比芯材的腐蚀电位低50mV-500mV。
  6. 如权利要求3所述的电池用包装材料，复合层铝箔中芯材为1系铝合金或8系铝合金，复合层铝箔的外侧皮材由1系铝合金或8系铝合金基础上添加1％-10％质量百分比的锌元素形成。
  7. 如权利要求2-6中任一种所述的电池用包装材料，该铝塑膜或铝塑膜中的铝箔的冲压深度值或杯突值大于5毫米。
  8. 如权利要求3所述的电池用包装材料，塑料层仅复合于铝箔层的内侧，内侧塑料层为热塑性树脂薄膜。
  9. 如权利要求2或3所述的电池用包装材料，该铝塑膜或其铝箔的耐OY水溶液腐蚀寿命大于500小时。
  10. 如权利要求1所述的电池用包装材料，由金属箔和位于金属箔内侧的热塑性树脂薄膜复合形成；其中，金属箔为不锈钢箔单层金属，或者，金属箔为包含有芯材和位于芯材外侧的皮材的复合层金属箔，金属箔的皮材的腐蚀电位低于芯材的腐蚀电位。
  11. 一种软包电池，包含有电极材料和电解质以及外部包裹用的如权利要求1至10所述任一种电池用包装材料，该软包电池本体具有如下耐冷却液腐蚀性能：耐腐蚀测试方法为OY水溶液腐蚀试验；将该软包电池的本体浸泡于水溶液中，该软包电池的在上述试验中的耐腐蚀寿命大于500小时；所述金属箔层内表面的塑料层将电解质与金属箔层隔离。
  12. 一种软包电池，包含有电极材料和电解质以及外部包裹用如权利要求1至10所述任一种电池用包装材料，所述金属箔层内表面的塑料层将电解质与金属箔层隔离；该软包电池在特定的软包电池的耐防冻液腐蚀寿命试验中，铝箔最大腐蚀深度值达到铝箔原始厚度值的10％时，该软包电池的寿命值大于336小时。
  13. 一种软包电池热控制装置，其软包电池采用如权利要求1至10所述任一种电池用包装材料包装；所述金属箔层内表面的塑料层将软包电池电解质与金属箔层隔离；该软包电池能够与水基冷却液直接接触换热。
  14. 如权利要求13所述的软包电池热控制装置，还包括隔板和水基冷却液；所述隔板的至少部分表面与所述软包电池至少部分外表面直接接触，并且隔板内设有流体通道；若干个软包电池组成一个电池单元，电池单元与隔板间隔设置；水基冷却液在隔板内流体通道中流动，水基冷却液与软包电池直接接触换热。
  15. 如权利要求14所述的软包电池热控制装置，所述隔板采用金属材料；隔板的腐蚀电位等于或负于铝塑膜中铝箔腐蚀电位，或者隔板的腐蚀电位等于或负于铝塑膜的铝箔的皮材的腐蚀电位。
  16. 一种制造如权利要求1至10所述任一种电池用包装材料的方法，
    首先通过如下耐水溶液腐蚀试验选择相应的铝箔：耐腐蚀测试采用OY水溶液腐蚀试验方法，该铝箔的在该腐蚀试验方法下的耐腐蚀寿命大于500小时；
    然后再将该铝箔和塑料薄膜进行复合形成铝塑膜。
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