CN101958438A - Thermal management multilayer film, sheet and hollow piece for secondary battery and super capacitor - Google Patents
Thermal management multilayer film, sheet and hollow piece for secondary battery and super capacitor Download PDFInfo
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- CN101958438A CN101958438A CN2009101501868A CN200910150186A CN101958438A CN 101958438 A CN101958438 A CN 101958438A CN 2009101501868 A CN2009101501868 A CN 2009101501868A CN 200910150186 A CN200910150186 A CN 200910150186A CN 101958438 A CN101958438 A CN 101958438A
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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Abstract
The invention relates to a thermal management multilayer film, sheet and hollow piece for the shell and casing pipe of a secondary battery and super capacitor, which can be used for effectively controlling the temperature of an operated secondary battery and super capacitor and comprise a plurality of replaceable laminated bodies of metal layers, plastic layers and adhesive layers, wherein the plastic layers and the adhesive layers comprise mother phase resin, heat conducting particles and particle coated phase change material (MCPCM) particles. The heat conducting particles promotes heat conduction, and the MCPCM particles absorb the heat generated when the secondary battery and super capacitor discharges.
Description
Technical field
The present invention relates to multilayer film, thin slice and the hollow object of heat treatment function of shell, the sleeve pipe of the power brick that a kind of use forms in single secondary cell and super capacitor and many secondary cells and super capacitor connection in series-parallel with heat conduction, isolated and absorption.Above-mentioned multilayer film, thin slice and hollow object are dispersed with particulate coated phase-change formed material (MCPCM) particle and heat conduction particle, with the heat that absorbs and disperse secondary cell and super capacitor to be produced between charge and discharge.Above-mentioned multilayer film, thin slice and hollow object can be used as the radiator and/or the insulation of phase change form, are not subjected to the thermal impact of hot environment with protection secondary cell and super capacitor.In multilayer film, thin slice and hollow object, plastic layer can be replaced with adhesion layer, or plastic layer is carried out chemical modification, to provide each interlayer enough tack strengths.
Background technology
A kind of known particulate coated phase-change heat-transmission absorbing material is documented in No. 5224356 bulletin case of United States Patent (USP), wherein disclosed and used the base material that comprises thermal energy absorbing material, with the electronic building brick of cooling, can reduce the surface temperature of about 65-80% effectively as integrated circuit and resistance.Alkane and congruent melting metal can be chosen as phase-transition material, to obtain the optimal heat character under the different operating temperature.
Then disclosed the another kind of heat management system that becomes known for having a plurality of secondary cells with reference to No. 7270910 bulletin case of United States Patent (USP), wherein a kind of heat management system that is used to cool off the secondary cell of wireless power tool, comprised colloid coating layer with particulate coated phase-change formed material (MCPCM), Figure 12 A with reference to No. the 7270910th, United States Patent (USP), 12B, the melting latent heat of the phase-transition material that above-mentioned heat management system use colloid coating layer is coated absorbs the heat that secondary cell sheds.The colloid coating layer has comprised plastic carrier and MCPCM.The advantage of this system is, the machine components that need not to move cool off, and decentralized photo fully is coated on the secondary cell bag, does not therefore need any extra air stream or radiator with the outside of heat transferred to secondary cell, can use more than thousands of times with being recycled.But the shortcoming of this system is, do not have the abundant heat conductivity that heat can be dispersed in the environment, and since the production of colloid coating layer, the necessary mode that adopts the plastics injection molding, therefore can't reach high efficiency production effectively, cause the waste of cost costliness and manpower.In order to improve the shortcoming of above-mentioned secondary cell colloid coating layer, the present invention proposes a kind of multilayer film, thin slice and hollow object with metal level and/or plastic layer of thermal conductive particles, wherein thermal conductive particles can be improved the heat conductivity that heat is dispersed to environment fully, and can be with heat absorption in the MCPCM material that disperses wherein.The multilayer film of manufacturing, thin slice and hollow object according to the present invention are to use coextrusion and extrusion coated processing procedure, but have the quantity-produced characteristic, can improve the efficient of production, reduce the cost of manpower simultaneously.Though the application of heat management multilayer film and MCPCM material discloses in above-mentioned prior art content to some extent, in the content of prior art all without any it being utilized coextrusion and extrusion coated processing procedure with improvement and be applied in the teaching of secondary cell and super capacitor.
In the content of Journal of Power Sources 99 (2001) 70-77, disclosed the generation of lithium rechargeable battery and nickel-hydrogen secondary cell heat in the charge and discharge process.The efficient of charge and discharge is to be subjected to the secondary cell Temperature Influence just as the life-span of secondary cell.Therefore, temperature control is very important for secondary cell, the shell with heat management function of secondary cell and super capacitor or sleeve pipe is provided thereby has practical significance.The invention provides a kind of multilayer film with heat management function, thin slice and hollow object of novelty, it has following character: effectively and efficiently when charge and discharge heat is absorbed or removes from secondary cell or super capacitor, good tackness between the unlike material of multilayer film, thin slice and hollow object, but and quantity-produced processing procedure.
Secondary cell bag and super capacitor bag are to be made of the secondary cell of plural number and the connection in series-parallel of super capacitor institute, wherein make shell and/or sleeve pipe by the multilayer film with heat management function, thin slice and hollow object, it can prolong the life-span of secondary cell and super capacitor effectively, provide preferable charge and discharge efficient and stability, and efficient and cost-effective ground produces secondary cell, super capacitor and secondary cell bag, super capacitor bag.
Summary of the invention
The present invention is by providing heat management multilayer film, thin slice and the hollow object of secondary cell and a kind of improvement of super capacitor, can overcome the shortcoming of using colloid coating layer method in the prior art effectively, and have preferable thermal diffusivity, simplified the processing procedure of secondary cell bag and super capacitor bag simultaneously.
The invention particularly relates to a kind of heat management shell and sleeve pipe that is used for secondary cell and super capacitor, have metal level by providing, multilayer film, thin slice and a hollow object of plastic layer and adhesion layer, can reach above-mentioned effect.
The structure of heat management multilayer film of the present invention, thin slice and hollow object has comprised the lamina of the selectable metal level of plural layer, plastic layer and adhesion layer.And the manufacture method of multilayer film, thin slice and hollow object can be coextrusion, casting coextrusion and plastics/adhesion layer is extrusion coated to another metal level.Therefore metal level can comprise nickel, copper, tungsten, molybdenum, aluminium, steel, silver, gold or other possible metal and metal alloy.
Plastic layer and adhesion layer are made of parent phase resin, heat conduction particle and particulate coated phase-change formed material (MCPCM) particle.MCPCM particle and heat conduction particle are dispersed among the parent phase resin of plastic layer and adhesion layer by the composite material processing procedure, and the parent phase resin of plastic layer and adhesion layer can be the acrylonitrile-butadiene-benzene diene copolymers (ABS) of extrusion grade, glassine paper (CEL), celluloid (CN), cellulose acetate (CA), low density polyethylene (LDPE) (LDPE), high density polyethylene (HDPE) (HDPE), oriented polypropylene (OPP) (OPP), ionomer (IO), PETG (PET), polybutylene terephthalate (PBT) (PBT), polystyrene (PS), Merlon (PC), polysulfones (PS), polyethers (PESU), polyimides (PI), Polyetherimide (Polyetherimides), polymethyl methacrylate (PMMA), polyamide (nylon 4, nylon 6, nylon 7, nylon 11, nylon 12, nylon (4,6), nylon (6,6), nylon (6,8), nylon (6,10), nylon (6,12), tetrafluoride polyethylene (PTFE) and other fluoropolymer, the EVOH copolymer, the EVA copolymer.The typical parent phase resin of adhesion layer is common adhesion layer, and its trade name is PLEXAR, BYNEL, ADMER, NOVATEC, CXA.Adhesion layer parent phase resin is characterised in that excellent tackness between metal level and plastic layer.
The present invention uses the adhesion layer parent phase resin of extrusion grade, utilizes coextrusion and extrusion coated processing procedure, with in conjunction with two not good unlike materials of tackness each other.Therefore make that heat management multilayer film of the present invention, thin slice and hollow object can have unique adhesive properties to the material of each.
For example, high density polyethylene (HDPE) is very poor for the tackness of ethylene-vinyl alcohol copolymer.By (for example using Plexar
1000), can create sandwich construction in conjunction with the rigidity of the low oxygen permeability of EVOH and high density polyethylene (HDPE) as above-mentioned adhesion layer material.And the parent phase resin of plastic layer also has enough penetration-resistants, to keep out outside moisture, oxygen and inner electrolyte.
For the heat conduction particle that is distributed in above-mentioned plastic layer and the adhesion layer parent phase resin, its material mainly is made of metallic element or pottery.The heat conduction particle is evenly distributed in the above-mentioned plastic layer, its main effect be effectively with heat by the conducted inside of secondary cell or super capacitor to outside environment.In other words, the heat conduction particle increases the heat conductivity of plastic layer and adhesion layer.In order to promote heat conducting validity and efficient effectively, when selecting the heat conduction particle, must consider size, the form of heat conduction particle and the interactive effect of using multiple heat conduction particle.
The material of desirable heat conduction particle can be selected from metal or carbonaceous material, for example be coated with copper powder, silver, nickel, aluminium, copper, glass putty, alloying metal powder, hydride-dehydrogenation titanium valve, stainless steel powder, powdered graphite, carbon black powder, CNT (carbon nano-tube) (CNTs), diamond powder, nano metal powder, ball-aluminium oxide powder, the ultra-fine ball-aluminium oxide powder that causes of silver, or the non-oxidized substance powder, as aluminium nitride powder, hexahedron boron nitride powder, boron carbide (B
4C), gallium phosphide (GaP), indium phosphide (InP), lanthanum boride (LaB
6), molybdenum bisuphide (MoS
2), silicon nitride (Si
3N
4), tantalum nitride (TaN), titanium carbide (TiC), titanium nitride (TiN), tungsten carbide (WC), tungsten carbide/cobalt (WC/Co), fluoridize ytterbium (YbF
3) and the sintered body of above-mentioned particle any mixture.
Also can select for example aluminium oxide (Al of oxide powder
2O
3), aluminium hydroxide (Al (OH)
3), diboron trioxide (B
2O
3), brium carbonate (BaCO
3), barium sulfate (BaSO
4), barium titanate (BaTiO
3), cerium oxide (CeO
2), cobalt ferrite (CoFe
2O
4), cobalt ferrite zinc (Co
0.5Zn
0.5Fe
2O
4), cobalt oxide (CoO), cobaltosic oxide (Co3O4), chromium trioxide (CrO3), phosphoric acid caesium (CsH
2PO
4), cupric oxide (CuO), dysprosia ((Dy
2O
3), erbium oxide (Er
2O
3), europium oxide (Eu
2O
3), iron oxide (Fe
2O
3), tri-iron tetroxide (Fe
3O
4), gadolinium oxide (Gd
2O
3), hafnium oxide (H
fO
2), indium oxide (In
2O
3), indium hydroxide (In (OH)
3), tin oxide (SnO
2), lanthana (La
2O
3), lithia titanium (Li
4Ti
5O
12), oxidation magnalium (MgAl
2O
4), magnesium oxide (MgO), magnesium hydroxide (Mg (OH)
2), manganous hydroxide (Mn
2O
3), molybdenum oxide (MoO
3), rubidium oxide (Nd
2O
3), oxidation ferronickel (NiFe
2O
4), nickel oxide zinc-iron (Ni
0.5Zn
0.5Fe
2O
4), nickel oxide (NiO), nickel sesquioxide (Ni
2O
3), praseodymium oxide (Pr
6O
11), antimonous oxide (Sb
2O
3), silicon dioxide (SiO
2), samarium sesquioxide (Sm
2O
3), tin ash (SnO
2), strontium oxide strontia aluminium (SrAl
12O
19), strontium carbonate (SrCO
3), strontium oxide strontia aluminium (SrFe
12O
19), tin oxide (Tb
4O
7), titanium dioxide (TiO
2), vanadium oxide (VO), vanadium trioxide (V
2O
3), vanadic oxide (V
2O
5), tungstic acid (WO
3), yttrium-aluminium-garnet (YAG), yttrium-aluminium-garnet/metal plate (YAG/Ce), yttrium-aluminium-garnet/cerium (YAG/Ce), yttrium-aluminium-garnet/neodymium (YAG/Nd), yittrium oxide (Y
2O
3), iron oxide zinc (ZnFe
2O
4), zinc oxide (ZnO), zirconia (ZrO
2), zirconia/yittrium oxide (ZrO
2/ Y
2O
3), zirconia/calcium oxide (ZrO
2/ CaO), zirconia/cerium oxide (ZrO
2/ CaO) and other nano level metal dust, the sintered body that mixes arbitrarily as Nano-class zinc oxide, nanometer-level silver, nanoscale gold, nano-scale magnetic powder and above-mentioned particle.
The mean particle diameter of above-mentioned thermal conductivity particle is 500 microns to 1 micron, and serves as preferred with 250 microns to 5 microns again.
About interspersing among the MCPCM particle in the parent phase resin, the MCPCM particle utilizes the latent heat of the wherein melting of phase-transition material to store the heat that secondary cell and super capacitor produce, and in after shed.For example the heat that secondary cell and high capacitance produced of self discharge is absorbed and is converted into the latent heat of melting by the phase-transition material in the MCPCM particle, and makes MCPCM remain on the constant temperature of melting temperature in the melting state, and is liquid by solid state transformation.And according to secondary cell and super capacitor in the discharge of using heat management multilayer film of the present invention, thin slice and hollow object, its temperature can remain on lower stable temperature compared to secondary cell that does not use heat management multilayer film of the present invention, thin slice and hollow object and super capacitor.The thermmal storage of MCPCM particle mainly is the phase-transition material by core, for example hydro carbons hydrocarbon.When phase change betides in the MCPCM particle, need quite high energy.
In the present invention, the selection of MCPCM particle under specific operation condition is to determine according to the heating of secondary cell and super capacitor or the temperature of cool cycles.But the phase change temperature of MCPCM particle has its restriction.For example, the phase change temperature of some pure alkene takes place from being lower than ambient temperature to being higher than 60 ℃.The change of phase change temperature is to determine according to the length of alkane carbochain and its purity.If the quantity of the carbon in the chain be odd number and/or chain length greater than 20 carbon, the latent heat of part with solid-state in second transition that produced relevant.MCPCM particle used in the present invention adopts little coating, so phase-transition material can be separated with its periphery.
When preventing the fusing of selected phase-transition material, little coating mixes with generation on every side.The diameter of MCPCM particle is preferably 1 micron to 500 microns 0.5 micron to 1000 microns scope.
The phase-transition material (PCM) that is fit to is to coat wall by heat conduction to be coated, and can be the phase-transition material of organic or inorganic.Usually the fusing point that has wide range as organic PCM of hydrocarbon alkane.Inorganic PCM is generally the material of moisture salt, has moisture and anhydrous form.
According to different execution modes of the present invention, the PCM with stable advantage has comprised many organic substances.For example, the PCM of hydrocarbon comprises as linear paraffin, the alkane hydrocarbon, branched paraffin, unsaturated hydrocarbons, halogenation alkane, alicyclic ring alkane, wax, oil, aliphatic acid, fatty acid ester, binary acid, dibasic acid ester, 1-halide, primary alcohol, aromatic compound, and anhydride, stretch ethyl ester as carbonic acid, polyalcohol, 2,2-dimethyl-1, ammediol, dihydroxymethyl-2-methyl isophthalic acid, ammediol, ethylene glycol, polyethylene glycol, pentaerythrite, the diisoamyl tetrol, five glycerol, tetra methylol ethane, neopentyl glycol, tetra methylol propane, new penta tetrol of amido, new penta tetrol of two amidos, trihydroxy methyl acetate, and polymer such as polyethylene, polyethylene glycol, polypropylene, polypropylene glycol, polytetramethylene glycol, and copolymer.Be suitable as in the alkane hydrocarbon of PCM, wherein the alkane hydrocarbon can be positive octacosane, heptacosane, n-hexacosane, pentacosane, n-tetracosane, n-tricosane, n-docosane, Heneicosane, n-eicosane, NSC 77136, n-octadecane, n-heptadecane, hexadecane, n-pentadecane, n-tetradecane, n-tridecane and composition thereof.Inorganic PCM is generally the material of moisture salt, wherein comprises one or more element and composition thereof or the alloy that is selected from Te, Se, Ge, Sb, Bi, Pb, Sn, As, S, Si, P, O.
PCM can be the mixture of two or more material, and by selecting two or more materials and form its mixture, the temperature stabilization scope can tune to the broad range of any required application.According to part execution mode of the present invention, PCM can comprise the material of above-mentioned two or more.
According to multilayer film, thin slice and the hollow object with heat management function of the present invention, comprise the combination in any of to 20 layer interchangeable metal level, plastic layer or adhesion layer.And needing under the situation of adhesion layer, adhesion layer can placed between metal level-plastic layer or the plastic layer-plastic layer.
Typical multilayer film, thin slice and hollow object have comprised five layers structure, have wherein comprised first plastic layer, first adhesion layer, central metal layer, second adhesion layer and second plastic layer, and wherein adhesion layer places between above-mentioned metal level and the plastic layer.Another typical structure is nine layers a structure, wherein comprises the metal level and the plastic layer of another layer, and the adhesion layer that is attached to two ends, the above-mentioned five-layer structure outside respectively.
The number of plies of any different metal level, plastic layer and adhesion layer changes and varied in thickness can be reached according to user's design.
Though each layer of multilayer film object structure can be made of different thickness, the preferable situation of the thickness of each layer of multilayer film object structure is next to be to be controlled between 5 microns to 1000 microns.Under the preferable situation, integral multi-layered film then is to be controlled at less than in 20000 microns the scope.The thickness of adhesion layer can change, and common thickness can be with the THICKNESS CONTROL of adhesion layer between 5 microns to 20 microns under the preferable situation then between 1 micron to 50 microns.
The processing procedure that heat conduction particle and MCPCM particle is added the parent phase resin of plastic layer and adhesion layer can be finished by the composite material processing procedure.The processing procedure of composite material uses an extruder, two groups of above gravity charging, a water bath and comminutors to carry out.Under the typical situation, extruder has the twin-screw melting district of the common rotation in five to Shi Wu districts.Be imported into the leading portion zone of extruder through the parent phase resin/polymer of the plastic layer of oven drying or adhesion layer, and in addition melting of the twin-screw by common rotation.The two sides charger that is arranged in the extruder zone line then is used for heat conduction particle and MCPCM particle are directed into the melting stream of parent phase resin/polymer.
The gravity charging is used for controlling exactly the heat conduction particle that joins extruder and the quantity of MCPCM particle.After the melting of resin/polymer, wherein be dispersed with heat conduction particle and MCPCM particle, after melting stream will pass the back segment zone of extruder, resin/polymer strip entered in the water-bath and solidifies.Resin/the polymer strip of solidifying is then passed comminutor and is produced about particle of 2 to 4mm.Behind the composite material processing procedure, compound resin (the parent phase resin of plastic layer or adhesion layer is scattered with heat conduction particle and MCPCM particle) is dried and is stored in the moisture barrier bag, to treat follow-up coextrusion or extrusion coated processing procedure.
Multilayer film, thin slice and hollow object with heat management function according to the present invention can be divided into multilayer film, the thin slice of four classes: 1.PPP (plastic layer-plastic layer-plastic layer) and PAP (plastic layer-adhesion layer-plastic layer) according to its manufacture method.The multilayer film hollow object of (2.PPP plastic layer-plastic layer-plastic layer) and PAP (plastic layer-adhesion layer-plastic layer).Multilayer film, the thin slice of (3.PMP plastic layer-metal level-plastic layer) and PAMAP (plastic layer-adhesion layer-metal level-adhesion layer-plastic layer).The multilayer film hollow object of (4.PMP plastic layer-metal level-plastic layer) and PAMAP (plastic layer-adhesion layer-metal level-adhesion layer-plastic layer).
The method of making multilayer film, the thin slice of PPP (plastic layer-plastic layer-plastic layer) and PAP (plastic layer-adhesion layer-plastic layer) adopt in the prior art common device and processing procedure.The coextrusion processing procedure as prior art disclosed is adopted in the multilayer film of PPP (plastic layer-plastic layer-plastic layer) and PAP (plastic layer-adhesion layer-plastic layer), the manufacturing of thin slice.Extruder comprises main extruder and coextrusion machine, is used to provide the polymer melting stream of composite material processing procedure, by control melting stream flow as the feed arrangement of gear pump, flows to feed block with the polymer melting that adds the composite material processing procedure.By the input port after the thermoplastic extruder is accepted melting stream, feed block spreads melting delivers to wherein mechanicalness operation section, wherein original melting stream is bonded to the multilayer flow structure that forms according to requirement and arrangement.This multilayer is flowed through and is formed by a multilayer manifold extrusion die, wherein optionally flows in conjunction with the multilayer from feed block from the extruder that adds.And last mould combines all melting stream and form final multilayer stream.The prolongation and the deformation of final multilayer stream are formed by annular cross section, and it comes from feed block, can also produce the smooth section of homogeneous thickness simultaneously in the mould.Therefore, final multilayer stream can be extruded the mould slit.The required thickness of each layer can be controlled and be got by the gap of runner between the flow of each corresponding melting stream and mould inner axes and the sleeve pipe.The multilayer stream that leaves the mould slit can further be cooled to solid-state by chilling roll, and forms multilayer film and the composite wafer of PPP or PAP.According to the variation design of mould slit areas and cross sectional shape, any required multilayer film and composite wafer structure can be formed according to width, thickness, or form flat surfaces and extensional surface, as the structure of fin.Heat conduction particle and MCPCM particle can intersperse among in each layer equably simultaneously.
The method of making the multilayer loop pipe of PPP (plastic layer-plastic layer-plastic layer) and PAP (plastic layer-adhesion layer-plastic layer) adopt in the prior art common co-extrusion device and processing procedure.The coextrusion processing procedure has comprised main extruder and coextrusion machine, be used for heating and plasticizing composite material processing procedure plastic grain to melting stream, the polymer melting that will add the composite material processing procedure by the feed arrangement as gear pump flow to mould, and flows flow in order to the melting that control flows in the die ontology.Mould itself has comprised the mold of a hollow, wherein have interior thorax, place the axle center of interior thorax, runner, the flow rate limiting device in formation ring-type charging cabin then to be used for again in conjunction with the melting stream that separates by the spider web device, and the flow of the extra melting stream that forms la m is provided in the hole, balanced runner and ring footpath, and the pressure balance storage tank is used for flowing of balance melting stream.In the inside of mould, pass flow rate limiting device and flow passage device to form ring-type multilayer melting stream from the melting stream of main extruder and coextrusion machine.This ring-type multilayer stream then flows in the ring-type exclusion sleeve.The profile of exclusion sleeve can be determined according to the profile of the multilayer film hollow object that will make, if exclusion sleeve is a ring-type, the profile of then final made multilayer film hollow object is tubulose.If the external form of exclusion sleeve is a rectangle, then finally the profile of made multilayer film hollow object is the rectangle column.By after the exclusion sleeve, the multilayer melting flows to into a size mould, and it is connected in a vacuum adjusted size device, to adjust the multilayer film pipe extruded or hollow object to desired size.Inside at vacuum adjusted size device has a cooling chamber, and this cooling chamber is used for solidifying multilayer melting stream.Multilayer film pipe that solidifies or hollow object are further by a stretching device.This stretching device stretches out by vacuum adjusted size device with multilayer film pipe or hollow object self-discharging sleeve pipe.The multilayer film hollow object of PPP or PAP form can be specified the thickness and the gross thickness of its cross sectional shape, size, the number of plies, individual layers, and when tack strength was not enough, necessary words added the adhesion layer of intermediary, and each layer includes heat conduction particle and MCPCM particle.
The method of making multilayer film, the thin slice of PMP (plastic layer-metal level-plastic layer) and PAMAP (plastic layer-adhesion layer-metal level-adhesion layer-plastic layer) adopt in the prior art common device and processing procedure.This processing procedure at first carries out preliminary treatment to the metal surface, so that sufficient tackness to be arranged between the plastic layer of guaranteeing metal surface and coating.Some optionally also exposure to some extent in the prior art of preliminary treatment.Comprised cleaning, pickling, sandblast and grinding in the preliminary treatment that prior art disclosed, be accompanied by and clean with dry.After pretreated program, metal level is rolled into web-like, and to make that plastic layer is carried out continuous extrusion coated.The metal level that curls is released subsequently and is moved to carry out the without interruption of online processing procedure by the suspention roller.Before carrying out the extruding of plastic layer, the metal level that moves optionally carries out opening stroke or corona discharge, reaching the desired surface activation degree, and produces the preferable tackness between plastic layer and the metal level.The multilayer melting stream of PPP or PAP type then is coated to the surface of moving middle sheet metal by the mould slit.The coextrusion melting stream of previous PPP that is narrated or PAP type can specific its desired width, thickness, the number of plies, flat shape or extensional surface shape.After extrusion coated program, the metal level that is coated with passes the pinching roller so that plastic layer firmly engages with sheet metal.Then, the plastics melting stream that is coated with is cured by a cooling bath or cooling bath.As the multilayer film or the thin slice of PPP or PAP type, the cross sectional shape of its mould or area determine width, thickness, the number of plies, flat shape or the extensional surface shape of desired coating multiple plastic layer.The arrangement of different plastic layers and adhesion layer is determined by the feed block of mould and coextrusion.Then add adhesion layer when the zygosity between metal level and plastic layer or plastic layer and plastic layer is not good.The composite material of required heat conduction particle and MCPCM number of particles can be made by main extruder and coextrusion machine in plastic layer and the adhesion layer parent phase resin.
The method of making the multi-layered composite pipe of PMP (plastic layer-metal level-plastic layer) and PAMAP (plastic layer-adhesion layer-metal level-adhesion layer-plastic layer) adopt in the prior art common device and processing procedure.This processing procedure at first carries out decontamination and preliminary treatment to the metal surface, just as above-mentioned preprocessor described in PMP and PAMAP multilayer film or the composite wafer.Then, the internal layer of PPP or PAP type is extruded or coextrusion goes out, and its method is as the above-mentioned processing procedure of extruding about PPP and PAP multilayer film pipe.The surface preparation metal tape is subsequently by a series of profile roll, as the forming mode of prior art institute teaching.Metal tape is shaped around PPP or PAP multilayer film pipe continuously.Then, the sealing of metal tape can be finished by any welding running, and for example laser welding, arc welding or resistance welded form the metal tube that seals thus.The diameter of closed metal pipe can reduce by taking out the program of falling together, makes the inner surface of closed metal pipe engage with the outer surface of PPP or PAP multilayer film pipe.Then, make generation joint between the surface by the fusing point that is heated to PPP or PAP multilayer film pipe again.In this stage, can obtain having the MP (metal level-plastic layer) of outer metal layer and inner plastic layer or plastic layer-adhesion layer or the multilayer film pipe of MAP (metal level-adhesion layer-plastic layer) form.Then, will desire the surface that coat plastics layer or plastic layer-adhesion layer are applied to the multilayer film pipe of above-mentioned MP or MAP form as the employed extrusion coated processing procedure of prior art.The multilayer film pipe of MP or MAP kenel being coated with adhesion layer and plastic layer continuously, and utilizes hydraulic means to come the multilayer film pipe of mobile MP or MAP kenel by a series of mould.Last cooling step is used for hardened plastic layer or adhesion layer.If necessary, extra metal level, plastic layer and adhesion layer can be added in a like fashion.At last, can obtain the multilayer film pipe of PMP or PAMAP.The manufacture method of PMP or PAMAP form multilayer film hollow object is same as the manufacture method of PMP or PAMAP form multilayer film pipe, and difference only is to adopt different metal tube profile rolls, to form needed cross sectional shape, as rectangle or triangle.And be used to extrude or coextrusion also can be adjusted mould according to required cross sectional shape with the mould that forms plastic layer or adhesion layer.PMP or PAMAP form multilayer film hollow object can specific its cross sectional shapes, the quantity of size and each metal level, plastic layer and adhesion layer, simultaneously thickness, integral thickness and the plane that also can specific individual layers or the shape of extensional surface simultaneously can specific indivedual plastic layers and heat conduction particle and the MCPCM particle kind and the quantity of adhesion layer.
Description of drawings
Fig. 1 is the schematic diagram of employed cylindrical lithium secondary battery/super capacitor in the prior art.
Fig. 2 A and Fig. 2 B are the schematic diagram of employed square lithium secondary battery/super capacitor in the prior art.
Fig. 3 is the amplification cross section structure schematic diagram of particulate coated phase-change formed material particle.
Fig. 4 is a kind of amplification profile schematic diagram with heat management multilayer film/thin slice of five-layer structure of the present invention.
Fig. 5 has the amplification profile schematic diagram of the heat management multilayer film/thin slice of multi-layer film structure for another kind of the present invention.
Fig. 6 A, Fig. 6 B and Fig. 6 C are the schematic diagram of the preferred implementation of heat management multilayer film/thin slice of having bilayer, three layers and five-layer structure according to the present invention.
Fig. 7 A, Fig. 7 B and Fig. 7 C are heat conduction particle, MCPCM particle and composition thereof plastic layer and adhesion layer distribution schematic diagram partly in multi-layer film structure.
Fig. 8 A and Fig. 8 B are the five-layer structure schematic diagram of PPP, PAP, PMP and PAMAP form multi-layer film structure.
Fig. 9 A and Fig. 9 B are the five-layer structure schematic diagram of PPP, PAP, PMP and PAMAP water chestnut cylindricality multilayer film tubular structure.
Figure 10 A and Figure 10 B are the five-layer structure schematic diagram of the cylindrical multilayer film tubular structure of PPP, PAP, PMP and PAMAP.
Figure 11 A and Figure 11 B are the five-layer structure schematic diagram of PPP, PAP, PMP and PAMAP arbitrary shape multilayer film hollow tubular structure.
Figure 12 A and Figure 12 B are the temperature graph that single secondary cell/high capacitance has or do not have multi-layer film structure shell of the present invention or sleeve pipe.
Figure 13 A, Figure 13 B and Figure 13 C are the block flow diagram of PPP and PAP multi-layer film structure fabrication schedule.
Figure 14 A, Figure 14 B, Figure 14 C and Figure 14 D are the block flow diagram of PMP and PAMAP multi-layer film structure fabrication schedule.
[primary clustering symbol description]
101 cathode layers
102 anode layers
103 separators
104 cathode wires
105 positive wires
106 safety valves
107 PTC resistors
108 top covers
109 sealing gland pads
110 insulating barriers
111 shells
201 cathode layers
202 anode layers
203 separators
204 cathode wires
205 positive wires
206 safety valves
207 negative electrodes lid
208 sealing gland pads
209 insulating barriers
210 shells
301 heat conduction layers
302 phase-transition materials
401 metal levels
402 plastic layers
403 adhesion layers
501 plastic layers
502 adhesion layers
503 outside plastic layers
601 adhesion layers
602 metal levels or plastic layer
701 heat conduction particles
702 MCPCM particles
703 heat conduction particles and MCPCM particles mixture
801 surfaces
802 fins
901 surfaces
902 fins
1001 surfaces
1002 fins
1101 surfaces
1102 fins
1103 sleeve pipes
1104 required objects
Embodiment
For understanding purpose of the present invention, feature and effect, now by following concrete execution mode, and cooperate appended graphicly, the present invention is done a detailed description, illustrate as afterwards:
With reference to Fig. 1, shown employed cylindrical lithium secondary battery/super capacitor in the prior art.Cylindrical lithium secondary battery/super capacitor in the known technology has comprised the plural layer such as separator 103 between cathode layer 101, anode layer 102 and cathode layer 101 and the anode layer 102.Cathode layer 101 is connected to cathode wire 104 and positive wire 105 with the end of anode layer 102, and the other parts of secondary cell comprise known cylindrical lithium secondary battery/super capacitor assembly, as make safety valve 106, PTC resistor 107 (PTC), top cover 108, sealing gland pad 109, the insulating barrier 110 that gas overflows and prevent that electrolyte from flowing out the shell of charging into foreign 111.As shown in Figure 1, in the process of secondary cell/super capacitor mould charge and discharge, produce the surface that is conducted to insulating barrier 110 and shell 111 from the heat energy of whole secondary cell/super capacitor mould.
With reference to Fig. 2 A and Fig. 2 B, shown employed square lithium secondary battery/super capacitor in the prior art.Square lithium secondary battery/super capacitor comprises plural layer usually, has wherein comprised the plural layer such as separator 203 between cathode layer 201, anode layer 202 and cathode layer 201 and the anode layer 202.When electrode layer and separator 203 overlapping during according to the order of cathode layer 201, separator 203, anode layer 202, separator 203 to required secondary cell/super capacitor quantity, the end of cathode layer 201 and anode layer 202 is connected to cathode wire 204 and positive wire 205, and the other parts of secondary cell comprise known square lithium secondary battery/super capacitor assembly, as make safety valve 206, negative electrode lid 207, sealing gland pad 208, the insulating barrier 209 that gas overflows and prevent that electrolyte from flowing out the shell of charging into foreign 210.Shown in Fig. 2 A, 2B, in the process of secondary cell/super capacitor mould charge and discharge, produce the surface that is conducted to insulating barrier 209 and shell 210 from the heat energy of whole secondary cell/super capacitor mould.
Fig. 3 shows that phase-transition material 302 (PCM) is coated the cross section structure that shows in particulate coated phase-change formed material (MCPCM) particle by heat conduction layer 301.Phase-transition material 302 heat is stored and in after dispel the heat.The heat that secondary cell/super capacitor discharged by discharge can be absorbed by the MCPCM particle, and makes PCM 302 produce by solid-state to liquid phase change result.The heat that is stored among the PCM 302 can suitably dissipate in the surrounding environment during heat radiation.The thermmal storage of PCM 302 mainly is the latent heat that comes from fusion.PCM 302 of the present invention adopts little coating to utilize the heat conduction layer 301 of shell as the material that selected material is separated with external environment condition.The heat conduction layer of using as the shell coating layer 301 can prolong its useful life effectively by PCM 302 is coated.The size of heat conduction particle can be 0.5 to 1000 micron.And the heat conduction layer 301 of shell is made of metal, pottery or polymer.
With reference to the content of Fig. 4 of the present invention and Fig. 5, two kinds of preferred implementations of the present invention have been shown.Fig. 4 has wherein comprised layer of metal layer 401, two layers of plastic layer 403 and two-layer adhesion layer 402 for a kind of preferred implementation with heat management multilayer film/thin slice of five-layer structure according to the present invention.And adhesion layer places between metal level 401 and the plastic layer 403.Multilayer film/thin slice of the present invention can have various structure by the joint of adhesion layer between the plastic layer.Typical multilayer film/flake structure is just as shown in the better embodiment of Fig. 4.Intermediate metal layer 401 provides necessary strength and heat conductivity in heat management multilayer film/thin slice.And metal level can comprise nickel, copper, tungsten, molybdenum, aluminium, steel, silver, gold and other available metal forming.The composition of adhesion layer 402 can be the polyolefin of alkyl ester copolymer and mixture, upgrading and mixture arbitrarily thereof according to the present invention.Heat conduction particle as the MCPCM particle also is scattered in the adhesion layer 402 equably, to absorb the heat that produces in secondary cell/super capacitor.The material of the plastic layer 403 in the two-sided outside of multi-layer film structure can be polyethylene, polyethylene and ethylene copolymers, polyamide, ethene and ethenol copolymer (EVOH), ethylene-vinyl acetate copolymer (EVA), polypropylene, high density polyethylene (HDPE), low density polyethylene (LDPE), LLDPE or other applicable material.The thickness of each of multilayer film/flake structure layer is preferably in 0.05 micron to 250 microns the scope.And better situation is that arbitrary layer thickness of multi-layer film structure is less than 50 microns.The thickness of adhesion layer 402 can change, but usually in 0.05 micron to 12 microns scope.The thickness of preferable this adhesion layer of situation is between 0.05 to 1.0 micron.And best situation is between 0.25 to 0.8 micron.Fig. 5 has wherein comprised one deck intermediate plastic layer 501, two-layer outside plastic layer 503 and two-layer adhesion layer 502 for another kind of the present invention has the better embodiment of the heat management multilayer film/thin slice of five-layer structure.And adhesion layer places between intermediate plastic layer 501 and the outside plastic layer 503.Each layer of the heat management multilayer film/thin slice of five-layer structure of the present invention can have various structure.And the composition of adhesion layer 502 can be the polyolefin of alkyl ester copolymer and mixture, upgrading and mixture arbitrarily thereof.Heat conduction particle as the MCPCM particle also is scattered in two-layer adhesion layer 502, one deck intermediate plastic layer 501 and the two-layer outside plastic layer 503 equably, to absorb the heat that produces in secondary cell/super capacitor.The material of the plastic layer 503 in the two-sided outside of multi-layer film structure can be polyethylene, polyethylene and ethylene copolymers, polyamide, ethene and ethenol copolymer (EVOH), ethylene-vinyl acetate copolymer (EVA), polypropylene, high density polyethylene (HDPE), low density polyethylene (LDPE), LLDPE or other applicable material.Each of multilayer film/flake structure layer can be different thickness, and its thickness is preferably in 0.05 micron to 250 microns the scope.And better situation is that arbitrary layer thickness of multi-layer film structure is less than 50 microns.The thickness of adhesion layer 502 can change, but usually in 0.05 micron to 12 microns scope.The thickness of preferable this adhesion layer of situation is between 0.05 to 1.0 micron.And best situation is between 0.25 to 0.8 micron.
Fig. 6 A, 6B, 6C show have bilayer according to the present invention, the better embodiment of the heat management multilayer film/thin slice of three layers and five-layer structure.According to heat management multilayer film/thin slice of the present invention, comprise layer of metal layer or plastic layer 602 and the minimum one deck adhesion layer 601 that comprises at least.And adhesion layer 601 places between intermediate metal layer or the plastic layer 602.As Fig. 6 A, 6B, shown in the 6C, multilayer film/flake structure can have the adhesion layer 601 that combines with metal level or plastic layer 602, or has two metal levels or the plastic layer 602 that is bonded to adhesion layer 601 two sides.And multilayer film/flake structure may extend to five layers structure, wherein comprised two-layer adhesion layer 601 gluings to three-layer metal layer or plastic layer 602, and adhesion layer 601 is as between metal level or the plastic layer 602.Heat management multilayer film/the thin slice of above-mentioned bilayer, three layers and five-layer structure also can add the two-sided or arbitrary face in the intermediate layer that places other, and intermediate plastic layer 501 as shown in Figure 5 forms the heat management multilayer film/thin slice of different sandwich constructions among the present invention thus.
With reference to Fig. 7 A of the present invention, Fig. 7 B and Fig. 7 C, heat conduction particle 701, MCPCM particle 702 and composition thereof 703 plastic layer and adhesion layer distribution partly in multi-layer film structure have been shown.At Fig. 7 A and Fig. 7 B, heat conduction particle 701 and MCPCM particle 702 are become by aforesaid material, and are scattered in the inside of multi-layer film structure equably.Fig. 7 C shows the homogeneous mixture of heat conduction particle 701 and MCPCM particle 702.Shown in Fig. 7 C, the distribution that mixture 703 shows at random makes heat to be absorbed equably and to be conducted by all directions.The parent phase resin of the homogeneous mixture of heat conduction particle 701 and MCPCM particle 702 and plastic layer and adhesion layer can be reached fully by disclosed composite material processing procedure.
With reference to Fig. 8 A of the present invention and Fig. 8 B, shown the five-layer structure of PPP, PAP, PMP and PAMAP form multi-layer film structure.The surface 801 of five-layer structure has shown the plastic layer that includes heat conduction particle and MCPCM particle.And second to the 4th layer can be respectively metal level, plastic layer or adhesion layer, and it is all formed by above-mentioned fabrication schedule manufacturing, and wherein bottom can be identical material with top layer or other intermediate layer.Fig. 8 A and Fig. 8 B show film and flake structure, and it is two kinds of possible execution modes of the present invention.Fig. 8 B has shown the extra plural number extension fin 802 that adds on the surface of five-layer structure.The shape of fin 802 can have the design of different external forms and size, and this profile also can put on each layer of inside of plural multilayer film and flake structure.
With reference to Fig. 9 A of the present invention and Fig. 9 B, shown the five-layer structure of PPP, PAP, PMP and PAMAP water chestnut cylindricality multilayer film tubular structure 901.As mentioned above, the available different material of each layer of water chestnut cylindricality multilayer film tubular structure 901 replaced, and can add extension fin 902 to adapt to different demands, particularly can reach the purpose that the heat that increases extensional surface is spreaded transmission.Central authorities at water chestnut cylindricality multilayer film tubular structure 901 have a hollow hole, make that the cylindrical or rectangular secondary cell or the super capacitor that have appropriate size and profile shown in the 2B can directly be placed into wherein as Fig. 1 or Fig. 2 A.The bottom of water chestnut cylindricality multilayer film tubular structure 901 can be the opening shape or seals shape.When secondary cell or high capacitance were placed into water chestnut cylindricality multilayer film tubular structure 901, the temperature of secondary cell or high capacitance rose and can be controlled well.
Figure 10 A and Figure 10 B have shown the embodiment of the another kind of cylindrical multilayer film tubular structure of the present invention.Figure 10 A and Figure 10 B have shown the five-layer structure of the cylindrical multilayer film tubular structure 1001 of PPP, PAP, PMP and PAMAP.As mentioned above, the available different material of each layer of cylindrical multilayer film tubular structure 1001 substituted, and extends fin 1002 and can be added into, and to adapt to different demands, particularly can reach the purpose that the heat that increases extensional surface is spreaded transmission.Make the cylindrical or rectangular secondary cell or the super capacitor that shown in Fig. 1 or Fig. 2 A, 2B, have appropriate size and profile directly to be placed into wherein, and the inside hole of cylindrical multilayer film tubular structure 1001 also can be taked and outside different shapes.And the profile of extending fin 1002 can be according to different demands and correct, and the internal holes in the middle of the cylindrical multilayer film tubular structure 1001 can be designed to square or other required shape.Can at random adjust the size and the profile of extending fin 1002 by coextrusion fabrication schedule of the present invention simultaneously.
Figure 11 A and Figure 11 B are the multilayer film hollow object structure of arbitrary shape.In Figure 11 A, middle hollow hole part 1101 can be placed into the program that does not need any complexity with the secondary cell/high capacitance of its size conforms.Figure 11 A shows that also multi-layer film structure can have different profiles and extension fin 1102 from the inner to the outer.In Figure 11 B, can be placed in the hollow hole 1101 as the required object 1104 of secondary cell or super capacitor.The formed sleeve pipe of this multilayer film hollow object has very sufficient elasticity at the composition of quantity, external form, size and the multilayer film of hollow hole.According to Figure 11 B, wherein shown a kind of preferred implementation of multilayer film sleeve structure, wherein can insert three secondary cells or super capacitor.Shown in Figure 11 B, this structure has comprised three hollow holes, make required object 1104 can be placed in the hollow hole 1101, the multilayer film sleeve pipe fully coats each secondary cell or super capacitor, and can be stored effectively or be shed by the heat energy that secondary cell or super capacitor produced in the charged.Therefore, secondary cell in the running or high capacitance can be maintained at stable and suitable low temperature.
With reference to Figure 12 A and Figure 12 B, Figure 12 A shows single secondary cell/high capacitance and does not have the temperature graph of multi-layer film structure shell of the present invention or sleeve pipe, clearly in Figure 12 A, time/be higher than during the maximum temperature of total discharge time=1 among Figure 12 B time/maximum temperature of total discharge time=1 o'clock.The result as can be known, single secondary cell/super capacitor or plural secondary cell/super capacitor with outside sandwich construction shell or sleeve pipe among the present invention can remain on a lower upper operating temperature.
With reference to Figure 13 A, Figure 13 B and Figure 13 C, whole PPP and PAP multi-layer film structure fabrication schedule have been disclosed.Figure 13 A has shown the composite material processing procedure, and it is used for making plastic layer or adhesion layer, heat conduction particle and the MCPCM particle that has particle in the parent phase resin.Used double screw extruder to carry out the multi-layer film structure fabrication schedule at this, and those skilled in the art can obtain such manufacture easily, therefore omit the narration of thin portion at this.The polymer melt-flow of parent phase resin, heat conduction particle and MCPCM particle are extruded to a cooling device, and then form plastic pellet by comminutor.With reference to Figure 13 B, the mixture particle is added in the coextrusion machine that reaches plural number in the main extruder.The arrangement of main extruder and plural coextrusion machine is the number of plies according to required PPP and PAP structure.For example, in the fabrication schedule of five layers of PAPAP structure, designed plastic layer particle is added in main extruder, the 3rd and the 5th coextrusion machine, designed plastic layer particle is added in main extruder, the 3rd and the 5th coextrusion machine, and designed adhesion layer particle is added in the second and the 4th coextrusion machine.By the coextrusion of main extruder and four coextrusion machines, the structure of five tunics/thin slice can be finished according to macromolecule coextrusion program of the prior art, and the operation sequence of thin portion does not repeat them here.With reference to Figure 13 C, the multilayer film hollow object can be by the extruder manufacturing of plural number, about exclusion sleeve, die size and stretching device, the operation of thin portion and the device of all coextrusion processing procedures is that those skilled in the art can carry out easily and obtain, so carefully the operation sequence of portion will repeat no more.
With reference to Figure 14 A, Figure 14 B, Figure 14 C, disclosed the global procedures of making PMP and PAMAP multi-layer film structure.With reference to Figure 14 A and Figure 14 C, shown the block flow diagram of the fabrication schedule of metal level in PMP and PAMAP.Metal forming/thin slice/band is by surface treatment, grinding, sandblast, cleaning and drying process.After the surface preparation step, treated metal forming/thin slice/band will be curled to form curling metal forming/thin slice/band.In follow-up cell operation, shown in Figure 14 B and Figure 14 D, the metal forming/thin slice that is curled/band will and/or extrusion coatedly combine or form the stratiform thing with plastic layer and adhesion layer by coextrusion.For example, shown in Figure 14 B, the metal forming/thin slice/band that curls is follow-up extrusion coated to receive by suspending roller, corona discharge and heater in midair.Designed plastic layer and adhesion layer are coated on the both sides of metal forming/thin slice respectively, and form required PMP and PAMAP multilayer film/thin slice.Above-mentioned processing procedure is common macromolecule fabrication schedule, and for those skilled in the art can carry out easily, the operation sequence of thin portion will repeat no more.
Embodiment 1
With reference to Figure 11 A, this figure has disclosed a kind of embodiment of preferable multilayer film sleeve pipe.The MAP loop pipe sleeve pipe that is used for 18650 lithium rechargeable batteries/super capacitor has comprised three kinds of different layers.The thickness that internal layer has comprised aluminium-magnesium (Al-Mg) metal alloy and its layer is 0.3mm.Extending fin length is that 2.5mm and width are 1.0mm.And the distance of extending the fin edge is 2.0mm.The coefficient of heat conduction of metal alloy layer is 200Wm
-1K
-1, and the inside diameter of metal level (hollow hole diameter) is 21mm.Middle adhesion layer is made of ADMER QF551E (40%), aluminium nitride (59.9%) and CNT (carbon nano-tube) (0.1%).The thickness of middle adhesion layer is 50 microns, and the coefficient of heat conduction is 10Wm
-1K
-1Outer plastic layer is made of polyethylene (PE) (40%), aluminium nitride (10%) and MCPCM 43D.Wherein thickness is 3mm, and the length of extending fin is 2.0mm, and width is 1.0mm.Distance between each fin is 2.0mm.The coefficient of heat conduction of outer plastic layer is 10Wm
-1K
-1(the hot-fluid method for measurement that ASTM F433 is adopted), and be 70KJKg at the latent heat of 43 ℃ of fusions
-1(measured by differential scanning calorimeter Perkin-Elmer DSC-7 (USA), the DSC-7 dynamic software be installed).The conductive adhesive layer that is brushed then is to be made of DX 2000 resins (40%), aluminium nitride (59.9%) and CNT (carbon nano-tube) (0.1%).PAMAP multilayer film pipe is by coextrusion coating process made.And it is the following step that sleeve pipe is made processing procedure: the first step is to cut the multilayer film pipe of manufacturing to desired size (be cylindrical 18650 lithium rechargeable batteries/super capacitor in this example, required length is 65mm).Second step was the surface of coating conductive adhesive layer to cylindrical 18650 lithium rechargeable batteries/super capacitor, and the 3rd step is for to insert cylindrical 18650 lithium rechargeable batteries/super capacitor in the hollow hole of sleeve pipe.Behind above-mentioned processing procedure, secondary cell/super capacitor can be controlled at preferable temperature range by multilayer film sleeve pipe of the present invention.
Embodiment 2
With reference to Fig. 9 B, embodiment 2 is a kind of embodiment of preferable PPP multilayer film square casing, and it is used for as the heat management sleeve pipe that has the aftermentioned bedded structure and be configured as square lithium ion secondary battery/super capacitor.The parent phase resin is EVA co-polymer (DuPontTM
CM555), account for 35% of total weight.Decentralized photo comprises the MPCM 43D (average grain diameter is that 10～20 microns and phase change temperature are 43 ℃) of 10% aluminium nitride (the aluminium nitride average grain diameter is 10 to 20 microns) and 55%.The width of the size in inner hollow hole is 10mm, and length is 100mm.The thickness of layer is 8mm.Outer surface has comprised several and has prolonged the matrix of fin, and wherein the length of fin extensional surface is 2.5mm, and fin width is 1.0mm, and the distance between the adjacent fin edge is 2.0mm.The measured coefficient of heat conduction is 0.4Wm
-1K
-1(the hot-fluid method for measurement that ASTM F433 is adopted), and be 90KJKg at the latent heat of 43 ℃ of fusions
-1(measured by differential scanning calorimeter Perkin-Elmer DSC-7 (USA), the DSC-7 dynamic software be installed).
Embodiment 3
With reference to Fig. 8 A, embodiment 3 is a kind of embodiment of preferable PPP multilayer film plane lamina, and it is used for as the heat management sleeve pipe that has the aftermentioned bedded structure and be configured as square lithium ion secondary battery/super capacitor.Internal layer (or ground floor) is a plastic layer, is made of polyethylene (PE) (35%), hexahedron boron nitride (h-BN) (64.9%) (obtained by Momentive Performance Materials Inc.) and CNT (0.1%).And the average thickness of its layer is 50 microns.Interlayer (intermediate layer) is an adhesion layer, is to be made of BYNEL 21E533 (40%), hexahedron boron nitride (h-BN) (64.9%) (obtained by MomentivePerformance Materials Inc.) and CNT (carbon nano-tube) (0.1%).Wherein outer thickness is 30 microns.Outer (or the 3rd layer) is made of plastic layer, has 35% polybutyl terapthalate (PBT), 15% hexahedron boron nitride (h-BN) and 40% MPCM 43D.Its average film thickness is 2.5mm.The evenly heat conductivity of three layers of thin slice is 1.0Wm
-1K
-1At 43 ℃ fusion latent heat is 85KJKg
-1
With reference to Figure 10 A, embodiment 4 is a kind of embodiment of hollow tube of preferable PAMAP five tunics, and it is used for as the heat management sleeve pipe that has the aftermentioned bedded structure and be configured as 18650 cylindrical lithium ion secondary batteries/super capacitor.Internal layer (or ground floor) is a plastic layer, be made of polybutyl terapthalate (PBT) (40%), aluminium nitride (60%), and the average thickness of its layer is 50 microns.Interlayer (intermediate layer) is an adhesion layer, is to be made of BYNEL 21E533 (40%), aluminium nitride (59.9%) and CNT (carbon nano-tube) (0.1%).Wherein outer thickness is 30 microns.The 3rd layer is made of the steel layer, and the average thickness of its layer is 100 microns.The 4th layer is adhesion layer, have 40% ADMER NF408E, 59.9% aluminium nitride and 0.1% CNT (carbon nano-tube), and its thickness is 30 microns.Layer 5 is a plastic layer, wherein is made of polyethylene (PE) (40%), aluminium nitride (10%) and MCPCM43D (50%), and the average thickness of its layer is 3mm.The inside diameter of hollow tube is 18mm.And the evenly heat conductivity of the hollow tube of five tunics is 1.0Wm
-1K
-1At 43 ℃ fusion latent heat is 85KJKg
-1
Embodiment 5
Embodiment 5 is a kind of embodiment of square hollow tube of preferable MAP trilamellar membrane, and it is used for as the heat management sleeve pipe that has the aftermentioned bedded structure and be configured as 18650 square lithium ion secondary batteries/super capacitor.Internal layer (or ground floor) is a steel layer, and the average thickness of this layer is 100 microns.The second layer (intermediate layer) is an adhesion layer, is to be made of ADMER NF408E (40%), aluminium nitride (59.9%) and CNT (carbon nano-tube) (0.1%).Wherein thickness is 50 microns.The 3rd layer is a plastic layer, wherein is made of polyethylene (PE) (40%), aluminium nitride (10%) and MCPCM43D (50%), and the average thickness of its layer is 3mm, and forms the fin that extends at the 3rd layer outer surface.
Embodiment 6
Embodiment 6 is a kind of embodiment of preferable PAMAP ring-type hollow tube, and it is used for as the heat management sleeve pipe that has the aftermentioned bedded structure and be configured as 18650 cylindrical lithium ion secondary batteries/super capacitor.The thickness that internal layer (ground floor) has comprised aluminium-magnesium (Al-Mg) metal alloy and its layer is 0.3mm.The second layer (intermediate layer) is an adhesion layer, is to be made of ADMER NF408E (40%), aluminium nitride (59.9%) and CNT (carbon nano-tube) (0.1%).Wherein thickness is 50 microns.The 3rd layer is a plastic layer, wherein is made of polyethylene (PE) (40%), aluminium nitride (10%) and MCPCM43D (50%), and the average thickness of its layer is 3mm, and forms the fin that extends at inner ground floor.
When some embodiment when describing as said method, should will be understood that those embodiment example only of the present invention as an illustration.Therefore, apparatus and method described herein are not the content that only is subject to the above embodiments and is disclosed.In addition, apparatus and method described herein should only can come claim is defined with reference to foregoing invention explanation and Figure of description content.
Claims (20)
1. heat management multilayer film/thin slice that is used for secondary cell and super capacitor comprises:
The heat conduction particle of plural number;
The particulate coated phase-change formed material particle of plural number; And
At least the plastic layer of one deck, wherein above-mentioned plural heat conduction particle and plural particulate coated phase-change formed material particle are scattered in this plastic layer equably;
Wherein this plastic layer forms lamina multilayer film/flake structure, and when this plastic layer surpassed the situation of one deck, this plastic layer was overlapping in regular turn each other.
2. heat management multilayer film/thin slice as claimed in claim 1, wherein plastic layer comprises any mixture of polyethylene, polyethylene and ethylene copolymers, polyamide, ethene and ethenol copolymer, ethylene-vinyl acetate copolymer, polypropylene, high density polyethylene (HDPE), low density polyethylene (LDPE), LLDPE or above-mentioned polymer.
3. heat management multilayer film/thin slice as claimed in claim 1, wherein at least one metal level optionally lamination and form lamina multilayer film/flake structure in arbitrary of this plastic layer.
4. heat management multilayer film/thin slice as claimed in claim 3, wherein this metal level comprises the alloy of nickel, copper, tungsten, molybdenum, aluminium, steel, silver, gold or other above-mentioned metal.
5. heat management multilayer film/thin slice as claimed in claim 2, wherein at least one adhesion layer optionally lamination in arbitrary of this plastic layer, and form lamina multilayer film/flake structure, and above-mentioned plural heat conduction particle and plural particulate coated phase-change formed material particle are scattered in this adhesion layer equably.
6. heat management multilayer film/thin slice as claimed in claim 4, wherein at least one adhesion layer optionally lamination in arbitrary of this plastic layer or metal level, and form lamina multilayer film/flake structure, and above-mentioned plural heat conduction particle and plural particulate coated phase-change formed material particle are scattered in this adhesion layer equably.
7. as claim 5 or 6 described heat management multilayer film/thin slices, wherein this adhesion layer comprises alkyl ester copolymer, Arrcostab or polyolefin and any mixture thereof.
8. heat management multilayer film/thin slice as claimed in claim 6, wherein the heat conduction particle comprises the copper powder, silver, nickel, aluminium, copper, glass putty, alloying metal powder, hydride-dehydrogenation titanium valve, stainless steel powder, powdered graphite, carbon black powder, CNT (carbon nano-tube), diamond powder, nano metal powder, ball-aluminium oxide powder that are coated with silver, ultra-finely causes the ball-aluminium oxide powder or as the non-oxidized substance powder of hexahedron boron nitride powder, and the sintered body of any mixture of above-mentioned particle.
9. heat management multilayer film/thin slice as claimed in claim 8, wherein phase-transition material is moisture salt, paraffin or alkene.
10. heat management multilayer film/thin slice as claimed in claim 9, wherein the diameter of this heat conduction particle and particulate coated phase-change formed material particle is 500 microns to 1 micron.
11. as claim 5 or 6 described heat management multilayer film/thin slices, wherein arbitrary layer thickness is between 250 microns to 0.05 micron.
12. heat management multilayer film/thin slice as claimed in claim 1, wherein multilayer film/flake structure is to use the method for coextrusion or coating coextrusion to form.
13. as claim 5 or 6 described heat management multilayer film/thin slices, wherein the surface of this lamina multilayer film/flake structure further comprises the plural number extension fin identical with outer surface plastic layer material.
14. a heat management multilayer hollow object that is used for secondary cell and super capacitor comprises:
The heat conduction particle of plural number;
The particulate coated phase-change formed material particle of plural number; And
At least the plastic layer of one deck, wherein above-mentioned plural heat conduction particle and plural particulate coated phase-change formed material particle are scattered in this plastic layer equably;
Wherein this plastic layer forms the stereochemical structure of cylindrical, square or other shape of one deck at least, wherein at least one hollow hole passes the two ends of the central part of this stereochemical structure, and the main body of the stereochemical structure of this cylindrical, square or other shape is become by the plastic layer of one deck at least.
15. heat management multilayer hollow object as claimed in claim 14, wherein at least one metal level optionally lamination and form lamina multilayer hollow object in arbitrary of this plastic layer.
16. heat management multilayer hollow object as claimed in claim 14, wherein at least one adhesion layer optionally lamination in arbitrary of this plastic layer, and form lamina multilayer hollow object, and above-mentioned plural heat conduction particle and plural particulate coated phase-change formed material particle are scattered in this adhesion layer equably.
17. heat management multilayer hollow object as claimed in claim 15, wherein at least one adhesion layer is optionally coated arbitrary of this plastic layer, and form lamina multilayer hollow object, and above-mentioned plural heat conduction particle and plural particulate coated phase-change formed material particle are scattered in this adhesion layer equably.
18. heat management multilayer hollow object as claimed in claim 17, wherein arbitrary layer of this lamina multilayer hollow object further comprises plural number extension fin.
19. heat management multilayer hollow object as claimed in claim 17, wherein this hollow hole is used for inserting cylindrical lithium ion secondary battery, square lithium ion secondary battery or super capacitor.
20. heat management multilayer hollow object as claimed in claim 14, wherein this lamina multilayer hollow object is to use the method for coextrusion or coating coextrusion to form.
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| CN103228120A (en) * | 2012-01-31 | 2013-07-31 | 曼埃利康有限公司 | Heat radiation sheet |
| CN103725019A (en) * | 2012-10-16 | 2014-04-16 | 神讯电脑(昆山)有限公司 | Heat dissipating material and preparation method thereof |
| CN104952700A (en) * | 2014-03-28 | 2015-09-30 | 古德里奇公司 | Peak temperature attenuation film |
| CN106025192A (en) * | 2015-03-27 | 2016-10-12 | Tdk株式会社 | Positive electrode active material, positive electrode using same, and lithium ion secondary battery |
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| CN104952700B (en) * | 2014-03-28 | 2019-01-08 | 古德里奇公司 | Peak temperature decaying film |
| CN106025192A (en) * | 2015-03-27 | 2016-10-12 | Tdk株式会社 | Positive electrode active material, positive electrode using same, and lithium ion secondary battery |
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| CN106900092A (en) * | 2017-01-13 | 2017-06-27 | 季文广 | A kind of self limiting temperature floor heating electricity consumption turns hot heating plant |
| CN106654343A (en) * | 2017-01-17 | 2017-05-10 | 华霆（合肥）动力技术有限公司 | Cable core sleeve as well as preparation method thereof, and cable core device |
| CN107749499A (en) * | 2017-09-15 | 2018-03-02 | 福建翔丰华新能源材料有限公司 | Application of the nano TiN as the additive for improving full battery heat dispersion |
| CN111162489A (en) * | 2019-12-25 | 2020-05-15 | 奇瑞汽车股份有限公司 | Wire harness heat dissipation pipe sleeve |
| CN111162489B (en) * | 2019-12-25 | 2021-05-28 | 奇瑞汽车股份有限公司 | Wire harness heat dissipation pipe sleeve |
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