CN100483831C - Bipolar electrode batteries and methods of manufacturing bipolar electrode batteries - Google Patents
Bipolar electrode batteries and methods of manufacturing bipolar electrode batteries Download PDFInfo
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- CN100483831C CN100483831C CNB2005800009240A CN200580000924A CN100483831C CN 100483831 C CN100483831 C CN 100483831C CN B2005800009240 A CNB2005800009240 A CN B2005800009240A CN 200580000924 A CN200580000924 A CN 200580000924A CN 100483831 C CN100483831 C CN 100483831C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The disclosure relates to bipolar cells including electrodes surrounding a collector. Embodiments of the bipolar cells include a collector containing a highpolymer material. The disclosure also relates to bipolar electrode batteries containing bipolar cells including a collector body containing electrically conductive highpolymer or electrically conductive particles distributed in a high-polymer. By adding such high molecular weight polymer material to the collector, the weight of the collector may be reduced and the output power density per weight of the battery may be improved. The disclosure further relates to methods of forming collecting bodies and electrodes for bipolar cells using an inkjet printing method. Bipolar cells according to the present invention may be used to fabricate batteries such as lithium ion batteries, which may be connected to form battery modules used, for example, to provide electrical power for a motor vehicle.
Description
The application requires the priority of Japanese patent application 2004-354526 that submitted on December 7th, 2004 and the Japanese patent application 2005-315147 that submitted on October 28th, 2005, and the full content that is incorporated herein these two applications as a reference.
Technical field
The present invention relates to the electrical power storage system, more specifically, the present invention relates to the bipolar electrode storage battery.
Background technology
Recently in order to protect environment, pursue the global emissions that reduces carbon dioxide all the time.In auto industry, by introducing, and actively make great efforts the CO2 emissions of reduction internal combustion engine by electric motor driven electric motor car (EV) and hybrid electric vehicle (HEV).Recently, this has produced progress in the exploitation of the low secondary cell (secondary storage batteries) of the light weight that is used for driving motivation and cost.
Although some secondary cell (for example lithium ion battery) can obtain high-energy-density and high-output power density, require polyphone to connect a plurality of batteries usually, so that obtain enough big power output, drive electric motor car.Yet when connecting battery by external electric link (for example outside lead) polyphone, power output is owing to the resistance of external electric link is lowered.In addition, the battery with external electric link spatially is disadvantageous.In other words, because the length of external electric link, the output power density of battery and energy density reduce, and the overall operation efficient of electric motor car reduces owing to the weight of external electric link.
In order to address this problem, developed bipolar cell (bipolar cell), wherein anodal (that is cathode type) active material and negative pole are (promptly, the anode type) active material be arranged on the two opposite side surfaces of collector body (referring to, for example day disclosure is examined patent application 2004-95400).A plurality of bipolar cell internal electrical can be connected together, form secondary battery module (module) (that is bipolar electrode battery pack (bipolarelectrode battery)).Known good electrical properties and the desirable physical property of demonstrating of this bipolar electrode battery pack, for example w/v is low, the cross section is thin and when operation and charging dissipation of heat speed good.
Because auto industry has adopted this bipolar electrode battery pack rapidly, might improve the output power density and the energy density of automotive battery.Yet, also continue to pursue the battery performance of further improvement bipolar cell.
Summary of the invention
In general, the present invention relates to bipolar cell.For example, an execution mode of bipolar cell described herein comprises electrode, and is arranged in the dielectric substrate between the electrode, and described electrode is made up of collector body, the negative pole that is electrically connected to the anodal of collector body one side and is electrically connected to the collector body opposite side.In some embodiments, collector body contains high polymer material.
In other embodiments, bipolar cell of the present invention can be used to make secondary cell, for example lithium ion battery.This battery can be used for providing electric energy to electric motor car, particularly provides energy to motor, to be used for driving electric motor car.Particularly, bipolar cell of the present invention can be joined together to form battery pack, and this battery pack can further be joined together to form the battery module that for example is used as power sources of motor vehicle.
Other execution mode of the present invention provides the method for making bipolar cell, can comprise by using the collector body China ink (ink) that the ink jet printing method deposition contains polymeric material to form collector body.As a kind of example, the method for making bipolar cell comprises: use ink jet printing method to deposit the collector body China ink that contains high polymer material from the teeth outwards, form collector body; Use ink jet printing method to deposit the negative electrode China ink that contains the cathode type active material from the teeth outwards, form negative electrode.This method further comprises by using ink jet printing method to deposit the anode ink that contains anode type active material from the teeth outwards, forms anode.
One or more execution modes of the present invention are shown in following accompanying drawing and the description.From this description, accompanying drawing and claim, further feature of the present invention, purpose and advantage will be tangible.
Description of drawings
Fig. 1 is the collector body side cross-sectional view that comprises high polymer material, and this collector body is arranged in the bipolar cell of the bipolar electrode battery pack of one embodiment of the present invention.
Fig. 2 A shows that for the side cross-sectional view of the bipolar cell of bipolar electrode battery pack conceptually is described electric current flows into the collector body that comprises high polymer material of one embodiment of the present invention.
Fig. 2 B shows that for the side cross-sectional view of the bipolar cell of bipolar electrode battery pack conceptually is described electric current flows into the collector body that comprises high polymer material of another embodiment of the present invention..
Fig. 3 is the perspective view of the bipolar electrode battery pack of another execution mode of the present invention.
Fig. 4 A is the top view of the secondary battery module of assembling, and this battery module comprises the bipolar electrode battery pack of a plurality of another execution modes of the present invention.
Fig. 4 B is the end view of the secondary battery module of assembling, and this battery module comprises the bipolar electrode battery pack of a plurality of another execution modes of the present invention.
Fig. 4 C is the end-view of the secondary battery module of assembling, and this battery module comprises the bipolar electrode battery pack of a plurality of another execution modes of the present invention.
Fig. 5 is the side cross-sectional view of motor vehicle that is equipped with the secondary battery module of assembling, and this battery module comprises the bipolar electrode battery pack of a plurality of another execution modes of the present invention.
Detailed Description Of The Invention
Embodiments of the present invention provide the bipolar electrode battery pack, and it comprises electrode, and described electrode is made up of collector body, the negative electrode (positive pole) that is electrically connected to collector body one side, the anode (negative pole) that is electrically connected to the collector body opposite side; Form with dielectric substrate around negative electrode and anode.As following further detailed description, the execution mode of bipolar electrode battery pack can comprise the current collection main body (collectingbody) that contains high polymer material.
Fig. 1 is the concept map of the structure of explanation bipolar electrode battery pack.The bipolar electrode battery pack has following structure, wherein collector body 10 (current collector or electric current current collection main body), anodal 20, dielectric substrate 30, negative pole 40 and current draw plate (extracting plate) 11 are laminated together, are placed on collector body 10 between the battery pack that polyphone each other connects not only as positive electrode collector but also as negative electrode collector.
Conventionally, the collector body of bipolar electrode battery pack is made by metal forming (for example aluminium foil and Copper Foil) usually.Yet embodiments of the present invention are used the collector body that contains high polymer material.
Battery pack commonly used is not the bipolar electrode battery pack, in the collector body of battery pack commonly used, electric charge is transmitted through the plate that is placed on the collector body marginal portion, and collector body has in plate the effect of collecting the electric charge that produces in the negative pole, perhaps has the effect from the charge transport of Plate supplying to positive pole.Therefore, the resistance of the collector body that the horizontal direction (surface direction) that moves through at electric charge upward produces must be low, and in order to reduce the resistance on the horizontal direction, use the metal forming with specific thicknesses.As a result, increased battery weight.
On the other hand, in the collector body 10 of bipolar electrode battery pack, the electric charge that produces in the negative pole 40 directly is fed to the positive pole 20 that is present on collector body 10 opposite sides.Therefore, electric current flows along the direction of laminate layers, and does not need along continuous straight runs to flow, and this laminate layers is the structural detail of bipolar electrode battery pack.Thereby the metal forming of using in conventional batteries in order to reduce the resistance on the horizontal direction is unnecessary.And because the resistance on the horizontal direction can be higher, the thickness of collector body can be thinner.
The preferred metallic plate (that is, electrode extracts plate) that uses contact collector body surface result supports collector body.The surface of collector body can contact with the surface electrical of metallic plate, and electric current flows to outside lead from collector body through metallic plate thus, and outside lead connects electric device (for example motor).Yet metallic plate does not need to contact with the collector body surface physics, but can selectively be electrically connected to the side of collector body, reduces contact resistance thus.
By from comprising the material preparation collector body 10 of high polymer material, the weight of scalable collector body and improve the energy density of bipolar electrode battery pack, and do not reduce battery performance.
Fig. 2 A and Fig. 2 B are side cross-sectional view, and the electric current of the collector body 10 that flows into bipolar electrode battery pack of the present invention has been described.Collector body 10 can comprise conductive particle 50 (shown in Fig. 2 B), and this conductive particle has high adherence to high polymer material 60; Or comprise conduction high polymer material curtain coating body (cast), as film 71 (shown in Fig. 2 A).Shown in Fig. 2 A and 2B, electric current flows through collector body 10 from an electrode with vertical direction, reaches another electrode, and the conductivity of vertical direction is provided by conductive particle 50 or conduction high polymer film 71.Thus, can reduce the quality of collector body 10.
When collector body contained the high polymer material with conductivity, conductive particle (it is also referred to as conductive particle) can join in the high polymer material, to improve its conductivity.Conductive particle can be selected from the material with ionic conductivity when as the charge transfer medium.And conductive particle can be selected from the material that can bear the high potential of spraying (apply) on anodal and the negative material.
Suitable conductive particle can comprise alumina particles, SUS (stainless steel) particle, carbon granule, silver-colored particle, gold grain, copper particle and titanium particle, but this material is not limited to these certain materials, can use other material and metal alloy.The form of conductive particle is not limited to previously described particle.Particularly, carbon nanotube particulate is available, and also can use granular conductive resin composition.
The distribution of conductive particle in collector body can be inhomogeneous.The distribution of particle in collector body can change.Can use multiple conductive particle, perhaps can change the distribution of conductive particle in collector body.For example, can in the parts of contact positive pole and in the parts of contact negative pole, use different required conductive particles.
The preferred embodiment that is used for anodal conductive particle can comprise alumina particles, SUS particle and carbon granule, and more preferably uses carbon granule.The example that is used for the conductive particle of negative pole can comprise silver-colored particle, gold grain, copper particle, titanium particle, SUS particle and carbon granule, more preferably uses carbon granule.
Carbon granule, for example carbon black and graphite have the voltage range (voltage window) of non-constant width, all are stable for anodal and negative pole in very large range, and have excellent conductivity.And, because the weight of carbon granule is very light, can further reduce battery quality by using the conductivity carbon granule, this is opposite with use conductive gold metal particles.In addition, because,, make contact resistance very low owing to they are manufactured from the same material if carbon granule contacts with this type of conductive additive usually with the additive of carbon granule as the intensifier electrode conductivity.When by during as conductive particle, reducing electrolytical mixing, make electrolyte be difficult to penetrate into the space of collector body thus at carbon surface deposition hydrophobicity handled thing and with carbon granule.
According to the present invention, collector body contains high polymer material that conductive particle is bonded together (below be called ＂ adhesive ＂).By using the structural material of adhesive, can increase the adhesiveness of conductive particle, and strengthen the reliability of battery as collector body.Adhesive can be selected from the material that can bear the high potential that sprays to anodal and negative pole.
The distribution of adhesive in collector body can be inhomogeneous.The distribution of adhesive in collector body can change.Multiple adhesive can be used, and the distribution of adhesive in collector body can be changed.For example can in the parts of contact positive pole with in the parts that contact negative pole, use different required adhesives.
Suitable bonding can comprise heavy polymer (that is high polymer) for example polyethylene (PE), polypropylene (PP), PETG (PET), polyethers nitrile (PEN), polyimides (PI), polyamide (PA), polytetrafluoroethylene (PTFE), styrene butadiene rubbers (SBR), polyacrylonitrile (PAN), poly-(methyl) acrylate (PMA), poly-(methyl) methyl acrylate (PMMA), polyvinyl chloride (PVC), polyvinylidene fluoride (PVdF) or its mixture.These materials have significantly big voltage range, all are stable for anodal and negative pole in scope widely, and can increase adhesiveness.
And, by using the key component of high polymer material, can reduce the deposition problems of metal on metal forming as the collector body main body.More preferably, polyvinylidene fluoride is as adhesive.Because polyvinylidene fluoride has high durability and chemical resistance, therefore it can increase the adhesiveness of two kinds of electrodes usually as the adhesive of two kinds of electrodes.As required, collector body can contain other material.
The ratio of adhesive and conductive particle is not particularly limited in the collector body, but preferably, should have the conductive particle of 2-20% quality in whole adhesives and the conductive particle.By having the conductive particle of q.s, can guarantee the conductivity of collector body.
The voidage of collector body is preferably 15% or lower.By keeping the low voidage of collector body, can prevent that electrolyte from penetrating collector body, and increase its durability.Can regulate voidage by the amount that control is used to produce the solvent of collector body.By increasing the amount of solvent, can increase voidage, by reducing the amount of solvent, can reduce voidage simultaneously.The lower limit of voidage is not particularly limited, but when considering to reduce the weight of collector body, preferred 5% or bigger.
The thickness of collector body is not limited to concrete size, but preferred enough thin so that increase the power output density of battery.As mentioned above, in the bipolar electrode battery pack, be present between positive pole and the negative pole collector body can with the direction of laminate layers level on have high resistance.Therefore, can reduce the thickness of collector body.In fact, the thickness of collector body is preferably the 0.1-15 micron.When manufacturing approaches collector body, preferably use following ink jet printing method herein.
Structure anodal and negative pole is not particularly limited.Can use known positive pole and negative pole.Positive pole contains positive active material and negative pole contains negative electrode active material.Anodal and negative electrode active material can be selected according to cell types.
For example, when battery was lithium rechargeable battery, the material that is suitable for use as positive active material can comprise for example LiCoO of Li-Co family composite oxides
2, Li-Ni family composite oxides are LiNiO for example
2, Li-Mn family composite oxides are spinelle LiMn for example
2O
4With Li-Fe family composite oxides LiFeO for example
2Suitable material can comprise the phosphate compounds that contains lithium and transition metal, for example LiFePO
4, the sulphation compound, transistion metal compound is V for example
2O
5, MnO
2, TiS
2, MOS
2And MoO
3, sulfide, PbO
2, AgO, NiOOH or the like.Also can use two or more combination and the mixture in these materials, to make positive pole.
The examples of materials that is suitable for making negative pole can comprise material with carbon element, for example crystalline carbon material and agraphitic carbon material, and metal material, for example Li
4Ti
5O
12In fact, they can comprise native graphite (balck lead), electrographite, carbon black, activated carbon, carbon fiber, coke, soft black, hard carbon black or the like.Also can use in these materials two or more combination and mixture to make negative pole.
Electrode can contain other element, for example conductive additive, ionic conduction high polymer and assisted electrolysis matter salt (supporting electrolyte salt).The example of suitable conductive additive can comprise acetylene black, carbon black and graphite.By adding conductive additive, can increase the conductivity of the electronics that produces in the electrode, and can improve battery performance.The example of suitable ionic conduction high polymer can comprise poly(ethylene oxide) (PEO), PPOX (PPO) or the like.Can select assisted electrolysis matter salt based on cell types.When battery was lithium ion battery, the example of suitable assisted electrolysis matter salt can comprise LiBF
4, LiPF
6, Li (SO
2CF
3)
2N, LiN (SO
2C
2F
5)
2Or the like.Also can use two or more combination and mixture of these materials.
According to the required purposes (for example whether emphasize power output or do not emphasize energy or the like) of battery and the ionic conductivity in the dielectric substrate, preferably be identified for making the mixing ratio and the amount of the structural material (comprising active material, lithium salts and conductive additive) of electrode.
Dielectric substrate can be liquid phase, gel and/or solid phase.Safety factor when considering cell fracture and prevent leak of liquid, dielectric substrate is gel polymer electrolyte layer or total solids dielectric substrate preferably.By using the gel polymer electrolyte layer as electrolyte, eliminated electrolytical flowability, prevented that electrolyte leakage from entering collector body, and can stop the ionic conduction between each layer.The example of the main polymer of gel polymer electrolyte can comprise PEO, PPO, PVdF, polyvinylidene fluoride-hexafluoropropylene copolymer (PVdF-HFP), PAN, PMA and PMMA.Usually the electrolyte that is applicable to lithium ion battery can be as the fluid electrolyte in the main polymer of gel polymer electrolyte.
In addition, when total solids dielectric substrate (all-solid electrolyte layer) is used as electrolyte, can prevent that electrolyte leakage from entering in the collector body, can stop the ionic conduction between each layer, this is to flow because suppressed electrolytical.When using the total solids dielectric substrate, because electrolyte does not need to penetrate collector body from dielectric substrate, so the voidage of collector body is uprised.
Can make the example gel polymer dielectric in the fully solid high polymeric solution (for example aqueous solution of PEO and/or PPO) by electrolyte (for example being generally used for the electrolyte of conventional lithium battery) is added.Also can make gel polymer electrolyte by mixed electrolytic solution and superpolymer adhesive (for example PVDF, PAN and the PMMA) solution that does not have lithium ion conductive basically.Constituting the high polymer of gel polymer electrolyte and the ratio of electrolyte is not particularly limited.The concentration range of high polymer can be 0-100 weight %.Similarly, the concentration range of electrolyte in electrolyte can be 0-100 weight %.In addition, the total solids electrolyte can comprise the additive agent electrolyte that has some lithium ion conductivities at least, the superpolymer adhesive of for example confirming previously, inoganic solids and conductive particle.
In order to strengthen ionic conductivity, preferably in dielectric substrate, contain auxiliary salt.When battery is lithium rechargeable battery, can use LiBF
4, LiPF
6, LiN (SO
2CF
3)
2, LiN (SO
2O
2F
5)
2Or its mixture is as auxiliary salt.Yet the auxiliary salt that can use in the present invention is not restricted to these specific lithium salts.As mentioned above, polyalkylene oxide family high polymer, for example PEO and PPO can dissolve for example LiBF of lithium salts
4, LiPF
6, LiN (SO
2CF
3)
2And LiN (SO
2O
2F
5)
2With can be suitable for as auxiliary salt.And, by in dielectric substrate, producing cross-linked structure, can obtain bipolar electrode battery pile (bipolarelectrode cell stack).
Can be electrically connected a plurality of battery pack, a plurality of battery pack or the polyphone and in parallelly be electrically connected a plurality of battery pack and make the battery module (assemblied batterymodule) of assembling simultaneously of being electrically connected in parallel by polyphone.By polyphone or the battery that is connected in parallel, the freely memory capacity of regulating cell and voltage.Number and the method that is connected them of battery can be determined based on the output of battery power demand and capacity in the battery module of assembling.When constructing the battery module of assembling, for single battery, the fail safe of battery increases.Battery module by the structure assembling can reduce the adverse effect of an element cell (unit cell) for entire cell.
The battery module of battery or assembling can be preferably used as the power supply of powered vehicle.When the battery module of battery of the present invention or assembling is used for hybrid electric vehicle or electric motor car, can improve the life-span and the reliability of vehicle and power supply thereof.Yet the use of battery of the present invention and battery module is not limited to vehicle, can for example use battery and battery module in other device of electric train or a large amount of electric energy of any needs.
The whole bag of tricks of preparation bipolar electrode battery pack of the present invention is described now.Can use cladding process, to make the collector body of making by adhesive and conductive particle.For example, in fact can use any painting method, wherein preparation contains the slurry of adhesive and conductive particle, applies and curing.Operable exemplary painting method comprises that forward roller coating and inverse roller coating, notch board apply, curtain is coated with, extrusion mould-outlet applies (extrusion die coating), spraying, silk screen printing or the like.Be suitable for preparing suitable bonding (high polymer material) and the conductive particle that applies slurry because the front has been described, describe these materials no longer in addition.
Although can make collector body by using painting method, in this example, contain the collector body China ink of collector body structural element by preparation, preferably use ink jet printing manufactured collector body.By using ink jet printing method, can make collector body with uniform thickness.And, when using ink jet printing method, can make thin collector body.Therefore, can improve the energy density of battery.In ink jet printing method, can spray the China ink that contains all structural elements, perhaps spray the multiple inks that contains various elements.When spraying multiple inks, be easy to prepare in proportion each element.
Ink jet printing method is following print process: liquid ink ejects from nozzle, and China ink is attached on the object.Depend on the mode that China ink sprays, ink jet printing method is divided into the piezoelectric ink jet print process, hot ink jet printing method and Bubble Jet (registered trade mark) method.The piezoelectric ink jet print process is following method: from the nozzle ejection China ink, this printhead arrangement is out of shape when electric current flows in the bottom, black chamber that stores China ink because the piezoelectricity print head element is out of shape.Hot ink jet printing method is following method: the energy that breaks out of the water vapour that produces when by heater heats and evaporation China ink sprays China ink.As hot ink jet printing method, BubbleJet
TM(Canon Corp., the registered trade mark of Tokyo Japan) method is following method: the energy of the water vapour that produces when the evaporation China ink sprays China ink.Although the heater block difference, hot ink jet printing method and theBubble Jet
TMMethod has identical basic printed element.When by ink jet printing manufactured collector body, can make thin collector body effectively with uniform thickness.
Can pass through ink jet printing method, make electrode by the preparation electrode ink.Preferably, make the bipolar electrode battery pack by following method, this method comprises: by ink jet printing method, deposition contains the step of the collector body China ink generation collector electrode of conductive particle; By ink jet printing method, the anodal China ink that contains positive active material by deposition produces anodal step; With by ink jet printing method, the negative pole China ink that deposition contains negative electrode active material produces the step of negative pole.When using ink jet printing method, when containing the China ink formation electrode of electrode material (for example active material or additional conductive bulk material), can make extremely thin electrode with uniform thickness by deposition.Ink jet printing method can not only be used to make collector body and electrode, and can make solid electrolyte layer.
To describe below and use ink jet printing method, make the method for bipolar electrode battery pack with solid electrolyte layer.Yet the present invention is not limited to following form.When using ink jet printing manufactured bipolar electrode battery pack, preparation collector body China ink, anodal China ink, negative pole is black and electrolyte ink, and uses ink discharge device to spray China ink.
The component that contains in the collector body China ink can comprise adhesive, conductive particle and solvent.The actual form of adhesive and conductive particle as mentioned above.
The component that contains in anodal China ink can comprise positive active material, adhesive, conductive additive and solvent.Anodal China ink can be single type or a plurality of type.The example of adhesive can comprise polyethylene (PE), polypropylene (PP), PETG (PET), polyethers nitrile (PEN), polyimides (PI), polyamide (PA), polytetrafluoroethylene (PTFE), styrene butadiene rubbers (SBR), polyacrylonitrile (PAN), polymethacrylates (PMA), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), polyvinylidene fluoride (PVdF) or its mixture.
In order to prevent the gathering of positive active material and conductive additive, can use dispersant.Suitable dispersant comprises having for the specific particle that uses in special adhesive and the solvent system and disperses or any compound of stably dispersing performance, and for example polyoxy stearmide (polyoxystearylamine) is used for being dispersed in the carbon black granules among the PVdF of N-methyl pyrrolidone (NMP).
The component of negative pole China ink can comprise negative electrode active material, adhesive, conductive additive and solvent.The negative pole China ink can be single type or polytype.As adhesive, can use the adhesive of the same type that uses with anodal China ink.
The component that is used to make the electrolyte ink of solid electrolyte layer can comprise solid electrolyte or its original material and solvent.Electrolyte ink contains solid electrolyte or its original material at least.When using following method, the obstruction that can keep the low viscosity of China ink and prevent to cause by ink discharge device, described method use solid electrolyte original material, apply and polymerization by using ink jet printing method.
Can comprise that solvent is as the black component that is used for any China ink.The solvent that is used for various China inks is not limited to specific solvent.The example of suitable solvent can comprise N-methyl pyrrolidone (NMP), dimethyl carbonate (DMC) and acetonitrile.Depend on the increase or the reduction of quantity of solvent, the viscosity of may command China ink.
The allocation ratio of the component that contains in various China inks is not restricted to special ratios.Yet the viscosity of China ink should be enough low, to use ink jet printing method.On the other hand, from improving the angle of operating efficiency, component concentrations is preferably high.Keeping the low method of viscosity to comprise increases black method of temperature.The compound that contains in China ink can change, so that viscosity.The viscosity that is fed to the various China inks in the ink discharge device is not particularly limited, but preferred viscosities is approximately 1-100 centipoise (cP).
After having prepared various China inks, use ink jet printing method spraying China ink, to produce collector body, electrode and solid electrolyte layer.Very little from the amount of the China ink of the nozzle ejection of ink discharge device, and can spray the China ink of almost equal volume.Therefore the electrode that is formed by the solid electrolyte layer of electrode ink and adhesion is extremely thin and even.And, when using ink jet printing method, accurately controlled the thickness and the form of collector body, electrode and solid electrolyte layer.
The mechanism that deposits the China ink that uses by ink discharge device can be piezoelectric ink jet print process, hot ink jet printing method or Bubble Jet
TMMethod.When forming collector body, electrode and solid electrolyte layer, pre-determine their form.If form collector body, electrode and solid electrolyte layer based on computer-generated image, it is excellent that their job specification becomes.Form by use a computer definite collector body, electrode and solid electrolyte layer and to make them are well-known.They can be along with using a computer and printing machine and output function are finished along with producing image.Therefore, the present invention can relatively easily realize suitability for industrialized production, because it can use the cognition of this area development.
The particle volume that sprays from ink discharge device is preferably 1-100 micromicron (picoliters).If the particle volume that sprays is too little, the reduction meeting deficiency of fluctuation.On the other hand, if the particle volume that sprays is too big, the reduction meeting deficiency of fluctuation.Particle volume by using ink discharge device to spray approximately is identical, and the homogeneity of electrode by this device manufacturing and battery can be very high.
The number of times that ink jet printing method sprays can be determined based on the thickness proportion and the structural material of collector body, electrode and solid electrolyte layer.When one-step print operation for thickness during deficiency, twice of the operation or repeatedly of on similar face, repeating print.In other words, the identical China ink of in identical substrate, repeating print.Therefore, can produce collector body, electrode and solid electrolyte layer with desired thickness.When using ink jet printing method to produce each layer, the homogeneity of each of generation layer is very high.Therefore, even when repeating these layers of lamination, can keep the height homogeneity.
When by ink jet printing manufactured collector body, positive pole and negative pole and solid electrolyte layer all these the time, coating procedure is not particularly limited.Can form each electrode layer by using a kind of ink discharge device, perhaps can operate (assembly-line operation) by assembly line, use an ink gun preparation anodal, use another ink gun to prepare solid electrolyte layer and prepare negative pole, thereby make the electrode assembly with another ink gun.
After producing electrode, dry removing desolvated.When the original material of solid electrolyte does not have polymerization to become solid electrolyte, can carry out polymerization.For example when China ink contains Photoepolymerizationinitiater initiater, can be by China ink being exposed to predetermined actinic radiation sources, for example ultraviolet ray or visible light, thus carry out the polymerization of original material.
The existence of particle not necessarily in collector body.High polymer itself also can have conductivity.In other words, can use the film made by conduction high polymer as collector body.Conduction high polymer is the heavy polymer that demonstrates conductivity, for example high-molecular polyazoles.As for the required molecular weight of high polymer, weight average molecular weight should be usually greater than about 5,000 dalton (Da), more preferably greater than 10, and 000Da, more preferably greater than 20,000Da, most preferably greater than 50,000Da is so that promote the excellent bonds of any coat to collector body.Preferably, weight average molecular weight is chosen as about 1,000 ten thousand Da or littler, more preferably 500 ten thousand Da or littler, and 1,000,000 Da or littler most preferably are so that it is receivable flexible to give collector body.
Conduction high polymer has conductivity, and is selected from the material with ionic conductivity, and described ion is as the charge transfer medium.In conduction high polymer, think that conductivity can is with and demonstrate to the polyenoid family generation of conjugation.Can use the polyenoid family conduction high polymer that is used for electrolytic capacitor as its representative example.More specifically, suitable conduction high polymer can comprise polyaniline, polypyrrole, polythiophene, polyacetylene, polyparaphenylene, polyphenylene vinylene, polyacrylonitrile, polyoxadiazole or its mixture.Because the resistance value of the collector body main body of Miao Shuing is different with the resistance value of metal forming, can use conduction high polymer, and the advantage that exists is: wide variety of materials is arranged herein.
The resistance value of collector body is not particularly limited, but the preferred conduction high polymer film of selecting makes collector body become 1/100 or littler for the resistance value of entire cell.The thickness of collector body is not particularly limited, but from the angle of the power output density that increases battery, is preferably thin collector body.As mentioned above, in the bipolar electrode battery pack, the collector body that is present between positive pole and the negative pole can have high resistance on the direction parallel with laminate layers.Therefore, can reduce the thickness of collector body.More specifically, the thickness of collector body is preferably the 0.1-15 micron.
Fig. 3 is the perspective view of the execution mode of explanation bipolar electrode battery pack of the present invention.In this example, the rectangular flat shape (rectangular flatshape) of bipolar electrode battery pack 100 shown in figure, and be used to extract the positive plate 11A of electric current and the two sides that negative plate 11B is placed on the bipolar electrode battery pack.With outer cover material material (jacket material) (for example laminated film) the parcel generating element 160 of bipolar electrode battery pack 100, will seal with positive plate 11A and the negative plate 11B that generating element 160 usefulness that outer cover material material package is wrapped up in are extracted out then.
Fig. 4 is the perspective view of the illustrative embodiments of the battery module 300 of explanation the present invention assembling.In this example, can contact or a plurality of bipolar electrode battery pack of electrical connection in parallel, form the battery module 300 of assembling.By polyphone and/or a plurality of battery pack 250 of electrical connection in parallel, can produce the battery module 300 of assembling.Fig. 4 has shown plane graph (figure A), front view (figure B) and the end view (figure C) of the battery module 300 of assembling.By using electrical connection, for example bus bar is electrically connected to each other battery pack 250.Can use jockey 310A that a plurality of bipolar electrode battery layers (bipolar electrode cell layer) of the battery pack 250 of assembling are laminated together.Can determine to be connected to form the number of bipolar electrode battery pack sheet of battery module 300 of assembling and lamination number based on battery capacity and the power output that has a vehicle (for example electric motor car) of battery with the bipolar electrode battery layers of the battery pack 250 of the assembling of the battery module 300 that forms assembling.
As shown in Figure 5, in order in electric motor car 400, to load the battery module 300 of assembling, battery is placed under the seat of main center of electric motor car 400.This is because if battery is placed under the seat, can have bigger inner space and bigger luggage case.Herein, the position that the battery module of assembling 300 is placed is not limited to below the seat, and this position can be more following part, i.e. luggage boot (rear-located trunk room) or be positioned at the engine bin of vehicle front.Use the electric motor car 400 of the battery module 300 of aforementioned assembling to have high durability, even and when long-time the driving, still can provide sufficient power to export.In addition, can provide electric motor car and hybrid vehicle with good mileage and excellent driveability.
Embodiment
Embodiment 1
1. make anodal
Mixing is as the LiMn of positive active material
2O
4(22wt%), as the acetylene black (6wt%) of conductive additive, as the poly(ethylene oxide) (PEO of ionic conduction high polymer; 18wt%), as the Li (C of auxiliary salt
2F
5SO
2)
2N (9wt%), regulate the N-methyl pyrrolidone (NMP of solvent as slurry viscosity; 45wt%) with as the azodiisobutyronitrile (AIBN of polymerization initiator; On a small quantity), preparation anode sizing agent.
It is 100 microns PET film one side that anode sizing agent is coated in thickness, then with the film that applies 110 ℃ of heating 4 hours to carry out thermal polymerization and curing, obtain anodal thus.By anode sizing agent being coated in thickness is 20 microns aluminium sheet, and it is carried out similar hot curing, and places contact with positive pole and form terminal, thereby positive pole is equipped be used for the terminal that electrically contacts in the generation of bipolar electrode battery pack.
2. manufacturing negative pole
Mixing is as the Li of negative electrode active material
4Ti
5O
12(14wt%), as the acetylene black (4wt%) of conductive additive, as the PEO (20wt%) of ionic conduction high polymer, as the Li (C of auxiliary salt
2F
5SO
2)
2N (11wt%), regulate the NMP (51wt%) of solvent and, prepare cathode size as the AIBN (on a small quantity) of polymerization initiator as slurry viscosity.
Cathode size is coated in the side that thickness is 100 microns PET film, and, carries out thermal polymerization and solidify the formation negative pole thus 110 ° of C heating 4 hours.By cathode size being coated in thickness is on 20 microns the SUS plate, and it is carried out similar hot curing, and places contact with negative pole and form terminal, thereby negative pole is equipped be used for the terminal that electrically contacts in the generation of bipolar electrode battery pack.
3. manufacturing dielectric substrate
By preparing PEO (64.5wt%) as ionic conduction high polymer and Li (C
2F
5SO
2)
2N (35.5wt%) uses acetonitrile as the viscosity adjustment solvent as auxiliary salt, the preparation electrolyte slurry.It is between 50 microns the glass plate that electrolyte slurry is poured over the slit, and dry, makes thickness thus and be 40 microns dielectric substrate.
4. manufacturing collector body
By preparing Au-Ag microparticle (average grain diameter: 10 microns; 90wt%) as conductive particle and polyvinylidene fluoride (PVdF; 10wt%) as high polymer material with use NMP as the viscosity adjustment solvent, preparation contains the collector body slurry of conductive particle.Use scraper that the collector body slurry is coated on the anodal top, described positive pole is formed on the above-mentioned PET film.Then, the coat film of compacting collector body slurry makes that the thickness of collector body is 30 microns.The voidage of collector body is 25%.
5. the assembling of bipolar electrode battery pack
Make and rectify the utmost point (terminal positive electrode), negative pole, end negative pole (terminal negativeelectrode), dielectric substrate and positive pole-collector body assembly, and cut into the plate of 120mm x 70mm.Then, will rectify the utmost point and be connected to dielectric substrate.After this, peel off negative pole from the PET film, the positive pole-collector body assembly that will peel off from the PET film and dielectric substrate be twice of lamination in succession.At last, the link negative pole is made three layers of bipolar electrode battery pack thus.Al plate and Ni plate are welded to respectively rectifies the utmost point and end negative pole.The battery vacuum seal that obtains is entered the aluminium layered product, finish the bipolar electrode battery pack thus.
Embodiment 2
By preparing (5 microns in graphite; 90wt%) as conductive particle and polyvinylidene fluoride (PVdF; 10wt% is in the N-methyl pyrrolidone) as high polymer material with use NMP as the viscosity adjustment solvent, preparation contains the collector body slurry of carbon granule.Use the process identical with embodiment 1, make the bipolar electrode battery pack, difference is by using above-mentioned collector body slurry, the collector body that generation is made by carbon granule (graphite).
Comparative Examples 1
The anode sizing agent that uses among the embodiment 1 is coated in the side that thickness is 30 microns SUS paper tinsel, it 110 ° of C heating 4 hours, is carried out thermal polymerization and curing, obtain positive pole-collector body assembly thus.Then, the cathode size that uses among the embodiment 1 is coated in the opposition side of SUS paper tinsel, dry then, obtain positive pole-collector body-negative pole assembly, wherein lamination positive pole, collector body and negative pole.
The assembly that forms above is cut into 120mm x 70mm.Then, connect the proper utmost point and the dielectric substrate that uses among the embodiment 1.Afterwards, the successive layer positive pressure utmost point-collector body-negative pole assembly and electrolyte are twice.At last, the link negative pole is made three layers of bipolar electrode battery pack thus.Al plate and Ni plate are connected respectively to be rectified on the utmost point and the end negative pole.The battery vacuum seal that obtains enters the aluminium layered product, finishes the bipolar electrode battery pack thus.
Battery assessment 1
To embodiment 1 and 2 and each battery of Comparative Examples 1 discharge and recharge test.In this test, make battery charge with the constant current (CC) of 0.5mA, be 8.1V until voltage, make battery charge with constant voltage (CV) then, total charging time is 10 hours.After this, the electric current with about 1mA made battery discharge 5 seconds.Voltage during based on discharge, the internal resistance of counting cell.When the internal resistance of Comparative Examples 1 battery is 100%, show this assessment with the ratio form.And, measure the weight of battery, and when the battery weight of Comparative Examples 1 is 100%, measure the weight of the battery of embodiment 1 and 2.The result is presented at table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Comparative Examples 1 | |
| The internal resistance of cell | 42％ | 60％ | 100％ |
| Battery weight | 90％ | 84％ | 100％ |
When Comparative Examples 1 compares with embodiment 1 and 2, find the resistance value of the resistance value of Comparative Examples 1 greater than embodiment 1 and 2.From this fact, suppose that the resistance between electrode and the collector body reduces by producing collector body with conductive particle.Its detailed mechanism is also unclear, but thinks that when using microparticle, the connection of the conductive additive in the electrode is good.And, find can realize weight saving and improve the power output density by producing collector body from conductive particle.
Embodiment 3
1. make anodal China ink
Preparation LiMn
2O
4(85wt%) as positive active material and acetylene black (5wt%) as conductive additive.Use NMP to regulate solvent, regulate the viscosity of China ink as slurry viscosity.At this moment, use ink jet printing method that above-mentioned anode sizing agent is coated on the aluminium, thickness is 20 microns, and drying is made the proper utmost point thus then.
2. make the negative pole China ink
Prepare hard carbon (90wt%) as negative electrode active material and PVdF (10wt%) as adhesive.NMP regulates solvent as slurry viscosity, regulates the viscosity of China ink.At this moment, use ink jet printing method that above-mentioned cathode size is coated on the aluminium, thickness is 20 microns, and drying is made the end negative pole thus then.
3. manufacturing electrolyte ink
Preparation PC-EC 1MLiBETI (90wt%) is as electrolyte and contain the PVdF-HFP of 10%HFP copolymer (10wt%) as main polymer.Use dimethyl carbonate (DMC) as solvent, regulate the concentration of China ink.
4. make the collector body China ink
Preparation comprises carbon granule (average grain diameter: 0.8m; Graphite 90wt%) as conductive particle and PVdF (10wt%) as adhesive.Use NMP as the viscosity adjustment solvent, regulate the collector body China ink that contains metal micro particles.
5. make the bipolar electrode battery pack
The proper utmost point that is cut into 120mm x 70mm is placed in the ink-jet coating unit, and by ink jet printing method coated electrolyte China ink, drying forms dielectric substrate thus then.
Use ink jet printing method spraying China ink by following process., be placed on the plastic components on the ink jet printing head herein, replace these parts that are positioned at the ink jet printing head inlet, and China ink directly is fed on the metal parts from black chamber with metal parts in order to prevent black dissolution with solvents.And, indoor in order to prevent black active material deposition or to be deposited in China ink, continue the agitating ink chamber by using the vane mixing arrangement.
Use commercially available PC and software control ink-jet printer.By the printing image that produces on computers, apply China ink by using ink-jet printer.Herein, when on metal forming, applying China ink,, metal forming is connected on the A4 paper that directly is fed to printing machine because be difficult to directly metal forming is fed to printing machine.
Behind the matter layer that produces electrolysis, apply the negative pole China ink by ink jet printing method, dry then, form negative pole thus.Then apply the collector body China ink by ink jet printing method, drying, generation thickness is 30 microns collector body (porosity 14%).In addition, apply anodal China ink, rectify the utmost point-dielectric substrate-negative electrode layer-current collector layer-positive pole layer thereby form.Repeat this process twice, by the link negative pole, make three layers of bipolar electrode battery pack then.Al plate and Ni plate are welded to respectively rectifies the utmost point and end negative pole.The battery that obtains is vacuum sealed in the aluminium layered product, finishes the assembly of bipolar electrode battery pack thus.
Embodiment 4
Use the process manufacturing bipolar electrode battery pack identical with embodiment 3, it has the collector body of voidage 11%, and difference is to change the suppression degree of collector body.
Embodiment 5
Use the process manufacturing bipolar electrode battery pack identical with embodiment 3, it has the collector body of voidage 16%, and difference is to change the suppression degree of collector body.
Comparative Examples 2
By using ink jet printing, it is on 30 microns the side of SUS paper tinsel that the anode sizing agent that uses among the embodiment 3 is coated in thickness, and dry, obtains positive pole-collector body assembly thus.Then, the cathode size that uses among the embodiment 3 is coated on the opposition side of SUS paper tinsel by using ink jet printing method, dry then, obtain positive pole-collector body-negative pole assembly thus, wherein positive pole, collector electrode main body and negative electrode layer force together.
The assembly of making is cut into 120mm x 70mm.Then, the proper utmost point that embodiment 3 is used is placed in the ink-jet coating unit, uses ink jet printing method coated electrolyte China ink, and is dry then, obtains dielectric substrate thus.After this, lamination positive pole-collector body-negative pole assembly uses ink jet printing method that electrolyte ink is coated on the positive pole, and is dry then, obtains dielectric substrate thus.Repeat identical process twice, final link negative pole is made three layers-bipolar electrode battery pack thus.Al plate and Ni plate are welded to the proper utmost point and end negative pole respectively.The battery that obtains is vacuum sealed in the aluminium layered product, finishes the bipolar electrode battery pack thus.
Battery assessment 2
Each battery to embodiment 3-5 and Comparative Examples 2 discharges and recharges test.In this test, make battery charge to 12.6V voltage with the constant current (CC) of 0.5mA, make battery charge with constant voltage (CV) then, total charging time is 10 hours.After this, the electric current with about 1mA made battery discharge 5 seconds.Voltage during based on discharge, the internal resistance of counting cell.When the internal resistance of Comparative Examples 2 batteries as 100% the time, show this assessment with the ratio form.And, measure the weight of battery, and when the battery weight of Comparative Examples 2 is 100%, measure the weight of the battery of embodiment 3-5.The result is presented at table 2.
Table 2
| Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative Examples 2 | |
| Porosity | 14％ | 11％ | 16％ | - |
| The internal resistance of cell | 86％ | 84％ | 82％ | 100％ |
| Battery weight | 85％ | 84％ | 83％ | 100％ |
In addition, the battery for embodiment 3 and 4 carries out charge and discharge cycles test (12.6-7.5V, 10mA (CC)).Even after 50 circulations, each battery has kept its voltage, and has shown good recursive nature.
From found that of embodiment 3-5 and Comparative Examples 2, the resistance value of Comparative Examples 2 is greater than the resistance value of embodiment 3-5.From this fact, suppose that the resistance between electrode and the collector body reduces by producing collector body with conductive particle.Its detailed mechanism is also unclear, but thinks that the connection of the conductive additive in electrode is good when using microparticle.And, find can realize weight saving and improve the power output density by producing collector body from conductive particle.
Embodiment 6
1. make anodal
By mixing LiMn
2O
4(22wt%) as positive active material, acetylene black (6wt%) as conductive additive, poly(ethylene oxide) (PEO; 18wt%) as ionic conduction high polymer, Li (C
2F
5SO
2)
2N (9wt%) is as auxiliary salt, N-methyl pyrrolidone (NMP; 45wt%) regulate solvent and azodiisobutyronitrile (AIBN as slurry viscosity; On a small quantity) as polymerization initiator, the preparation anode sizing agent.
2. manufacturing negative pole
By mixing Li
4Ti
5Oi
2(14wt%) as negative electrode active material, acetylene black (4wt%) as conductive additive, PEO (20wt%) as ionic conduction high polymer, Li (C
2F
5SO
2)
2N (11wt%) prepares cathode size as slurry viscosity adjusting solvent and AIBN (on a small quantity) as polymerization initiator as auxiliary salt, NMP (51wt%), the preparation cathode size.
3. manufacturing dielectric substrate
By mixing PC-EC 1M LiPF
6(90wt%) as electrolyte, contain the 10%HFP copolymer PVdF-HPF (10wt%) as main polymer and DMC as the viscosity adjustment solvent, the preparation electrolyte slurry.
4. manufacturing collector body
Conduction high polymer below using prepares collector body:
Conduction high polymer film 1: polypropylene is used as conductive particle as high polymer material and Au micro particulate materials.
Conduction high polymer film 2: polyimides is used as conductive particle as high polymer material and Au micro particulate materials.
Conduction high polymer film 3: polypropylene is used as conductive particle as high polymer material and carbon microparticle.
Conduction high polymer film 4: polyimides is used as conductive particle as high polymer material and carbon microparticle.
Conduction high polymer film 5: polypropylene is used as conductive particle as high polymer material and carbon microparticle.
Conduction high polymer film 6: polypropylene is used as conductive particle as high polymer material and carbon microparticle.
Conduction high polymer film 7: polypropylene is used as conductive particle as high polymer material and carbon microparticle.
Conduction high polymer film 8: polypropylene is used as conductive particle as high polymer material and carbon microparticle.
Conduction high polymer film 9: polyaniline film (thickness: 30 microns) is as the conduction high polymer film.
Comparative Examples 3
The SUS metal forming is as collector body.Each film of conduction high polymer film 1-9 and Comparative Examples 3 is of a size of 140mm x 90mmx30 micron (thickness).The measurement result of the specific insulation of conduction high polymer film thickness direction sees Table 3.In the time of every kind among the conduction high polymer film 1-9 relatively, are components identical even suppose them, for example conduction high polymer film 3 and 5 situation, their resistance is different because of configuration proportion.
Table 3
| Collector body | The specific insulation of thickness direction (Ω .cm) |
| Conduction high polymer film 1 | 1×10 -2 |
| Conduction high polymer film 2 | 1×10 -2 |
| Conduction high polymer film 3 | 1×10 -1 |
| Conduction high polymer film 4 | 1×10 -1 |
| Conduction high polymer film 5 | 1×10 3 |
| Conduction high polymer film 6 | 1×10 2 |
| Conduction high polymer film 7 | 1×10 |
| Conduction high polymer film 8 | - |
| Conduction high polymer film 9 | 1×10 -4 |
On a side of collector foil (conduction high polymer film 1-9 and Comparative Examples 2), use scraper to apply anode sizing agent, and dry.On the opposite side of collector foil, apply cathode size, and dry.Hot-rolling compacting bipolar electrode, with the lamination bipolar electrode stack, anodal as mentioned above and negative pole is coated in each side of collector body in bipolar electrode.
5. the assembling of bipolar electrode battery pack
It is square that the gained bipolar electrode is cut into 140mm x 90mm, comprises 120mm x 70mm square-shaped electrode, and electrode four square rings are wound with the seal cavity of 10mm.The thickness of anodal layer, collector foil and negative electrode layer is respectively 30 microns, causes the bipolar electrode of 90 microns of gross thickness.Use with the outer identical independent manufacturing of process of making bipolar electrode and only be coated with the collector foil part of anodal layer and the collector foil part that only is coated with negative electrode layer.
By both sides with 20 microns perforated membrane dividing plates of above-mentioned electrolyte injection, and dry DMC, obtaining the gel polymer electrolyte layer, described perforated membrane dividing plate is made by polypropylene.The gel polymer electrolyte layer is placed on aforementioned only being coated with on the anodal layer collector foil, and places the wide thick PE film of 12mm of 12mm on the seal cavity of collector foil, makes encapsulant thus.Similarly, four layers of bipolar electrode and four layers of dielectric substrate be lamination one after the other, to form the bipolar electrode assembly.By negative pole being faced the surface of bipolar electrode assembly downwards, lamination only is coated with the collector foil of negative electrode layer, forms 5 layers of bipolar electrode battery pack thus then.
5 layers of bipolar electrode battery pack are 0.2MPa pressure, 160 ° of C hot pressings of temperature 5 seconds, to eliminate the interface between dielectric substrate and bipolar electrode.By further heating the bipolar electrode battery pack 1 hour, it is sealed with encapsulant then.
By clamp-oning thickness is that 100 microns, area are that (it is used for extracting electric current from the both sides of 5 layers of bipolar electrode for the square Al plate of 130mm x 80mm, and obtain in the above described manner) be placed between 5 layers of bipolar electrode, obtain 5 layers of bipolar electrode battery pack thus.Herein, be that the terminal of the extraction electric current of 30x50mm is placed on the Al plate with area.
Vacuum seal bipolar electrode battery pack makes the terminal that extracts electric current be exposed in the aluminium layered product layer, finishes bipolar layered product battery thus.
Battery assessment 3
Each battery to conduction high polymer film 1-9 and Comparative Examples 4 discharges and recharges test.In this test, make battery charge to 12.5V voltage with the constant current (CC) of 0.5mA, make battery charge with constant voltage (CV) then, total charging time is 10 hours.After this, the electric current with about 1mA made battery discharge 5 seconds.Measure the weight of battery, and when the battery weight of Comparative Examples 3 is 100%, measure the weight of the battery of embodiment 1-9.The result is presented at table 4.
Table 4
| Collector body | Battery weight |
| Conduction high polymer film 1 | 76％ |
| Conduction high polymer film 2 | 79％ |
| Conduction high polymer film 3 | 70％ |
| Conduction high polymer film 4 | 74％ |
| Conduction high polymer film 5 | 69％ |
| Conduction high polymer film 6 | 69％ |
| Conduction high polymer film 7 | 70％ |
| Conduction high polymer film 8 | 70％ |
| Conduction high polymer film 9 | 72％ |
| Comparative Examples 3 | 100％ |
Table 4 demonstration uses the weight ratio of the current collection main body of conduction high polymer film not use the in light weight of conduction high polymer film.Therefore, the power output density of this class collector body Unit Weight obtains significant improvement than common metal collector body.This feature is identical with the feature of embodiment 1 and 2.And weight saving has played decisive role to carbon granule for collector body.
Made battery discharge 5 seconds with 1mA, and based on the internal resistance of the voltage measurement battery in when discharge.Resistance value when the internal resistance of conduction high polymer film 1 is 100% is shown in table 5.
Table 5 shows that the internal resistance of the current collection main body of using the conduction high polymer film is lower than the internal resistance of not using the conduction high polymer film, and their internal resistance obtains significant improvement than common metal collector body.This feature is identical with embodiment 1 and 2.Its detailed mechanism and unclear, but think when collector body uses conductive particle and high polymer material, the improvement that is connected of the interior collector body of electrode and conductive additive.
Table 5
| Collector body | Internal resistance |
| Conduction high polymer film 1 | 100％ |
| Conduction high polymer film 2 | 105％ |
| Conduction high polymer film 3 | 102％ |
| Conduction high polymer film 4 | 99％ |
| Conduction high polymer film 5 | 121％ |
| Conduction high polymer film 6 | 108％ |
| Conduction high polymer film 7 | 103％ |
| Conduction high polymer film 8 | 101％ |
| Conduction high polymer film 9 | 92％ |
| Comparative Examples 3 | 125％ |
In addition, 1-9 compares each other when the conduction high polymer film, uses the resistance value itself of the current collection main body of conduction high polymer diminish (conduction high polymer film 9).Although its detailed mechanism is unclear, think that when collector body use conduction high polymer itself, collector body contacts with the point that contacting of the electric conducting material that constitutes electrode material improved conductive particle.
The resistance value ratio of conduction high polymer film on its thickness direction, promptly the resistance value of conduction high polymer film on its thickness direction sees Table 6 with respect to the ratio (resistance of collector body parts/entire cell) of the resistance value of entire cell.Herein, as Comparative Examples 3,, it has been omitted because this ratio is almost 0 herein.
It is very little that table 6 shows that the current collection volume resistance is equivalent to the ratio of cell resistance, even and when collector body use high polymer material, resistance does not produce material impact for battery performance.
Table 6
| Collector body | The resistance of conduction high polymer film on thickness direction is equivalent to the ratio of entire cell resistance |
| Conduction high polymer film 1 | 1/1000000 |
| Conduction high polymer film 2 | 1/1000000 |
| Conduction high polymer film 3 | 1/100000 |
| Conduction high polymer film 4 | 1/100000 |
| Conduction high polymer film 5 | 1/10 |
| Conduction high polymer film 6 | 1/100 |
| Conduction high polymer film 7 | 1/1000 |
| Conduction high polymer film 8 | 1/1000 |
| Conduction high polymer film 9 | 1/10000000 |
Improved battery output by reducing contact resistance.Yet when resistance value becomes the about 1/10 time of entire cell, it becomes influential for the internal resistance of battery, and the output of battery trends towards reducing.Therefore, believe that it is preferred selecting 1/100 or lower resistance value of entire cell.For porosity, think that it does not almost have the space, and the infiltration of electrolyte does not take place because collector body uses high polymer material as essential element.
Each execution mode of the present invention has been described.These and other execution mode within the scope of the appended claims.
Claims (18)
1. battery comprises:
Bipolar electrode stack; comprise collector body, be electrically connected to the negative electrode of first side of collector body, the anode of second side that is electrically connected to collector body and one or more layers dielectric substrate of covered cathode and anode; wherein collector body comprises high polymer material; wherein collector body also comprises a plurality of conductive particles; perhaps described high polymer material is the conduction high polymer material, and the conductivity of the vertical direction of described collector body is provided by the film of described conductive particle or conduction high polymer material.
2. the battery of claim 1, wherein conductive particle is metallic particles or carbon granule.
3. the battery of claim 1, wherein high polymer comprises one or more of following material: polyethylene, polypropylene, PETG, polyethers nitrile, polyimides, polyamide, polytetrafluoroethylene, styrene butadiene rubbers, polyacrylonitrile, poly-(methyl) acrylate, poly-(methyl) methyl acrylate, polyvinyl chloride and polyvinylidene fluoride.
4. the battery of claim 1, wherein high polymer is an electric conductive polymer.
5. the battery of claim 4, wherein electric conductive polymer comprises one or more in the following material: polyaniline, polypyrrole, polythiophene, polyacetylene, polyparaphenylene, polyphenylene vinylene, polyacrylonitrile He polyoxadiazole.
6. the battery of claim 1, wherein the weight average molecular weight of high polymer material is that about 50,000 dalton are to about 1,000,000 dalton.
7. the battery of claim 1 comprises that also the electrode that is electrically connected to the collector body side extracts plate.
8. the battery of claim 7, wherein electrode extracts plate and comprises metal forming.
9. battery module comprises:
The bipolar electrode stack of a plurality of electrical connections;
Wherein each bipolar electrode stack comprises collector body, is electrically connected to the negative electrode of first side of collector body, the anode of second side that is electrically connected to collector body and one or more layers dielectric substrate of covered cathode and anode; And
Wherein the collector body of each bipolar electrode stack comprises high polymer material; wherein collector body also comprises a plurality of conductive particles; perhaps described high polymer material is the conduction high polymer material, and the conductivity of the vertical direction of described collector body is provided by the film of described conductive particle or conduction high polymer material.
10. the battery module of claim 9, wherein battery module is installed on the vehicle or in the vehicle.
11 1 kinds of methods of making the bipolar electrode assembly comprise:
Use ink jet printing method that high polymer material is sprayed on the collector body surface, form collector body;
Cathode material layer is sprayed to first side of collector body;
Anode material layer is sprayed to second side of collector body;
Spray first dielectric substrate, the covered cathode material layer; With
Spray second dielectric substrate, cover anode material layer.
12. the method for claim 11 is wherein used ink jet printing method sprayed cathode layer.
13. the method for claim 11 is wherein used ink jet printing method spraying anode layer.
14. the method for claim 11, wherein ink jet printing method is the piezoelectric ink jet print process.
15. the method for claim 11 also comprises and solidifies described high polymer material.
16. the method for claim 15, wherein curing is to use hot curing or radiation curing to carry out.
17. the method for claim 11 also comprises first dielectric substrate, cathode layer, collector body, anode layer and second dielectric substrate laminated togetherly, forms the bipolar electrode battery.
18. the method for claim 17 also comprises:
Form a plurality of bipolar electrode batteries of heap form; And
Be electrically connected each bipolar electrode battery, form battery pack.
19. the method for claim 18 also comprises:
Form a plurality of battery pack; And
Be electrically connected this a plurality of battery pack, form battery module.
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