CN102763253A - Positive electrode current collector for lithium ion secondary battery, positive electrode for lithium ion secondary battery, and process for production of positive electrode current collector for lithium ion secondary battery - Google Patents
Positive electrode current collector for lithium ion secondary battery, positive electrode for lithium ion secondary battery, and process for production of positive electrode current collector for lithium ion secondary battery Download PDFInfo
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- CN102763253A CN102763253A CN201180010391XA CN201180010391A CN102763253A CN 102763253 A CN102763253 A CN 102763253A CN 201180010391X A CN201180010391X A CN 201180010391XA CN 201180010391 A CN201180010391 A CN 201180010391A CN 102763253 A CN102763253 A CN 102763253A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion 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
- Y02E60/10—Energy storage using batteries
Abstract
Disclosed is a positive electrode current collector for a lithium ion secondary battery, which is characterized by comprising an aluminum foil comprising pure aluminum or an aluminum alloy and a surface layer formed on one surface or both surfaces of the aluminum foil, wherein the surface layer contains C in an amount of 10 to 95 at.% and additionally contains at least one element selected from Group 4 to Group 6 elements in an amount of 5 to 90 at.%. Also disclosed is a positive electrode for a lithium ion secondary battery, which is characterized by having a positive electrode active material layer that covers the surface layer of the positive electrode current collector for a lithium ion secondary battery. It becomes possible to prevent the elution of the current collector into an electrolytic solution to improve the adhesion between the current collector and the active material in the interface therebetween and increase the service life of a battery.
Description
Technical field
The present invention relates to the employed positive electrode collector of lithium rechargeable battery, the manufacturing approach of positive pole and positive electrode collector.
Background technology
In recent years, because the miniaturization and the high performance of mobile device, improve day by day for the requirement of the energy density (charge/discharge capacity) of the secondary cell that this mobile device carried.Wherein lithium rechargeable battery (below, suitable abbreviate as secondary cell) and NI-G secondary cell and nickel-hydrogen secondary cell etc. are compared, so demonstrate the energy density of higher voltage and Geng Gao, so begin to be widely used as the power supply of mobile device.In addition, along with the raising of environmental consciousness, expectation from the automobile that uses present fossil fuel to CO
2Electric automobile that discharge capacity is few or hybrid vehicle transition as the battery that it carried, uprise the expectation of lithium rechargeable battery.
The desired characteristic of secondary cell as being equipped on electric automobile, the hybrid vehicle etc. can be listed below: energy density high (the distance travelled prolongation of charging each time needs the number of times of charging to reduce); The speed that discharges and recharges is high speed (efficient activity of the raising of maximum output=acceleration performance, the shortening in charging interval, regenerative braking); Battery life is long etc.At this, so-called battery life is long, is meant the circulation time of repeated charge, and secondary cell can deterioration yet, the character that the battery performance of charge/discharge capacity/battery power output etc. can not reduce.
As the essential factor of the speed that discharges and recharges that determines lithium rechargeable battery, can enumerate internal resistance as battery.The internal resistance of battery is made up of the interface impedance that the impedance and the member of the employed member of battery self produces each other.As the employed member of lithium rechargeable battery, can enumerate collector body, active material, conductive auxiliary agent, electrolyte etc.
In addition, as the essential factor of the battery life that determines lithium rechargeable battery, can enumerate collector body and active material layer connecting airtight property at the interface.The major part of the lithium rechargeable battery that existing market is sold; Its use be the positive pole of making through following mode, that is, and constitute the aluminium foil of collector body (below; The suitable Al paper tinsel that is called) on, is coated on the slurry that is mixed with following material in the solvent: the LiCoO that constitutes active material
2Deng the powder of pottery of storage Li; The micro mist carbon of the acetylene black of formation conductive auxiliary agent (electric conducting material) etc.; The fluoride of the PVdF (polyvinylidene fluoride thing) of formation adhesive etc. makes it the positive pole that drying forms afterwards.
If above-mentioned slurry can not the wetting equably diffusion on the collector body surface, then become the reason of the peeling off of inhomogeneous (battery life reduction), active material in the face of electrode (rate of finished products worsens, charge/discharge capacity reduces, fail safe reduce) etc., take place bad.Therefore, the wetability of electrode surface goes out very important.
In addition, on the collector body surface of the positive pole of so making, under the high-tension influence of lithium ion battery, react with electrolyte and be formed with and fluoridize aluminium lamination.Usually, aluminum fluoride demonstrates highly corrosion resistant.Yet in the employed positive pole of lithium rechargeable battery, collector body and active material layer form the some state of contact at the interface, so the area at movement of electric charges position is little, uprises to current density part property, and collector body is easily to the electrolyte stripping.Then, if, then forming the collector body and the contact area of active material layer at the interface of some contact condition so to the electrolyte stripping, collector body further reduces both connecting airtight property reductions.Therefore, can reduce with reference to the amount certainty ground of the active material that discharges and recharges, charge/discharge capacity will reduce.
In addition, if the contact area of collector body and active material layer reduces, then collector body and active material layer also increase at the resistance (internal resistance) at interface, and therefore, as if when discharging, discharging big electric current, then the inner voltage of secondary cell descends and increases the reduction of battery power output.In addition, when charging, charging rate also will reduce.
In addition,,, between collector body and active material layer, hinder the conduction of electronics, become the reason that the internal resistance that makes battery increases so the collector body surface becomes fluoride because it is low to be formed at the electronic conductivity of aluminum fluoride on collector body surface.
If the resistance of secondary cell inside is big, the Joule heat when then discharging increases, and therefore causes the increase of energy loss; And, the thermal conductance that takes place rises because sending a telegraph the temperature in pond; Also can cause the decomposition of active material and electrolyte, perhaps on fire/heat dissipation etc. produce great influence to fail safe.
Therefore; It constitutes in patent documentation 1; On the collector body that forms by electric conducting material, the intermediate coat of carbon or the intermediate coat of the metal more expensive than electric conducting material are set, lining active material layer on it; Thereby prevent the stripping of collector body, make the connecting airtight property raising of collector body and active material layer at the interface to electrolyte.
In addition, in patent documentation 2, disclose a kind of method, it is at the surface-coated amorphous carbon layer that is dispersed with graphite particle of collector body paper tinsel, thereby prevents fluoridizing and oxidation of collector body paper tinsel surface.
The look-ahead technique document
Patent documentation
Patent documentation 1: TOHKEMY 2000-164466 communique
Patent documentation 2: TOHKEMY 2009-187772 communique
Yet, on the surface of collector body, can exist usually owing to atmosphere in oxygen react the very thin autoxidation epithelium that forms (below, be called oxide scale film).And; In general connecting airtight property is poor for such oxide scale film and carbon (C), even therefore as the invention of patent documentation 1 and patent documentation 2, at the surface of collector body formation carbon intermediate coat; Follow to discharge and recharge, still can produce the problem that this carbon intermediate coat is peeled off from collector body.In addition, if the carbon intermediate coat is peeled off from collector body like this, then active material layer of lining is also peeled off simultaneously on it, therefore also becomes the essential factor that battery life reduces.Therefore, the invention of patent documentation 1 and patent documentation 2 can not make the connecting airtight property raising at the interface of collector body and active material layer.
Summary of the invention
The present invention does in view of such problem points; Its problem is; The manufacturing approach of a kind of lithium ion secondary battery anode collector body, lithium ion secondary battery anode and lithium ion secondary battery anode collector body is provided; It can also improve collector body and active material layer the connecting airtight property at the interface except preventing collector body to the stripping of electrolyte, thereby battery life is increased.
In order to solve aforementioned problems; Lithium ion secondary battery anode collector body of the present invention, it constitutes, and has the aluminium foil that is made up of fine aluminium or aluminium alloy; Superficial layer with the one or both sides that are formed at said aluminium foil; In the lithium ion secondary battery anode collector body, it is 10～95 atom % that said superficial layer contains C, contain in addition among tetrels～the 6th family's element any one or be 5～90 atom % more than two kinds.
The lithium ion secondary battery anode collector body that constitutes by this structure; In the superficial layer that makes the surface of being located at aluminium foil; With ormal weight contain among the tetrels strong～the 6th family's element with the adhesion of oxygen any one or more than two kinds, can improve the adhesive force of this superficial layer and the very thin oxide scale film on the surface that is formed at aluminium foil.Therefore, superficial layer is difficult to peel off, so can prevent the stripping of aluminium foil to electrolyte.
In addition, lithium ion secondary battery anode collector body of the present invention preferably constitutes, and it is 30～95 atom % that said superficial layer contains C, contain in addition among tetrels～the 6th family's element any one or be 5～70 atom % more than two kinds.
By the lithium ion secondary battery anode collector body that such structure constitutes, the wetability of passable inhibition aluminium foil surface reduces, and applies when containing the slurry of active material when therefore making positive pole, can apply uniformly.
In addition, lithium ion secondary battery anode collector body of the present invention, the thickness that preferably makes said superficial layer are 10nm～1 μ m.
The lithium ion secondary battery anode collector body that is made up of such structure, the thickness through making superficial layer can improve the corrosion resistance of aluminium foil in prescribed limit.
In addition, lithium ion secondary battery anode of the present invention, it constitutes, and has described lithium ion secondary battery anode collector body and covers the positive electrode active material layer of the superficial layer of said lithium ion secondary battery anode collector body.
Lithium ion secondary battery anode by such structure constitutes prevents the stripping of aluminium foil to electrolyte through described collector body.Therefore, can improve collector body and active material layer connecting airtight property at the interface.
In addition; The manufacturing approach of lithium ion secondary battery anode collector body of the present invention; Be to carry out forming operation, promptly become embrane method, on the surface of aluminium foil through gas phase like undersurface layer; Make that to contain C be 10～95 atom %, contain in addition among tetrels～the 6th family's element any one or be that the superficial layer of 5～90 atom % is piled up more than two kinds.
The manufacturing approach of the lithium ion secondary battery anode collector body that is made up of such structure becomes embrane method through using gas phase, and superficial layer is piled up.
According to lithium ion secondary battery anode collector body of the present invention and the lithium ion secondary battery anode that has used this collector body; Through form on the surface of aluminium foil contain with ormal weight among tetrels～the 6th family's element any one or more than two kinds; And the superficial layer that contains C with ormal weight; Can prevent of the stripping of this aluminium foil, improve collector body and active material layer connecting airtight property at the interface to electrolyte.Therefore, can provide battery life more in the past than collector body that increased and positive pole.In addition, according to the manufacturing approach of lithium ion secondary battery anode collector body of the present invention, can be easily and positively make collector body with said characteristic.
Description of drawings
Fig. 1 is the skeleton diagram of positive pole that expression has the lithium ion secondary battery anode collector body of execution mode; (a) be the lithium ion secondary battery anode collector body and profile that is formed with superficial layer in the one side of aluminium foil, (b) be the profile that is formed with the lithium ion secondary battery anode collector body of superficial layer on the two sides of aluminium foil with its lithium ion secondary battery anode.
Fig. 2 is the lithium ion secondary battery anode collector body of expression execution mode and the skeleton diagram of the manufacturing approach of the lithium ion secondary battery anode with it; (a) be the figure of expression aluminium foil manufacturing process; (b) being the figure that the presentation surface layer forms operation, (c) is the figure that the expression positive electrode active material layer forms operation.
Fig. 3 is Ti (tetrels), V (the 5th family's element), the content of Cr (the 6th family's element) of superficial layer of the lithium ion secondary battery anode of expression embodiment, with the curve chart of the relation of the adhesive force of active material layer.
Fig. 4 is Ti (tetrels), V (the 5th family's element), the content of Cr (the 6th family's element) of superficial layer of the lithium ion secondary battery anode of expression embodiment, with the curve chart of the relation of water contact angle.
Fig. 5 is the cross section tem observation picture of superficial layer of embodiment 3 of the lithium ion secondary battery anode of embodiment.
Fig. 6 is the cross section tem observation picture of superficial layer of embodiment 13 of the lithium ion secondary battery anode of embodiment.
Fig. 7 is the cross section tem observation picture of superficial layer of comparative example 9 of the lithium ion secondary battery anode of embodiment.
Embodiment
Below, on one side with reference to accompanying drawing, on one side for the lithium ion secondary battery anode collector body of execution mode (below, the suitable collector body that abbreviates as) and lithium ion secondary battery anode (below, positive pole suits to abbreviate as) explanation at length with this collector body.Also have the size/engineer's scale of the formation shown in each figure, enlarged and displayed for the convenience of explaining is suitable.
At first, so-called lithium rechargeable battery is meant that the lithium ion in the electrolyte undertaking the secondary cell of the conduction of electric charge.Lithium rechargeable battery, at positive pole and negative pole as electrode, the active material layer of lithium ion can be stored/emitted to formation respectively, moves in electrolyte through lithium ion and work.Also have, state after the detailed formation about lithium rechargeable battery.
(collector body)
The base material of the positive pole 100 that collector body 10 is stated after being is the terminals that are used to draw electricity.As the former material that constitutes collector body 10, need satisfy excellent electric conductivity, at the important document of the existence of secondary cell internal stability, handling ease etc.Therefore, in this execution mode, the aluminium sheet that use will be satisfied these important documents has carried out rolling aluminium foil 1 as former material.
As the thickness of aluminium foil 1, be preferably 1～100 μ m.When the thickness of aluminium foil 1 is lower than 1 μ m, the weak strength of paper tinsel, therefore when the formation of superficial layer 2, or after during the formation of the positive electrode active material layer 20 stated, the fabrication stage of this external secondary cell, have the possibility of the fracture that paper tinsel takes place.On the other hand, though thicken the intensity that aluminium foil 1 can improve paper tinsel, when the thickness of aluminium foil 1 surpassed 100 μ m, collector body 10 shared volume in secondary cell integral body became big, has the possibility of the energy density reduction of secondary cell.
As said, usually, on the surface (surface of aluminium foil 1) of collector body 10, exist with atmosphere in oxygen react and the very thin oxide scale film (diagram is omitted) that forms.And this oxide scale film and connecting airtight property of C are poor, and therefore if only constitute superficial layer 2 with C, then superficial layer 2 is peeled off from aluminium foil 1, and there be the possibility of aluminium foil 1 to the electrolyte stripping in the corrosion resistance forfeiture.
But; The collector body 10 of execution mode; Through make in the superficial layer 2 with ormal weight contain among the tetrels strong～the 6th family's element with the adhesion of oxygen any one or more than two kinds; Thereby the content with the poor C of the adhesive force of the surperficial formed very thin oxide scale film of aluminium foil 1 is reduced, make the adhesive force raising of this oxide scale film and superficial layer 2.That is, superficial layer 2 is difficult to peel off from aluminium foil 1, thereby can prevent to indirect the stripping of aluminium foil 1 to electrolyte.Therefore, use secondary cell for a long time after, still can keep collector body 10 and after conducting between the positive electrode active material layer 20 stated, the result is the deterioration that can prevent the battery performance of secondary cell.
At this, the content of the tetrels that superficial layer 2 is contained～the 6th family's element is 5～90 atom % (content of C is 10～95 atom %).That is, the content of the tetrels that superficial layer 2 is contained～the 6th family's element is lower than 5 atom % when (content of C surpasses 95 atom %), and the metallic element in the superficial layer 2 is insufficient, so superficial layer 2 is little with the raising effect of the adhesive force of oxide scale film.On the other hand, when the content of the tetrels that superficial layer 2 is contained～the 6th family's element surpassed 90 atom % (content of C is lower than 10 atom %), the proterties of superficial layer 2 was near metal, and the surface of superficial layer 2 self can form oxide scale film.Then, this oxide scale film becomes the essential factor of connecting airtight that hinders superficial layer 2 and positive electrode active material layer 20.
In addition, as preferred form, be that the content of tetrels～the 6th family's element of being contained of superficial layer 2 is 5～70 atom % (content of C is 30～95 atom %).That is, when the content of the tetrels that superficial layer 2 is contained～the 6th family's element was lower than 5 atom % less than (content of C surpasses 95 atom %), the metallic element in the superficial layer 2 was insufficient, so the raising effect of the adhesive force of superficial layer 2 and oxide scale film is little.On the other hand; Consider the wetability of superficial layer 2; In order to make the slurry coating in the active material layer formation operation better, the content of the tetrels that preferred surface layer 2 is contained～the 6th family's element is (content of C is more than the 30 atom %) below the 70 atom %.Also have the content of the tetrels that superficial layer 2 is contained～the 6th family's element, more preferably 10～65 atom % (content of C is 35～90 atom %).
So; The collector body 10 of execution mode; Superficial layer 2 contains the C of 30～95 atom %, contains tetrels～the 6th family's element of 5～70 atom % in addition, thereby the wetability that can suppress aluminium foil surface reduces; Therefore when positive pole is made contain the active material slurry coating time, can apply uniformly.
Also have; Superficial layer 2 is with the purpose that ormal weight contains tetrels～the 6th family's element; Make to help the content of tetrels～the 6th family's element that oxide scale film and superficial layer 2 connect airtight to increase, and make the content minimizing that hinders the C that oxide scale film and superficial layer 2 connect airtight.Therefore; No matter make superficial layer 2 contain two kinds situation among tetrels～the 6th family's element; Still make it to contain the two or more situation among tetrels～the 6th family's element; As long as can limit for the content of the C in the superficial layer 2, the effect that is then played when making 2 of superficial layers contain among tetrels～the 6th family's element any one is identical.
The content of C that superficial layer 2 is contained and tetrels～the 6th family's element for example can be through AES (Auger Electron Spectroscopy: Auger electron spectroscopy) measure.So-called AES is meant detection under the irradiation of electron ray and the auger electrons of emitting from the surface of solids, thus the method for the surperficial composition of measure solid.
The thickness of superficial layer 2 (thickness) is 10nm～1 μ m.If the thickness of superficial layer 2 is lower than 10nm, then be diffused among the superficial layer 2 from the aluminium component of aluminium foil 1, can arrive the collector body surface easily, because the result can give play to sufficient corrosion resistance.In addition, if the thickness of superficial layer 2 surpasses 1 μ m, then productivity ratio reduces, and is not preferred therefore.Also have, the thickness of superficial layer 2 is 15nm～0.5 μ m more preferably.
The gas phase that superficial layer 2 can be received sputter etc. becomes embrane method to form, about stating after its detailed formation method.In addition, superficial layer 2 is except C and tetrels～the 6th family's element, also can in the scope that does not hinder the invention effect, contain the unavoidable impurities of Al, O etc.
In addition; The form of superficial layer 2 can change according to the ratio of the composition of the 4th wherein contained family～the 6th family's element and C, but if having the scope of corrosion resistance; Be the form of crystalline metal carbides all then, or the form of dispersed metal carbide all can in amorphous carbon.
(positive pole)
Anodal 100 is one of main members that constitute by secondary cell, plays a role as electrode with paired negative pole.Positive pole 100 is via the electrolyte storage or go into out lithium ion, bears the reaction that discharges and recharges of secondary cell.Anodal 100 shown in Fig. 1 (a), is made up of with positive electrode active material layer 20 described collector body 10.
Positive electrode active material layer 20 is the layers with material of storing/emitting lithium ion, is undertaking the central task that discharges and recharges reaction of lithium rechargeable battery.Positive electrode active material layer 20 is by the LiCoO as active material that stores/emit lithium ion
2, LiMn
2O
4, LiNiO
2Etc. formation, but especially preferably by LiCoO
2Constitute.
Positive electrode active material layer 20 forms through following mode: described active material is mixed in solvent with conductive auxiliary agent and adhesive, be coated with the mode that on superficial layer 2, covers this this mixture, make it dry.At this, for example can use acetylene black as conductive auxiliary agent, for example can use polyvinylidene fluoride as adhesive, for example can use 1-Methyl-2-Pyrrolidone etc. as solvent, the allotment ratio of these compositions does not have special qualification.Also have, the thickness of positive electrode active material layer 20, the viewpoint from the volume capacity of secondary cell is preferably 0.1～100 μ m.
So; The collector body 10 of execution mode and anodal 100; Form superficial layer 2 on the surface of aluminium foil 1, its with ormal weight contain among the tetrels strong～the 6th family's element with the adhesion of oxygen any one or more than two kinds, and contain C with ormal weight; Thereby can prevent of the stripping of this aluminium foil 1, improve collector body 10 and the connecting airtight property of positive electrode active material layer 20 at the interface to electrolyte.Therefore, can keep the amount of the active material that can participate in discharging and recharging, can be more in the past than the battery life that improved secondary cell.
(manufacturing approach of collector body)
Below, on one side with reference to Fig. 2, one side describes for the manufacturing approach of the collector body 10 of execution mode.The manufacturing approach of the collector body 10 of execution mode is characterized in that, carries out superficial layer and forms operation.In addition, be to carry out aluminium foil manufacturing process as its prerequisite.
(1) aluminium foil manufacturing process
This operation is a Rolling Aluminium Plate and make the operation of the aluminium foil 1 with specific thickness and regulation area shown in Fig. 2 (a).At this, the final thickness of the aluminium foil of making by aluminium sheet 1, the viewpoint from the volume capacity of paper tinsel intensity and secondary cell is preferably 1～100 μ m.
(2) superficial layer forms operation
This operation is the operation of the one or both sides formation superficial layer 2 on aluminium foil 1 shown in Fig. 2 (b).In this operation, use gas phase to become the one or both sides of embrane method on aluminium foil 1, make as the C of film forming element with among tetrels～the 6th family's element any one or pile up and formation superficial layer 2 more than two kinds.Also have, so-called gas phase becomes embrane method, is meant in gas phase at substrate surface atom to be separated out pile up and form the one-tenth embrane method of the film of solid.
Become the concrete example of embrane method as gas phase, for example, can enumerate sputter and vacuum evaporation etc.At this, so-called sputter is that the target plasma sputter is hit its atom, makes atom packing method on (surface) on base material, and so-called vacuum evaporation is heated to high temperature with target exactly and makes it the evaporation gasification, makes the method for atom packing on base material.At this, if a little less than the combination of superficial layer 2 and aluminium foil 1, then superficial layer 2 might be peeled off, therefore become embrane method as the gas phase of using in this operation, preferably adopt and compare the sputter that can form the stronger film of adhesion with vacuum evaporation.
Condition optimization as sputter does, indoor at not shown sputter equipment accommodated aluminium foil 1 and the C target corresponding with the formation element of superficial layer 2 and the target of tetrels～the 6th family's element respectively, makes internal pressure 1 * 10
-3Below the Pa and import sputter gas (Ar gas), will become film pressure to maintain the surface of 0.2～0.3Pa one side sputter each target on one side.In addition, sputtering power is preferably 1～2kW.
The collector body of making through these operations 10 shown in Fig. 2 (b), forms the superficial layer 2 of specific thickness on aluminium foil 1.In addition, the composition of this superficial layer 2 is controlled at 10～95 atom % to major general C, and tetrels～the 6th family's element is controlled at 5～90 atom %.Also have, the composition of superficial layer 2 preferably is controlled at 30～95 atom % with C, and tetrels～the 6th family's element is controlled at 5～70 atom %.In addition, for example can use Ti, can use V, can use Cr as the 6th family's element as pentels as described tetrels.
In addition, the thickness of superficial layer 2 for more than the 10nm, is 1 μ m below from the viewpoint of having boosted productivity from the viewpoint of bringing into play sufficient corrosion resistance.The thickness of superficial layer 2 is 15nm～0.5 μ m more preferably.
(anodal manufacturing approach)
In addition, after having carried out described aluminium foil manufacturing process and superficial layer formation operation, form operation, also can make positive pole 100 with collector body 10 through carrying out positive electrode active material layer.
(3) positive electrode active material layer forms operation
This operation is the operation that on superficial layer 2, forms positive electrode active material layer 20 shown in Fig. 2 (c).In this operation, active material is mixed in solvent with conductive auxiliary agent and adhesive, this mixture is coated on the superficial layer 2, make it dry and formation positive electrode active material layer 20.At this, for example can use LiCoO as active material
2, for example can use acetylene black as conductive auxiliary agent, for example can use polyvinylidene fluoride as adhesive, for example can use 1-Methyl-2-Pyrrolidone etc. as solvent, the allotment ratio of these compositions does not have special qualification.In addition, baking temperature for example is 100～150 ℃.Also have, the thickness of positive electrode active material layer 20 is preferably 0.1～100 μ m from the viewpoint of the volume capacity of secondary cell.
Through the positive pole 100 of these operation manufacturings, shown in Fig. 2 (c), have aluminium foil 1, the formed superficial layer of the one side of aluminium foil 12, on superficial layer 2 formed positive electrode active material layer 20.In addition, the composition of superficial layer 2, C is controlled at 10～95 atom % at least, and tetrels～the 6th family's element is controlled at 5～90 atom %, and preferred C is controlled at 30～95 atom %, and tetrels～the 6th family's element is controlled at 5～70 atom %.In addition, the THICKNESS CONTROL of superficial layer 2 is at 10nm～1 μ m.
Therefore; Surface at aluminium foil 1; Be formed with ormal weight and contain any one or the superficial layer more than two kinds 2 among the tetrels strong～the 6th family's element with the adhesion of oxygen; Therefore the stripping of aluminium foil 1 be can prevent, collector body 10 and the connecting airtight property of positive electrode active material layer 20 improved at the interface to electrolyte.In addition, the amount of the active material that can participate in discharging and recharging can be kept, the battery life that in the past improved secondary cell can be compared.
In addition; Through among tetrels～the 6th family's element that superficial layer 2 is contained any one or be controlled at 5～70 atom % more than two kinds; Can suppress aluminium foil 1 wetting of surfaces property reduction, therefore when positive pole is made contain the active material slurry coating time, can apply uniformly.In addition, the thickness through making superficial layer 2 can improve the corrosion resistance of aluminium foil 1 in prescribed limit.
(lithium rechargeable battery)
The positive pole 100 of execution mode can be clipped in dividing plate between this positive pole 100 and the not shown negative pole, and it is reeled, and sealing is accommodated in cylindric, the rectangle that is filled with electrolyte, range upon range of (laminate) type shell, thereby constitutes secondary cell.Below, carry out simple declaration for the formation of the secondary cell beyond the positive pole 100.
Negative pole is same with anodal 100, is one of main member that constitutes by secondary cell, brings into play function with paired positive pole 100 as electrode.Negative pole is via the electrolyte storage or emit lithium ion, bears the reaction that discharges and recharges of secondary cell.Negative pole is by constituting as follows in addition: the collector body that is made up of aluminium foil or Copper Foil; Be formed at collector body on, the negative electrode active material layer that constitutes by graphite, Si, Ge, Ag, In, Sn, lithium titanate etc.
Dividing plate is to be clipped in the perforated membrane that disposes between positive pole 100 and the negative pole, is to be used to prevent internal short-circuit, and keeps the member of electrolyte.The function that dividing plate has is, if in the inner minute short circuit that takes place of secondary cell, temperature rises, and then closes each micro hole that constitutes perforated membrane and inner impedance is increased, to stop the movement of electric charges of lithium ion carrying.As dividing plate, be the dielectric film of the lithium ion porous matter that can move, for example, can use the perforated membrane of polypropylene and polyolefin.
Electrolyte is the interior liquid of shell that is filled in secondary cell, is the medium that lithium ion is used to carry electric charge.In secondary cell, if the amount of lithium ion is many, then many more, the electric charge of drawing is many more, so electrolyte also preferably uses the solution of lithium.That is,, preferably use in the cyclic ester of ethylene carbonate, propene carbonate etc., be added with the rudimentary linear carbonate of dimethyl carbonate etc. and the mixed organic solvents of fluorophosphoric acid lithium salts as electrolyte.
(action of lithium rechargeable battery)
Below, on one side according to anodal 100 effects played, the operation during on one side for the discharging and recharging of the secondary cell of the positive pole with execution mode 100 describes.
If secondary cell charges, the lithium ion of then anodal 100 sides moves to negative side via electrolyte, stores in the negative electrode active material layer.On the other hand, if secondary cell discharges, the lithium ion of then storing in the negative electrode active material layer is emitted, and is stored at anodal 100 sides once again via electrolyte.So because so repeatedly discharging and recharging, if in the past, then have can be to the electrolyte stripping for anodal 100 aluminium foil 1.But, have the secondary cell of the positive pole 100 of execution mode, because between anodal 100 aluminium foil 1 and positive electrode active material layer 20, be formed with superficial layer 2, so can prevent the stripping of aluminium foil 1 to electrolyte.
In addition, if in the past, then owing to the surperficial formed oxide scale film at aluminium foil 1 might cause superficial layer 2 to be peeled off.But; The secondary cell of execution mode; In superficial layer 2, contain among the tetrels strong～the 6th family's element any one, thereby can prevent the stripping of aluminium foil 1, collector body 10 and the connecting airtight property raising of positive electrode active material layer 20 at the interface to electrolyte with the adhesion of oxygen.Therefore, can keep the amount of the active material that can participate in discharging and recharging, and compare the battery life that can improve secondary cell in the past.
Embodiment
[first embodiment]
Next, just satisfy the positive pole of important document of positive pole and the discontented unabridged version invention of important document of the present invention, show the embodiment that collector body and the adhesive force of positive electrode active material layer at the interface are compared.At first, the positive pole for using in the present embodiment describes along manufacturing process.Also have, the comparative example 4 of present embodiment is assumed to be the positive pole that is formed with the intermediate coat of carbon on the aforementioned patent document collector body 1 described, that formed by electric conducting material.
(1) aluminium foil manufacturing process
Aluminium foil manufacturing process carries out same processing in embodiment 1～12 and comparative example 1～10.That is, Rolling Aluminium Plate is made the aluminium foil of long 50mm * horizontal 50mm * thick 15 μ m.
(2) superficial layer forms operation
Superficial layer forms operation, the different processing of enforcement in embodiment 1～12 and comparative example 1～10.That is, in embodiment 1～12 and comparative example 5～7,9～10, forming by any one superficial layer that constitutes among C and tetrels～the 6th family's element through sputter on the aluminium foil.At this, use Ti as tetrels, use V as pentels, use Cr as the 6th family's element.On the other hand, in comparative example 1～3, on aluminium foil, form any one superficial layer that constitutes by Ti, V, Cr through sputter.In addition, in comparative example 4, on aluminium foil, form the superficial layer that only constitutes by C through sputter.In addition, in comparative example 8, unreal applying covered (surface treatment) on aluminium foil.Also have, the thickness of superficial layer makes it to take place various variations through changing film formation time respectively.In addition, the form of superficial layer all is the form that forms the mixture of crystalline metal or metal carbides and amorphous carbon.
Also have; In the present embodiment; What show is only to make in the superficial layer with ormal weight to contain any one the example among tetrels～the 6th family's element, but makes superficial layer contain the purpose of tetrels～the 6th family's element with ormal weight, as aforementioned; Be to make the content of the tetrels that connects airtight～the 6th family's element that helps oxide scale film and superficial layer to increase, and make the content minimizing that hinders the C that oxide scale film and superficial layer connect airtight.Therefore; No matter be to make superficial layer contain two kinds situation among tetrels～the 6th family's element; Still make it to contain the two or more situation among tetrels～the 6th family's element; As long as can limit for the content of the C in the superficial layer, the effect that is then played when making superficial layer only contain among tetrels～the 6th family's element any one is identical.
As the condition of sputter, be indoor at sputter equipment, accommodate aluminium foil, C target
Among Ti target/V target/Cr target any one
Making internal pressure is 1 * 10
-3Below the Pa and import sputter gas (Ar gas), will become film pressure to maintain 0.26Pa on one side, sputter is carried out to the surface of C target and Ti target/V target/Cr target in one side.In addition, sputtering power is 1.5kW.
(3) positive electrode active material layer forms operation
Positive electrode active material layer forms operation, in embodiment 1～12 and comparative example 1～10, carries out same processing.That is, on the superficial layer of the collector body of embodiment 1～12 and comparative example 1～10, form positive electrode active material layer.Specifically, use LiCoO as active material
2, use acetylene black as conductive auxiliary agent, use polyvinylidene fluoride as adhesive, itself and 1-Methyl-2-Pyrrolidone as solvent are mixed be pasty state, be coated on equably on the superficial layer, carry out drying with 120 ℃.
(4) measurement of the composition of superficial layer
After described superficial layer forms operation, through the composition of AES meter surface layer.
(5) adhere to force measurement and evaluation
After aforesaid positive electrode active material layer forms operation; Measure the size of positive electrode active material layer through SAICAS (Surface and Interfacial Cutting Analysis System: サ イ カ ス, surface and interface cutting analytical system) method for the adhesive force of collector body.At this, so-called SAICAS method is meant and uses sharp blade, cuts along the base material of test portion and the interface of adherend, measures the method for the adhesive force of base material and adherend.
In the present embodiment, use " the system SAICASDN-20 of ダ イ プ ラ ウ イ Application テ ス society ", cut, measure adhesive force along the interface of collector body and positive electrode active material layer.Then, adhesive force is be evaluated as qualified (being expressed as " zero " in the table) more than the 0.20kN/m, is lower than to be being evaluated as of 0.20kN/m defective (being expressed as " * " in the table).Also have,, be as preventing peeling off of active material layer, and prevent the stripping of aluminium foil, the standard that can extend the life of a cell and experimental value of trying to achieve to electrolyte as the value (0.20kN/m) of the adhesive force of the standard of estimating.
The relation of the adhesive force of the composition of the superficial layer of demonstration embodiment and comparative example and active material layer in the table 1.Also have, below shown in table in " M [atom %] ", represent the amount of quaternary element～hexa-atomic element.
[table 1]
As shown in table 1ly know that embodiment 1～12, any one amount of C that superficial layer contained and Ti, V, Cr (tetrels～the 6th family's element) within the scope of the invention, so adhesive force is qualified.Can know on the other hand, comparative example 1～3, because do not contain C fully, thus the influence of the wetability difference of stating after having, or adhesive force is 0kN/m.At this, so-called adhesive force is the state of 0kN/m, and when being meant based on SAICAS method measurement adhesive force, positive electrode active material layer is peeled off easily, the state that adhesive force can not be measured.Then, can know comparative example 4,, peel off easily so the connecting airtight property of Al collector body and superficial layer is poor because superficial layer only is made up of C.
In addition, if with reference to Fig. 3, then also can know the dependency relation of Ti, V, Cr content and the adhesive force of superficial layer.That is, can know according to the curve chart of Fig. 3, be 0.20kN/m in order to make adhesive force, and the content that makes Ti, V, Cr is that general 5～90 atom % get final product.Therefore, provable by present embodiment, satisfy the positive pole of important document of the present invention, with the positive pole of the important document of discontented unabridged version invention relatively, positive electrode active material layer is bigger for the adhesive force of collector body, promptly battery life is high.
[second embodiment]
Then, in order to investigate, show the relatively embodiment of collector body wetting of surfaces property for collector body of the present invention and anodal preferred form.Also have, this characteristic only is as desired characteristics of the present invention, even therefore do not satisfy this characteristic, satisfies the adhesive force of first embodiment, just the MIN purpose of attainable cost invention.In the present embodiment, use embodiment 1～12 and comparative example 1～3,5～8, carry out following such measurement and evaluation through making with the same manufacturing process of aforementioned first embodiment.
(1) measurement of the composition of superficial layer
After aforesaid superficial layer forms operation, through the composition of AES meter surface layer.
(2) measurement of water contact angle and evaluation
After aforesaid superficial layer forms operation, carry out water contact angle for the wettability hundred of estimating the current collection surface and measure.So-called contact angle, the meaning are the tangent lines and the angle of the surface of solids of fluid drips formed drop surface and contact site of solid when falling the surface of solids, are the indexs of representing the diffusion difficulty of the liquid on the surface of solids.
In the present embodiment, use " consonance interface industry system contact angle meter CA-A type ",, measure through the water contact angle after 30 seconds at the aluminium foil surface of each collector body ion exchange water 2 μ L that drip.Then; Water contact angle is evaluated as qualified (being expressed as " zero " in the table) than little (wetability is good) of aluminium foil of not implementing the comparative example 8 of coating (surface treatment), and (wetability bad) bigger than the aluminium Al paper tinsel of comparative example 8 is evaluated as defective (being expressed as " △ " in the table).
The composition of the superficial layer of embodiment and comparative example and the relation of wetability are presented in the table 2.
[table 2]
As shown in table 2ly know that embodiment 1～12, because any one amount of C that superficial layer contained and Ti, V, Cr (tetrels～the 6th family's element) is in the scope of 5～70 atom %, so water contact angle is included appropriate scope in.Can know that on the other hand comparative example 1～3,5～8 is because the amount of Ti, V, Cr breaks away from the scope of 5～70 atom %, or enforcement applies, so collector body wetting of surfaces property is poor.
In addition, if can know then that with reference to Fig. 4 the Ti of superficial layer, V, Cr content and collector body wetting of surfaces property (water contact angle) are in dependency relation.Therefore, better in order to make water contact angle than untreated foil, can know that the content that makes Ti, V, Cr probably is that 5～70 atom % get final product.
[the 3rd embodiment]
Then, in order to investigate, show the relatively embodiment of corrosion resistance for collector body of the present invention and anodal preferred form.Also have, this characteristic only is as desired characteristics of the present invention, even therefore do not satisfy this characteristic, the adhesive force of satisfied first embodiment, still can reach MIN purpose of the present invention.In the present embodiment, use embodiment 3～5,8,9,13 and comparative example 8～10, carry out following such processing through making with the same manufacturing process of aforementioned first embodiment.
(1) measurement of the composition of superficial layer
After aforesaid superficial layer forms operation, through the composition of AES meter surface layer.
(2) evaluation of corrosion resistance
The positive pole that use is made with said method; The manufacture batteries unit; After enforcement discharges and recharges test, estimate the corrosion resistance of the electrode that the battery unit decomposition is obtained, and use TEM (transmission electron microscope) to carry out the observation at the interface of active material layer and collector body.
The evaluation result of the corrosion resistance that respectively applies thickness (thickness of superficial layer) of embodiment and comparative example is presented in the table 3.
[table 3]
As shown in table 3ly know that embodiment 3～5,8,9,13, therefore the thickness of its superficial layer demonstrate good anti-corrosion in the scope of 10nm～1 μ m.On the other hand, can know that the thickness of comparative example 8～10 its superficial layers breaks away from the scope of 10nm～1 μ m or implements coating, so corrosion resistance is bad.
In addition, if can know with reference to Fig. 5,6, therefore the thickness of embodiment 3,13 its superficial layers do not corrode on the surface that discharges and recharges test back paper tinsel in the scope of 10nm～1 μ m.On the other hand, if can know then that with reference to Fig. 7 the thickness of comparative example 9 its superficial layers is in the scope of 10nm～1 μ m, therefore after discharging and recharging test, corrode on the surface of paper tinsel.
Can know by above result; In collector body and positive pole; Through form any one or 5～90 atom % more than two kinds that contain among tetrels～the 6th family's element on the surface of aluminium foil; And the superficial layer that contains the C of 10～95 atom % can make the connecting airtight property raising at the interface of collector body and active material layer.
Can know in addition; In collector body and positive pole; Further form any one or 5～70 atom % more than two kinds that contain among tetrels～the 6th family's element, and contain the superficial layer of the C of 30～95 atom %, wetability is improved on the surface of aluminium foil.
Can know that in addition in collector body and positive pole, the thickness of the superficial layer through further making aluminium foil is 10nm～1 μ m, corrosion resistance is improved.
More than; Manufacturing approach with regard to lithium ion secondary battery anode collector body of the present invention, lithium ion secondary battery anode and lithium ion secondary battery anode collector body; Mode and embodiment through being used to carry out an invention more specifically are illustrated; But aim of the present invention is not recorded and narrated by these to be limited, and must broadly explain based on the scope of Patent right requirement is said.In addition, carried out being also contained in certainly in the aim of the present invention of various changes, change etc. based on these records.
The application is based on the Japanese patent application (patent application 2010-269224) of the Japanese patent application (patent application 2010-039629) of on February 25th, 2010 application, application on December 2nd, 2010, its content this with reference to and quote.
Utilizability on the industry
The present invention is useful for the lithium rechargeable battery of the lift-launch of electric automobile, hybrid vehicle etc.
Symbol description
1 aluminium foil
2 superficial layers
10 lithium ion secondary battery anode collector bodies (collector body)
20 positive electrode active material layers
100 lithium ion secondary battery anodes (positive pole)
Claims (5)
1. a lithium ion secondary battery anode collector body is characterized in that, has the superficial layer on aluminium foil that is made up of fine aluminium or aluminium alloy and the one or both sides that are formed on said aluminium foil, wherein,
Said superficial layer contains the C of 10～95 atom %, and, also contain any one or the element more than two kinds among tetrels～the 6th family's element of 5～90 atom %.
2. lithium ion secondary battery anode collector body according to claim 1; It is characterized in that; Said superficial layer contains the C of 30～95 atom %, and, also contain any one or the element more than two kinds among tetrels～the 6th family's element of 5～70 atom %.
3. lithium ion secondary battery anode collector body according to claim 1 and 2 is characterized in that, the thickness of said superficial layer is 10nm～1 μ m.
4. lithium ion secondary battery anode is characterized in that having:
Each described lithium ion secondary battery anode collector body in the claim 1～3; With
Cover the positive electrode active material layer of the superficial layer of said lithium ion secondary battery anode collector body.
5. the manufacturing approach of a lithium ion secondary battery anode collector body is the manufacturing approach of each described lithium ion secondary battery anode collector body in the claim 1～3, it is characterized in that,
The superficial layer that becomes embrane method to pile up at the surperficial enterprising enforcement superficial layer of aluminium foil through gas phase forms operation; This superficial layer contains the C of 10～95 atom %; And, also contain any one or the element more than two kinds among tetrels～the 6th family's element of 5～90 atom %.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010039629 | 2010-02-25 | ||
| JP2010-039629 | 2010-02-25 | ||
| JP2010-269224 | 2010-12-02 | ||
| JP2010269224A JP5097260B2 (en) | 2010-02-25 | 2010-12-02 | Method for producing positive electrode for lithium ion secondary battery and positive electrode current collector for lithium ion secondary battery |
| PCT/JP2011/054034 WO2011105451A1 (en) | 2010-02-25 | 2011-02-23 | Positive electrode current collector for lithium ion secondary battery, positive electrode for lithium ion secondary battery, and process for production of positive electrode current collector for lithium ion secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102763253A true CN102763253A (en) | 2012-10-31 |
| CN102763253B CN102763253B (en) | 2016-02-17 |
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| CN201180010391.XA Expired - Fee Related CN102763253B (en) | 2010-02-25 | 2011-02-23 | Lithium ion secondary battery anode collector body, the manufacture method of lithium ion secondary battery anode and lithium ion secondary battery anode collector body |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5097260B2 (en) |
| CN (1) | CN102763253B (en) |
| WO (1) | WO2011105451A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108649192A (en) * | 2018-04-08 | 2018-10-12 | 河南大学 | A method of it is tested based on contact angle and prepares the uniform decorative layer of electrode material surface |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP2903059B1 (en) * | 2012-09-26 | 2017-07-26 | Showa Denko K.K. | Negative electrode for secondary batteries, and secondary battery |
| KR102232050B1 (en) * | 2013-11-27 | 2021-03-24 | 제이엔씨 주식회사 | Photocurable inkjet ink |
Citations (3)
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|---|---|---|---|---|
| JP2007265852A (en) * | 2006-03-29 | 2007-10-11 | Matsushita Electric Ind Co Ltd | Compound current collector and its manufacturing method |
| JP2009187772A (en) * | 2008-02-06 | 2009-08-20 | Toyota Motor Corp | Manufacturing method of electrode foil for nonaqueous electrolyte battery, and manufacturing method of electrode plate for nonaqueous electrolyte battery |
| WO2010004398A1 (en) * | 2008-07-11 | 2010-01-14 | Toyota Jidosha Kabushiki Kaisha | Battery-dedicated electrode foil, positive electrode plate, battery, vehicle, and battery-equipped appliance, and manufacture method for the battery-dedicated electrode foil, and manufacture method of the positive electrode plate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000164466A (en) * | 1998-11-26 | 2000-06-16 | Toyota Motor Corp | Manufacture of electrode used for capacitor or cell |
| JP2003109582A (en) * | 2001-09-27 | 2003-04-11 | Hitachi Metals Ltd | Laminated strip material, laminated strip material for battery using the same, and manufacturing method of the same |
| US7521153B2 (en) * | 2004-03-16 | 2009-04-21 | Toyota Motor Engineering & Manufacturing North America, Inc. | Corrosion protection using protected electron collector |
| JP5239311B2 (en) * | 2006-11-27 | 2013-07-17 | 株式会社デンソー | Current collector, electrode and power storage device |
| JP5145794B2 (en) * | 2007-06-29 | 2013-02-20 | 株式会社デンソー | Electrode manufacturing method |
| JP2010086866A (en) * | 2008-10-01 | 2010-04-15 | Toyota Motor Corp | Electrode sheet and method of manufacturing the same |
-
2010
- 2010-12-02 JP JP2010269224A patent/JP5097260B2/en not_active Expired - Fee Related
-
2011
- 2011-02-23 WO PCT/JP2011/054034 patent/WO2011105451A1/en active Application Filing
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007265852A (en) * | 2006-03-29 | 2007-10-11 | Matsushita Electric Ind Co Ltd | Compound current collector and its manufacturing method |
| JP2009187772A (en) * | 2008-02-06 | 2009-08-20 | Toyota Motor Corp | Manufacturing method of electrode foil for nonaqueous electrolyte battery, and manufacturing method of electrode plate for nonaqueous electrolyte battery |
| WO2010004398A1 (en) * | 2008-07-11 | 2010-01-14 | Toyota Jidosha Kabushiki Kaisha | Battery-dedicated electrode foil, positive electrode plate, battery, vehicle, and battery-equipped appliance, and manufacture method for the battery-dedicated electrode foil, and manufacture method of the positive electrode plate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108649192A (en) * | 2018-04-08 | 2018-10-12 | 河南大学 | A method of it is tested based on contact angle and prepares the uniform decorative layer of electrode material surface |
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| Publication number | Publication date |
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| CN102763253B (en) | 2016-02-17 |
| WO2011105451A1 (en) | 2011-09-01 |
| JP5097260B2 (en) | 2012-12-12 |
| JP2011198743A (en) | 2011-10-06 |
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