CN102420339A - Lithium secondary battery possessing stress relaxation layer - Google Patents
Lithium secondary battery possessing stress relaxation layer Download PDFInfo
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- CN102420339A CN102420339A CN2011102603315A CN201110260331A CN102420339A CN 102420339 A CN102420339 A CN 102420339A CN 2011102603315 A CN2011102603315 A CN 2011102603315A CN 201110260331 A CN201110260331 A CN 201110260331A CN 102420339 A CN102420339 A CN 102420339A
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- relaxation layer
- stress relaxation
- stress
- secondary battery
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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
- H01M4/70—Carriers or collectors characterised by shape or form
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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
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
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- Cell Electrode Carriers And Collectors (AREA)
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a high-capacity lithium secondary battery which relaxes the stress on the electrode to prevent the falling or loosing of the electrode. The degradation of the lithium secondary battery caused by the charging-discharging circulation is not serious. The lithium secondary battery includes a winding group which is formed by winding the anode and the cathode together, and a baffle plate is arranged between the anode and the cathode. The anode and the cathode can absorb and discharge lithium ions reversibly. The lithium secondary battery also includes an organic electrolyte solution which dissolves the electrolytes containing the lithium ions. The cathode s formed by coating an agent-mixed layer which contains an active material and an adhesive on a collector electrode. The collector electrode is formed by arranging the stress relaxation layer possessing the inner stress on at least one side of a surface or the back of a copper foil.
Description
Technical field
The present invention relates to have high input and output performance and be suitable for the new lithium secondary battery of hybrid electric motor vehicle etc.
Background technology
In recent years, in order to protect environment and to suppress global warmingization, expectation reduced carbon dioxide output.There is the practical application of hybrid electric motor vehicle (H EV) and electric motor vehicle (EV) etc. in method as reducing carbon dioxide output.As the energy of these motor vehicles that drive through motor, the secondary cell that can carry out charging and discharging repeatedly is necessary technology.Lithium secondary battery is because its operation voltage is high and obtain high output easily, therefore causes concern as the power supply of the motor vehicle that is driven by motor.In addition, the multifunction that portable phone etc. can move the electronic equipment of use makes progress year by year, and its consumes electric power increases together therewith.Therefore, small-sized, light weight and secondary cell capacious are developed in expectation.
For the high capacity of battery, need to use the big active material of theoretical capacity.For example, for negative electrode active material, the theoretical capacity of metal of Si, Sn etc. and lithium alloyage etc. is big, is preferable material.But the volumetric expansion the when negative electrode active material that theoretical capacity is big charges becomes big, between negative pole-collector body, produces stress.Consequently, electrode produces fold or lax, and perhaps active material is peeled off from collector body, thus the problem that exists cycle life to shorten.
To this problem several solutions have been proposed.In patent documentation 1, proposing has following method, that is, in the bend of electrode, make the concentration of iron in the active material layer of the inboard that is configured in negative electrode collector higher than the concentration of iron in the active material layer in the outside that is configured in negative electrode collector.In patent documentation 2, propose to form the method for the structure with stress mitigation portion, this stress mitigation portion is by the collector body curved surface continuous with respect to length direction constituted.
[patent documentation 1] TOHKEMY 2007-95569 communique
[patent documentation 2] TOHKEMY 2009-181831 communique
Yet, in the technology that above-mentioned patent documentation 1 is proposed, separately use two kinds of active materials and the time of needs coating, the problem that exists cost to rise.In addition, in the technology that above-mentioned patent documentation 2 is proposed,, there is the problem of the energy density reduction of battery because of have volume and the weight increase that stress mitigation portion collector body occupies in battery.
Summary of the invention
The present invention is in view of such problem and proposing, and its purpose is to provide a kind of electrode of lithium secondary cell and battery that improves the cycle life of lithium secondary battery and be suitable for hybrid electric motor vehicle or the portable set etc. of high power capacity.
Lithium rechargeable battery possesses: the coiling group, and it is through forming positive pole and negative pole across the dividing plate coiling, and said positive pole and negative pole can the occlusion of reversible ground be emitted lithium ion; Organic electrolyte; It has dissolved the electrolyte that contains said lithium ion; Wherein, Said negative pole is coated on the collector body through the mixture layer that will contain active material and adhesive and forms, and said collector body constitutes through the stress relaxation layer that surface or at least one side's setting in the back side at Copper Foil have internal stress.
Lithium secondary battery of the present invention can improve the cycle life of lithium secondary battery through relaxing the stress that between electrode composition layer and collector body, produces.
Description of drawings
Fig. 1 is the figure in the cross section of the secondary lithium batteries collector body that relates to of expression present embodiment.(embodiment 1)
Fig. 2 is the figure in the cross section of the secondary lithium batteries collector body that relates to of expression present embodiment.(embodiment 2)
Fig. 3 is the figure in the cross section of the secondary lithium batteries collector body that relates to of expression present embodiment.(embodiment 3)
Fig. 4 is the figure in the cross section of the secondary lithium batteries collector body that relates to of expression present embodiment.(embodiment 4)
Fig. 5 is the figure in the cross section of the secondary lithium batteries collector body that relates to of expression present embodiment.(embodiment 5)
Fig. 6 is the figure in the one-sided cross section of the lithium secondary battery that relates to of expression present embodiment.
Symbol description:
1 Copper Foil
2 first stress relaxation layers
3 second stress relaxation layers
101 positive electrode collectors
102 anode mixture layers
103 negative electrode collectors
104 anode mixture layers
107 dividing plates
109 negative wires
110 positive wires
111 anodal insulators (insulate)
112 negative pole insulators
113 negative battery housings
114 bed courses
115 positive battery lid
Embodiment
The present invention is characterized in that in order to relax the stress that between electrode composition layer and collector body, produces, the compression stress that the collector body outside is produced is bigger than the compression stress of the inboard generation of collector body.Through this method, can under the situation of the formation method that does not change active material layer, relax the stress that between electrode composition layer and collector body, produces, can suppress the fold of electrode or lax generation and active material peeling off from collector body.
Below, with reference to accompanying drawing, secondary lithium batteries collector body that execution mode of the present invention is related to and lithium secondary battery and their manufacturing side describe.
(structure of negative electrode for lithium secondary battery collector body)
The lithium battery that the execution mode of the present invention of expression shown in Fig. 1 relates to is with the cross-sectional schematic of the example of negative electrode collector.This collector body forms to has first stress relaxation layer 2 and has the structure of second stress relaxation layer 3 overleaf on the surface of Copper Foil 1.The stress of film is different with second stress relaxation layer at first stress relaxation layer, and the compression stress of the stress relaxation layer outside in the bend of electrode, becoming is big.As stress relaxation layer, can use with the film of copper as main component.The existence of this collector body stress relaxation layer and can to become the mode of protrusion with the outside at the bend of electrode crooked.On this collector body, form the mixture layer that contains active material, adhesive, electric conducting material etc., come as negative electrode for lithium secondary battery.
About membrane stress is the stress that film self has, and below the direction of power effect is described.Film has tensile stress and is meant that film is the state that stretches, and film self will shrink.On the contrary, film has compression stress and is meant that film is the state that shrinks, and film self will extend.In addition, be normally defined stress under situation about stretching for just, under the situation of compression for bearing.
In addition, on Copper Foil 1, produce stress through stress relaxation layer.Therefore, when effect has crooked power on Copper Foil 1, produce compression and this two side's that stretches power in the compression stress of stress relaxation layer or tensile stress in the inside of Copper Foil 1.
The lithium battery that the execution mode of the present invention of expression shown in Fig. 2 relates to is with the cross-sectional schematic of the example of negative electrode collector.This collector body forms to have on the two sides of Copper Foil 1 to be formed identical and has the structure of two stress relaxation layers of compression stress.The thicker of the stress relaxation layer that the thickness of the stress relaxation layer through the collector body in the bend that the makes electrode outside is more inboard than collector body, thus the compression stress that becomes the stress relaxation layer of inboard in the bend of electrode is diminished.This collector body can become the mode bending of protrusion with the outside at the bend of electrode because of the existence of the different stress relaxation layer of thickness.
The lithium battery that the execution mode of the present invention of expression shown in Fig. 3 relates to is with the cross-sectional schematic of the example of negative electrode collector.This collector body forms to have on the two sides of Copper Foil to be formed identical and has the structure of two stress relaxation layers of tensile stress.The thin thickness of the stress relaxation layer that the thickness of the stress relaxation layer through the collector body in the bend that the makes electrode outside is more inboard than collector body, thus the tensile stress that becomes inboard stress relaxation layer in the bend of electrode is become greatly.This collector body can become the mode bending of protrusion with the outside at the bend of electrode because of the existence of the different stress relaxation layer of thickness.
The lithium battery that the execution mode of the present invention of expression shown in Fig. 4 relates to is with the cross-sectional schematic of the example of negative electrode collector.This collector body forms the structure that possesses the stress relaxation layer with tensile stress in the one side of Copper Foil.Become big through the inboard tensile stress of the collector body in the bend that makes electrode, thereby can become the mode bending of protrusion with the outside at the bend of electrode.
The lithium battery that the execution mode of the present invention of expression shown in Fig. 5 relates to is with the cross-sectional schematic of the example of negative electrode collector.This collector body forms the structure that possesses the stress relaxation layer with compression stress in the one side of Copper Foil.Compression stress through the outside of the collector body in the bend that makes electrode becomes big, can become the mode bending of protrusion with the outside at the bend of electrode.
As stress relaxation layer, can use not occlusion to emit lithium and do not form the metal of the common collector body of formation of alloy with lithium.For example, enumerate copper, stainless steel, nickel, titanium or their alloy.
(manufacturing approach of negative electrode for lithium secondary battery collector body)
Lithium battery of the present invention is narrated with the manufacturing approach of negative electrode collector particularly.
As the Copper Foil that in the making of negative pole, uses, can use the Copper Foil that in the past in lithium secondary battery, used as collector body with collector body.Copper Foil can use any in electrolytic copper foil or the rolled copper foil.Do not limit especially for the thickness of Copper Foil, the roughness on surface or the chemical treatment on surfaces such as form, molecular modification, can use desired Copper Foil as required.Especially under the stable on heating situation of needs, as Copper Foil, the Copper Foil after can using copper alloy to copper and tin, silver, zirconium etc. to be rolled.The thickness of Copper Foil is preferably 8～20 μ m.When Copper Foil was too thin, it is difficult that operation becomes, and when too thick, the weight energy density of battery reduces.
Copper Foil preparing is under the situation of rolled copper foil, implements electrolytic degreasing attached to the oil content on surface in order to remove.This purified treatment is for example carried out through utilizing aqueous slkalis such as NaOH to implement the catholyte degreasing.Then, for the neutralization of the lip-deep alkali that remains in Copper Foil and removing of copper oxide-film and implement pickling processes.This pickling processes is carried out through impregnated in acidic aqueous solutions such as sulfuric acid.Liquid as pickling is used can use copper etchant solution.
Form processing as stress relaxation layer, can use damp process such as plating, electroless plating, vapor deposition, sputter, CVD dry processes such as (Chemical Vapor Deposition).
Damp process especially uses in the manufacturing process of Copper Foil, can form stress relaxation layer with low cost.Using under the situation of copper facing as stress relaxation layer,, carry out electrolytic treatments and form copper plate as negative electrode with Copper Foil being in the acid copper plating bath of main component with copper sulphate or sulfuric acid.The copper sulphate, the liquid composition of sulfuric acid bath, liquid temperature, the electrolytic condition that are used to be provided with copper plate can be selected in the scope of broad, do not limit especially, but preferably select from following scope.
Cupric sulfate pentahydrate: 20～300g/dm
3
Sulfuric acid: 10～200g/dm
3
Liquid temperature: 15～50 ℃
Plating current density: 0.5～30A/dm
2
The plating time: 1～60 second
Can in plating solution, add the additive that is used to make surface smoothing.As additive, can the combinations such as surfactants such as compound, polyethylene glycol or polypropylene glycol, chloride ion that 3-sulfydryl-1-sulfonic acid or two (3-sulfopropyl) disulphide etc. have a sulfydryl be used.In addition, can use the various copper facing of in printed wiring board making etc., using to use additive.Use additive as copper facing, can use the wild pharmacy system ト of society Star プ Le チ Na LS difficult to understand, the system カ パ one グ リ one system CLX of meltexInc society, society of weak former excellent Gilat makes CU-BRITE TH-RIII, attendes the system ス of village industry society Le カ Star プ EUC etc.
Preferred plating current density changes according to the surface configuration that will form.Under the situation that makes the surface smoothings beyond the particle part such as active material, preferred plating current density ratio boundary current density is little.Under the shaggy situation that makes beyond particle such as the active material part, preferred plating current density is more than the boundary current density.Because the high situation of plating current density improves productivity ratio, therefore more preferably the plating current density fixedly uprises in the scope of particle on the surface.As the bath of using in electroplating,, can also use and watt bathe nickel plating solutions such as (Watts bath), sulfamic acid bath now except the copper sulphate plating solution.
As stress relaxation layer, under the situation of the coating more than formation is two-layer, then form second copper plate.The liquid composition, liquid temperature, the electrolytic condition that are used to be provided with second coating can be selected in the scope of broad, limit especially, can use above-mentioned plating operation.
In the manufacturing approach of lithium battery with collector body of this execution mode, after final coating is set, can carry out reprocessing in order to obtain preferred characteristic.At first, form nickel coating or nickel alloy coating, then, form zinc-plated tunicle or galvanized alloy tunicle in order to improve thermal endurance for the oxidation that prevents copper.Afterwards, use the response type chromic acid salt liquid of trivalent chromium type and carry out trivalent chromium and change into processing.At last, in order to improve the connecting airtight property with adhesive, can form silane coupled processing layer as changing into the processing tunicle.
(structure of lithium secondary battery)
Lithium secondary battery of the present invention can be cylinder type, cascade type, Coin shape, and any in the card-type etc. limits especially, but as an example following, and the structure of convoluted lithium secondary battery is described.
The one-sided cutaway view of winding type battery shown in Fig. 6.
Lithium secondary battery has following structure, that is, electrode body is loaded in the battery case; And injection electrolyte; Afterwards battery case is sealed, wherein, electrode body is wound into helical form through the multilayer electrode that anodal and negative pole are cascaded across dividing plate and makes.In Fig. 6,109 is negative wire, and 110 is positive wire, and 111 is anodal insulator, and 112 is the negative pole insulator, and 114 is bed course, and 115 are the positive battery lid.
Can use the material of following narration in the above-mentioned lithium secondary battery of the present invention.
(positive pole)
Anodal through containing positive active material such as lithium composite xoide, being that the carbon material is that the anode mixture of master's conductive agent and adhesive is coated in and forms on the aluminium foil with graphite, preferably the emptying aperture volume of anode mixture layer is more than 25% and below 40% with respect to the volume of anode mixture layer.When the emptying aperture volume of anode mixture layer with respect to the volume of said anode mixture layer less than 25% the time; The amount that is impregnated into the electrolyte in the anode mixture layer reduces and the minimizing of lithium ion number; Therefore especially when low temperature, lithium ion can not get sufficient output to the undersupply of positive active material.On the other hand, when the ratio of emptying aperture volume surpassed 40%, the ratio of anode mixture reduced and causes the reduction of input and output.
Can use lithium composite xoide as positive active material.A lithium composite xoide preferred group accepted way of doing sth is by Li
αMn
xM1
yM2
zO
2The material of (in the formula, M1 is at least a for what from Co, Ni, select, and M2 is at least a for what from Co, Ni, Al, B, Fe, Mg, Cr, select, x+y+z=1,0＜α＜1.2,0.2≤x≤0.6,0.2≤y≤0.4,0.05≤z≤0.4) expression.
In addition, especially preferred M1 is Ni or Co, and M2 is Co or Ni.If LiMn
1/3Ni
1/3Co
1/3O
2Then more preferably.In the composition, when Ni for a long time, capacity can be obtained bigger, Co can improve the output under the low temperature for a long time, Mn can suppress material cost for a long time.In addition, add element and have effect cycle characteristics is stablized.In addition, can also be that general formula is LiM
xPO
4(M:Fe or Mn, 0.01≤X≤0.4) or LiMn
1-xM
xPO
4The symmetric orthorhombic phosphate cpd with space group Pmnb of (cation of the divalence beyond the M:Mn, 0.01≤X≤0.4).LiMn
1/3Ni
1/3Co
1/3O
2Low-temperature characteristics and cyclical stability high, especially be suitable as hybrid motor vehicle and use lithium battery material.As the adhesive that uses when the making of positive pole, for example, enumerated Kynoar (PVDF), polytetrafluoroethylene (PTFE), polyacrylic acid, gathered imide resin, butadiene-styrene rubber (SBR) etc.
As conductive agent, except for example graphite, acetylene black, carbon black, Ketjen black, CNT or derivatives thereof, the carbon fiber, also enumerated metal dust, metallic fiber etc.
(negative pole)
Negative pole is coated in through the cathode agent that will comprise negative electrode active material such as amorphous carbon, conductive agent, adhesive and forms on the Copper Foil, and the emptying aperture volume in the preferred anode mixture layer is more than 25% and below 40% with respect to the volume of anode mixture layer.When the emptying aperture volume of anode mixture layer with respect to the volume of anode mixture layer less than 25% the time, the amount that is impregnated into the electrolyte in the anode mixture layer reduces.Therefore, especially when low temperature, lithium ion is to the undersupply of negative electrode active material and can not get sufficient input.On the other hand, when the ratio of emptying aperture volume surpassed 40%, the ratio of cathode agent reduced and causes the reduction of input and output.
The material that uses as negative electrode active material have material with carbon element or with the compound of lithium alloyage, lithium metal etc.As material with carbon element; Have with native graphite; Complex carbon material; With resin raw materials such as epoxy or phenolic aldehyde, or will be the raw material Delanium that burns till manufacturing, amorphous carbon material etc. by the pitch based material that oil or coal obtain, wherein, complex carbon material obtains through the tunicle that the spraying process that on native graphite, forms the CVD method of utilizing dry type or wet type forms.As with the compound of lithium alloyage, the oxide or the nitride of tetrels such as silicon, germanium, tin are arranged.
Wherein, material with carbon element is conductivity height and low-temperature characteristics, cyclical stability aspect excellent material.In material with carbon element, the wide material of carbon wire side interlayer (d002) is good on fast charging and discharging, low-temperature characteristics, thereby preferred.But there is the problem that capacity reduces, efficiency for charge-discharge is low at the initial stage of charging in the wide material of d002, and therefore preferred d002 is below the 0.39nm, is again also such material with carbon element to be called doubtful anisotropic carbon (pseude isotropis carbon).
As the adhesive that uses when the making of negative pole, for example, row have Kynoar (PVDF), polytetrafluoroethylene (PTFE), polyacrylic acid, gather imide resin, butadiene-styrene rubber (SBR) etc.
As conductive agent, except for example graphite, acetylene black, carbon black, Ketjen black, CNT or derivatives thereof, the carbon fiber, also enumerated metal dust, metallic fiber etc.
(dividing plate)
As the dividing plate of nonaqueous electrolytic solution secondary battery, can use the dividing plate that uses in the known lithium secondary battery.For example, as dividing plate, enumerate microporosity film or nonwoven fabrics of polyolefin systems such as polyethylene, polypropylene etc.From the viewpoint of the high capacity of battery, the thickness of preferred separator is below the 20 μ m, more preferably below the 18 μ m.Through using the dividing plate of such thickness, can make the capacity of the unit volume of battery become big.But when dividing plate was too thin, it was insufficient and be easy to generate short circuit to damage isolation between operability or both positive and negative polarity, so the following 10 μ m that are limited to of preferred thickness.
(battery case)
Battery case can use the battery case that adopts in the known lithium secondary battery.For example, be the container of aluminum or stainless steel, battery cover can use laser welding in battery case or through be sealed in the battery cover of battery case via the curling sealing of filler.In addition, anodal and negative pole pass through glass or resinous insulator from vessel isolation in battery case.
(electrolyte)
As electrolyte, can use the nonaqueous electrolytic solution of the organic solvent system of in organic solvent, having dissolved lithium salts.
Organic solvent as electrolyte; Do not limit especially; But chain esters such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, carbonic acid first propyl ester have for example been enumerated; Or the high cyclic ester of dielectric constant such as ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, the perhaps mixed solvent of chain ester and cyclic ester especially can use with the chain ester to be main solvent and mixed solvent cyclic ester.
As the lithium salts that uses in the electrolyte, do not limit especially, but in inorganic lithium salt, can use LiPF
6, LiBF
4, LiClO
4, LiI, LiCl, LiBr etc., in addition, in organic lithium salt, can use LiB [OCOCF
3]
4, LiB [OCOCF
2CF
3]
4, LiPF
4(CF
3)
2, LiN (SO
2CF
3)
2, LiN (SO
2CF
2CF
3)
2Deng.From the stability of quality, the people's livelihood is with widely used LiPF in the battery
6Be special preferable material.
(manufacturing approach of lithium secondary battery)
As an example, the manufacturing approach to convoluted lithium secondary battery below describes.
In lithium composite xoide particle, add electric conducting materials such as graphite, acetylene black, carbon black and mix as positive active material; Add binding agent such as the PVDF be dissolved in N-N-methyl-2-2-pyrrolidone N-(NMP) equal solvent then and carry out mixing, thereby obtain anodal slip.Then, this slip is coated on the aluminum metallic foil, makes its drying afterwards and the making positive pole.
In as the graphitic carbon of negative electrode active material or soft carbon, add electric conducting materials such as carbon black, acetylene black and carbon fiber and mix.To wherein add as adhesive be dissolved in the PVDF among the NMP or be the SBR etc. of adhesive as rubber after carry out mixing, thereby obtain the negative pole slip.Then, this slip is coated on the Copper Foil, makes its drying afterwards and the making negative pole.
Above-mentioned positive pole and negative pole carry out drying after the two sides of electrode applies slip.And then make its densification and cut into desired shape through rolling processing and make electrode.Then, the lead wire that on above-mentioned electrode, is formed for making electric current to flow.Between above-mentioned positive pole and negative pole, sandwich the dividing plate of porous matter insulating material and they are reeled.When reeling,, reel towards the compression stress that produces in the collector body outside direction bigger than the compression stress that produces in the collector body inboard at the bend of electrode in order to relax the stress that between electrode composition layer and collector body, produces.Through this method, can relax the stress that between electrode composition layer and collector body, produces, can suppress the fold of electrode, lax generation and active material peeling off from collector body.In addition, behind coiling through keeping official hour at a certain temperature, thereby can make the difference of stress become big.Electrode behind the coiling is inserted in the battery container by stainless steel or aluminium moulding.Then, with lead wire with after battery container is connected, inject non-aqueous electrolyte, at last the battery container sealing is obtained lithium secondary battery.
(battery module)
As the form of using above-mentioned lithium secondary battery, enumerate the lithium secondary battery module that a plurality of batteries are connected in series.
Utilize embodiment, the present invention will be described in more detail.
(embodiment 1)
(1) making of negative electrode for lithium secondary battery collector body
It is the rolled copper foil of 9 μ m that the Copper Foil that becomes metal support uses the thickness contain tin 0.01 quality %.Surperficial in order to purify this rolled copper foil, and implemented electrolytic degreasing, pickling processes.Electrolytic degreasing is handled and is being contained NaOH 40g/dm
3, sodium carbonate 20g/dm
3The aqueous solution in 40 ℃ of temperature, current density 5A/dm
2Handled for 10 seconds.Pickling processes is containing sulfuric acid 150g/dm
3The aqueous solution in handled for 5 seconds with 25 ℃.Afterwards, utilize flowing water that this Copper Foil is washed.
Then, carry out electro-coppering at this copper foil surface.The copper plating solution uses and contains cupric sulfate pentahydrate 185g/dm
3, sulfuric acid 80g/dm
3, chloride ion 0.05g/dm
3, two (3-sulfopropyl) disulphide 0.001g/dm
3, polyethylene glycol 0.2g/dm
3The aqueous solution of (mean molecule quantity 1000).
The plating condition is with 30 ℃ of plating solution temperature, plating current density 15A/dm
2Carry out 9 second plating, the copper plate that forms 0.5 μ m is as first stress relaxation layer.
Then, this Copper Foil is washed, carried out nickel plating at the opposite face that has carried out electro-coppering.The nickel plating solution uses and contains nickel sulfamic acid 350g/dm
3, nickel chloride 5g/dm
3, boric acid 50g/dm
3, the system NFS-E5vol% of Japanese chemical industry society and be adjusted into the plating solution of 50 ℃ of temperature.The plating condition is with current density 10A/dm
2Carried out for 9 seconds and electroplate, the nickel coating that forms 0.5 μ m is as second stress relaxation layer.
Through above operation, can produce the negative electrode collector that is formed with stress relaxation layer.
(2) making of lithium secondary battery
Using amorphous carbon is that doubtful anisotropic carbon is used as negative electrode active material; Use carbon black (CB1) as electric conducting material; Use PVDF as adhesive, and the solid state component part by weight during with drying is doubtful anisotropic carbon: CB1: PVDF=88: 5: 7 mode uses NMP to modulate the negative material paste as solvent.
On the negative electrode collector 103 that this negative material paste coating is produced in (1), and 80 ℃ dry down, through the backer roll punching press, dry down and on negative electrode collector 103, form anode mixture layer 104 at 120 ℃.The ratio of the volume that the emptying aperture volume in the anode mixture layer is whole with respect to anode mixture layer is 35vol%.
Use LiMn
1/3Ni
1/3Co
1/3O
2As positive active material, use carbon black (CB2) and graphite (GF2) as electric conducting material, use PVDF as adhesive, and so that the ratio of the solid state component weight during drying is LiMn
1/3Ni
1/3Co
1/3O
2: CB2: GF2: PVDF=86: 2: 9: 3 mode uses NMP to modulate the positive electrode paste as solvent.
With this positive electrode paste coating to the aluminium foil that becomes positive electrode collector 101, and 80 ℃ down dry, through the backer roll punching press, dry down and on positive electrode collector 101, form anode mixture layer 102 at 120 ℃.The ratio of the volume that the emptying aperture volume of anode mixture layer is whole with respect to the anode mixture layer is 30vol%.
Between the electrode of producing, sandwich dividing plate 107, form the coiling group.When reeling, in order to relax the stress that between anode mixture layer and collector body, produces, inboard and second stress relaxation layer that becomes coiling body to first stress relaxation layer becomes the direction in the outside of coiling body and reels.Afterwards, this coiling body is inserted negative battery housing 113, and inject electrolyte.Afterwards, the positive battery lid that bed course 114 has been installed 115 is anchored on negative battery housing 113 and it is sealed, thereby produce the winding type battery of diameter 18mm, length 65mm.It is the LiPF that has dissolved 1.0 mol in 1: 2 the mixed solvent that electrolyte uses volume ratio at ethylene carbonate (EC), dimethyl carbonate (DMC)
6And the solution that obtains.
(embodiment 2)
(1) making of negative electrode for lithium secondary battery collector body
On the basis of the making of the negative electrode for lithium secondary battery of embodiment 1; The electrolytic copper foil of used thickness 12 μ m is as Copper Foil; And to produce first stress relaxation layer that thickness is 0.2 μ m, in addition to make negative electrode collector with embodiment 1 same sequential system with the same method of second stress relaxation layer.The thickness of nickel plating is because of the attenuation that shortens of plating time.Through above operation, can produce the negative electrode collector that is formed with stress relaxation layer.
(2) making of lithium secondary battery
The negative electrode collector of making in above-mentioned except using (1), to go out winding type battery with embodiment 1 same sequentially built.
(embodiment 3)
(1) making of negative electrode for lithium secondary battery collector body
On the basis of the making of the negative electrode for lithium secondary battery of embodiment 1; The electrolytic copper foil of used thickness 12 μ m is as Copper Foil; And to produce second stress relaxation layer that thickness is 0.1 μ m with the same method of first stress relaxation layer, in addition with embodiment 1 same sequential system make negative electrode collector.Copper-plated thickness is because of the attenuation that shortens of plating time.Through above operation, can produce the negative electrode collector that is formed with stress relaxation layer.
(2) making of lithium secondary battery
The negative electrode collector of making in above-mentioned except using (1), to go out winding type battery with embodiment 1 same sequentially built.
(embodiment 4)
(1) making of negative electrode for lithium secondary battery collector body
On the basis of the making of the negative electrode for lithium secondary battery of embodiment 1, the rolled copper foil of used thickness 18 μ m does not form second stress relaxation layer as Copper Foil, in addition to make negative electrode collector with embodiment 1 same sequential system.Through above operation, can produce the negative electrode collector that is formed with stress relaxation layer.
(2) making of lithium secondary battery
The negative electrode collector of making in above-mentioned except using (1), to go out winding type battery with embodiment 1 same sequentially built.
(embodiment 5)
(1) making of negative electrode for lithium secondary battery collector body
On the basis of the making of the negative electrode for lithium secondary battery of embodiment 1, the rolled copper foil of used thickness 18 μ m is as Copper Foil, and do not form first stress relaxation layer, in addition to make negative electrode collector with embodiment 1 same sequential system.Through above operation, can produce the negative electrode collector that is formed with stress relaxation layer.
(2) making of lithium secondary battery
The negative electrode collector of making in above-mentioned except using (1), to go out winding type battery with embodiment 1 same sequentially built.
(comparative example 1)
(1) making of negative electrode for lithium secondary battery collector body
On the basis of the making of the negative electrode for lithium secondary battery of embodiment 1, except not forming stress relaxation layer, to make negative electrode collector with embodiment 1 same sequential system.
(2) making of lithium secondary battery
The negative electrode collector of making in above-mentioned except using (1), to go out winding type battery with embodiment 1 same sequentially built.
(comparative example 2)
(1) making of negative electrode for lithium secondary battery collector body
On the basis of the making of the negative electrode for lithium secondary battery of embodiment 2, except not forming stress relaxation layer, to make negative electrode collector with embodiment 1 same sequential system.
(2) making of lithium secondary battery
The negative electrode collector of making in above-mentioned except using (1), to go out winding type battery with embodiment 1 same sequentially built.
(evaluation method)
(evaluation of stress)
The stress of stress relaxation layer utilizes rattan to change into society's system belt electro-deposition stress test device and estimates.On the test tape of Be-Cu system and thickness 48 μ m, form each stress relaxation layer, obtain stress according to the amount of warpage of test tape.
(cell evaluation)
Variation to the discharge capacity under 25 ℃ of winding type battery shown in Figure 6 is estimated.The presented higher holdup as maximum discharge capacity be 100% and 10000 the circulation after rate of change estimate.Before estimating the presented higher holdup, this winding type battery is carried out 5 hours constant-current constant-voltage charging with 0.3C, make it reach upper voltage limit 4.2V, discharge into lower voltage limit 2.7V afterwards, carry out repeatedly discharging and recharging for three times and carry out initialization.The discharge capacity of battery is discharged to lower voltage limit 2.7V and measures through after being charged to upper voltage limit 4.2V with 0.3C.
Evaluation result at the presented higher holdup of each embodiment and comparative example shown in the table 1.
[table 1]
Table 1
Can know by table 1, through having stress relaxation layer, thereby can improve the presented higher holdup at the current collection copper foil surface.
Lithium secondary battery of the present invention is compared with existing lithium secondary battery, also can not damage capacity even carry out charge and discharge cycles repeatedly.Therefore; Lithium secondary battery of the present invention can extensively utilize as the power supply of the electronic control system of the power supply of hybrid motor vehicle, motor vehicle or stand-by power supply, also is suitable as the power supply of commercial plants such as electric tool, forklift, the power supply of portable set.
Claims (6)
1. lithium rechargeable battery, it possesses:
The coiling group, it is through forming positive pole and negative pole across the dividing plate coiling, and said positive pole and negative pole can the occlusion of reversible ground be emitted lithium ion;
Organic electrolyte, it has dissolved the electrolyte that contains said lithium ion,
Said lithium rechargeable battery is characterised in that,
Said negative pole is coated to collector body through the mixture layer that will contain active material and adhesive and forms,
Said collector body constitutes through the stress relaxation layer that surface or at least one side's setting in the back side at Copper Foil have internal stress.
2. lithium secondary battery according to claim 1 is characterized in that,
Said stress relaxation layer is formed on bend inboard of said collector body and has tensile stress.
3. lithium secondary battery according to claim 1 is characterized in that,
Said stress relaxation layer be formed on said collector body bend the outside and have compression stress.
4. lithium secondary battery according to claim 1 is characterized in that,
Said stress relaxation layer is made up of first stress relaxation layer and second stress relaxation layer,
Said first stress relaxation layer is formed on bend inboard of said collector body and has tensile stress,
Said second stress relaxation layer be formed on said collector body bend the outside and have compression stress.
5. lithium secondary battery according to claim 1 is characterized in that,
Said stress relaxation layer is made up of first stress relaxation layer with same composition and second stress relaxation layer,
Said first stress relaxation layer is formed on bend inboard of said collector body and has compression stress,
Said second stress relaxation layer be formed on said collector body bend the outside and have compression stress,
The thickness of said second stress relaxation layer is than the thicker of said first stress relaxation layer.
6. lithium secondary battery according to claim 1 is characterized in that,
Said stress relaxation layer is made up of first stress relaxation layer with same composition and second stress relaxation layer,
Said first stress relaxation layer is formed on bend inboard of said collector body and has tensile stress,
Said second stress relaxation layer be formed on said collector body bend the outside and have tensile stress,
The thickness of said second stress relaxation layer is than the thin thickness of said first stress relaxation layer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010216331A JP5372881B2 (en) | 2010-09-28 | 2010-09-28 | Lithium secondary battery having a stress relaxation layer |
| JP2010-216331 | 2010-09-28 |
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| CN102420339A true CN102420339A (en) | 2012-04-18 |
| CN102420339B CN102420339B (en) | 2014-12-10 |
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| KR (1) | KR101311076B1 (en) |
| CN (1) | CN102420339B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9806334B2 (en) | 2012-11-02 | 2017-10-31 | Semiconductor Energy Laboratory Co., Ltd. | Power storage device electrode, method for forming the same, power storage device, and electrical device |
| CN108432027A (en) * | 2015-12-25 | 2018-08-21 | 株式会社丰田自动织机 | The manufacturing method of electrical storage device and electrode unit |
| CN110380136A (en) * | 2019-08-29 | 2019-10-25 | 东莞塔菲尔新能源科技有限公司 | A kind of winding battery core, preparation process and lithium ion battery |
| CN112103548A (en) * | 2019-06-18 | 2020-12-18 | 北京小米移动软件有限公司 | Power supply module and electronic device |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140108380A (en) * | 2013-02-25 | 2014-09-11 | 엠케이전자 주식회사 | Secondary battery including silicon-metal alloy-based negative active material |
| KR102297634B1 (en) | 2013-04-19 | 2021-09-02 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Secondary battery and a method for fabricating the same |
| KR101812574B1 (en) * | 2014-07-24 | 2017-12-27 | 주식회사 엘지화학 | Curved-shaped Electrode Stack Having Elastic Restoring Force And Battery Cell Comprising The Same |
| KR102276426B1 (en) * | 2015-01-08 | 2021-07-12 | 삼성전자주식회사 | Secondary battery having high rate capability and high energy density |
| KR102234212B1 (en) * | 2015-11-03 | 2021-03-31 | 주식회사 엘지화학 | Electrode Controllable Bending Structure and Electrochemical Cell Comprising the Same |
| JP6615660B2 (en) * | 2016-03-17 | 2019-12-04 | 株式会社東芝 | Non-aqueous electrolyte battery, battery pack and vehicle |
| KR102040819B1 (en) * | 2016-10-07 | 2019-11-06 | 주식회사 엘지화학 | electrode unit and manufacturing the same |
| PL3582295T3 (en) * | 2017-10-25 | 2023-02-27 | Lg Energy Solution, Ltd. | One-sided electrode with reduced twisting for a secondary battery, and method for producing same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007323901A (en) * | 2006-05-31 | 2007-12-13 | Sony Corp | Battery electrode and its manufacturing method, and secondary battery |
| CN101288197A (en) * | 2004-12-28 | 2008-10-15 | 波士顿电力公司 | Lithium-ion secondary battery |
| CN101393981A (en) * | 2007-09-18 | 2009-03-25 | 深圳市比克电池有限公司 | Lithium ionic cell pole piece, production thereof, and lithium ionic battery produced by using the pole piece |
| WO2009141691A2 (en) * | 2008-05-22 | 2009-11-26 | Toyota Jidosha Kabushiki Kaisha | Secondary-battery current collector foil and method of manufacturing the same |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0992274A (en) * | 1995-09-27 | 1997-04-04 | Shin Kobe Electric Mach Co Ltd | Winding type battery electrode plate |
| CA2202604C (en) | 1997-04-14 | 2000-12-26 | Hydro-Quebec | Dense alloy anode strip with local stress relief |
| JP4967267B2 (en) * | 2005-07-19 | 2012-07-04 | パナソニック株式会社 | Laminated metal foil for lithium ion battery and lithium ion battery using the same |
| JP4953610B2 (en) * | 2005-09-29 | 2012-06-13 | 三洋電機株式会社 | Lithium secondary battery |
| JP4918243B2 (en) * | 2005-10-06 | 2012-04-18 | 三洋電機株式会社 | Nonaqueous electrolyte secondary battery |
| JP2009181831A (en) * | 2008-01-31 | 2009-08-13 | Panasonic Corp | Electrode plate for nonaqueous secondary battery and nonaqueous secondary battery using the same |
| JP2010062049A (en) | 2008-09-05 | 2010-03-18 | Panasonic Corp | Nonaqueous secondary battery |
-
2010
- 2010-09-28 JP JP2010216331A patent/JP5372881B2/en not_active Expired - Fee Related
-
2011
- 2011-09-02 KR KR1020110088802A patent/KR101311076B1/en not_active IP Right Cessation
- 2011-09-05 CN CN201110260331.5A patent/CN102420339B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101288197A (en) * | 2004-12-28 | 2008-10-15 | 波士顿电力公司 | Lithium-ion secondary battery |
| JP2007323901A (en) * | 2006-05-31 | 2007-12-13 | Sony Corp | Battery electrode and its manufacturing method, and secondary battery |
| CN101393981A (en) * | 2007-09-18 | 2009-03-25 | 深圳市比克电池有限公司 | Lithium ionic cell pole piece, production thereof, and lithium ionic battery produced by using the pole piece |
| WO2009141691A2 (en) * | 2008-05-22 | 2009-11-26 | Toyota Jidosha Kabushiki Kaisha | Secondary-battery current collector foil and method of manufacturing the same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9806334B2 (en) | 2012-11-02 | 2017-10-31 | Semiconductor Energy Laboratory Co., Ltd. | Power storage device electrode, method for forming the same, power storage device, and electrical device |
| CN108432027A (en) * | 2015-12-25 | 2018-08-21 | 株式会社丰田自动织机 | The manufacturing method of electrical storage device and electrode unit |
| CN108432027B (en) * | 2015-12-25 | 2021-02-02 | 株式会社丰田自动织机 | Power storage device and method for manufacturing electrode unit |
| CN112103548A (en) * | 2019-06-18 | 2020-12-18 | 北京小米移动软件有限公司 | Power supply module and electronic device |
| CN110380136A (en) * | 2019-08-29 | 2019-10-25 | 东莞塔菲尔新能源科技有限公司 | A kind of winding battery core, preparation process and lithium ion battery |
Also Published As
| Publication number | Publication date |
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| JP5372881B2 (en) | 2013-12-18 |
| KR20120032413A (en) | 2012-04-05 |
| KR101311076B1 (en) | 2013-09-25 |
| JP2012074166A (en) | 2012-04-12 |
| CN102420339B (en) | 2014-12-10 |
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