CN104393231A - Electrode for secondary battery, preparation thereof, and secondary battery and cable-type secondary battery comprising the same - Google Patents

Electrode for secondary battery, preparation thereof, and secondary battery and cable-type secondary battery comprising the same Download PDF

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Publication number
CN104393231A
CN104393231A CN201410191341.1A CN201410191341A CN104393231A CN 104393231 A CN104393231 A CN 104393231A CN 201410191341 A CN201410191341 A CN 201410191341A CN 104393231 A CN104393231 A CN 104393231A
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China
Prior art keywords
electrode
secondary battery
cable type
polymer
type rechargeable
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CN201410191341.1A
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CN104393231B (en
Inventor
权友涵
郑惠兰
金银卿
金帝映
金忍哲
金孝美
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LG Energy Solution Ltd
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LG Chemical Co Ltd
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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
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Abstract

The invention relates to an electrode for a secondary battery, preparation thereof, and a secondary battery and a cable-type secondary battery comprising the same. The electrode for a secondary battery, comprising a current collector; an electrode active material layer formed on one surface of the current collector; a porous polymer layer formed on the electrode active material layer; and a first porous supporting layer formed on the porous polymer layer. The sheet-form electrode for a secondary battery according to the present disclosure has supporting layers on at least one of surfaces thereof to exhibit surprisingly improved flexibility and prevent the release of the electrode active material layer from a current collector even if intense external forces are applied to the electrode, thereby preventing the decrease of battery capacity and improving the cycle life characteristic of the battery.

Description

Electrode for secondary battery, its preparation and comprise its secondary cell and cable Type Rechargeable Battery
The cross reference of related application
This application claims the priority of No. 10-2013-0051566, the korean patent application submitted in Korea S on May 7th, 2013, be incorporated herein by reference to by its content.
Technical field
The present invention relates to a kind of electrode for secondary battery, relate more specifically to prevent electrode active material layers from coming off and there is the electrode for secondary battery of the flexibility of improvement, prepare the method for described electrode and comprise secondary cell and the cable Type Rechargeable Battery of described electrode.
Background technology
Secondary cell is also can change into electric energy when needed with the device of generating with chemical species storage power.Also it secondary cell is called rechargeable battery, because can recharge repeatedly.Common secondary cell comprises lead accumulator, NiCd battery, NiMH storage battery, Li ion battery, Li ion polymer cell etc.When compared with disposable primary cell, secondary cell is not only effective more economically, and is more eco-friendly.
At present secondary cell is used for the application needing low electric power, such as, for making the equipment, mobile device, instrument, uninterrupted power supply etc. of vehicle launch.Recently, the development along with wireless communication technology causes the universal of mobile device, and even causes the mobile of multiple conventional equipment, sharply increases the demand of secondary cell.Also secondary cell is used for eco-friendly vehicle of future generation as in motor vehicle driven by mixed power and motor vehicle to reduce costs with weight and to increase useful life of vehicle.
Usually, secondary cell has cylindrical, prismatic or bag shape.This is relevant to the manufacture method of secondary cell, is arranged on by the electrode assemblie be made up of in the process in the bag shape shell of cylindrical or prismatic metal shell or aluminum-laminated sheets, and utilizes electrolyte to fill described shell negative pole, positive pole and barrier film.Because the predetermined installing space in the method for electrode assemblie is necessary, so cylindrical, the prismatic or bag shape of secondary cell is a kind of restriction when developing the mobile device of various shape.Therefore, need that there is the secondary cell that shape is easy to the new construction adapted to.
In order to meet the need, propose the very large cable-type battery of the exploitation ratio of length to cross-sectional diameter.Described cable-type battery is being easy to while experiencing stress owing to causing the external force of change of shape change of shape occurs.In addition, the electrode active material layers of cable-type battery may come off because the fast volume during charging and discharging process expands.According to these reasons, the capacity of battery can decline and its cycle life characteristics can deterioration.
By improving the amount of the adhesive used in electrode active material layers with bending or providing flexible during distortion, can address this is that to a certain extent.But the amount of binder improved in electrode active material layers causes electrode resistance to raise and deterioration.In addition, when applying strong external force, such as, when being folded completely by electrode, even if the quantitative change of adhesive is large, still coming off of electrode active material layers can not be prevented.Therefore, the method is not enough to address this is that.
Summary of the invention
The present invention is devised in order to solve the problem of correlation technique, therefore the present invention relates to and a kind of electrode for secondary battery is provided, prepare the method for described electrode and comprise secondary cell and the cable Type Rechargeable Battery of described electrode, described electrode for secondary battery can alleviate crackle in the electrode active material layers caused by external force and produce, even and if there is serious crackle and still can prevent electrode active material layers from coming off from current-collector.
According to an aspect of the present invention, the electrode for secondary battery of a kind of form is provided, comprises: current-collector; Electrode active material layers, it is formed on a surface of described current-collector; Porous polymeric nitride layer, it is formed in described electrode active material layers; First porous support layer, it is formed in described porous polymeric nitride layer.
Described current-collector can by making as follows: stainless steel, aluminium, nickel, titanium, sintered carbon or copper; In its surface with the stainless steel that carbon, nickel, titanium or silver processed; Aluminium-cadmium alloy; In its surface with the non-conductive polymer of electric conducting material process; Conducting polymer; Comprise Ni, Al, A u, Ag, Pd/Ag, Cr, Ta, Cu, Ba or ITO the metal paste of metal dust; Or comprise the carbon paste cream of the carbon dust of graphite, carbon black or carbon nano-tube.
In addition, described current-collector can be the form of mesh.
In addition, described current-collector can also comprise the priming coat be made up of electric conducting material and adhesive.
Described electric conducting material can comprise and is selected from following any one: carbon black, acetylene black, Ketjen black, carbon fiber, carbon nano-tube, Graphene and composition thereof.
Described adhesive can be selected from polyvinylidene fluoride (PVDF), polyvinylidene fluoride-altogether-hexafluoropropylene, polyvinylidene fluoride-altogether-trichloroethylene, butyl polyacrylate, polymethyl methacrylate, polyacrylonitrile, PVP, polyvinyl acetate, polyethylene-altogether-vinyl acetate, poly(ethylene oxide), polyarylate, cellulose acetate, cellulose acetate-butyrate, cellulose-acetate propionate, cyanoethyl pullulan, cyanoethyl polyvinylalcohol, cyanethyl cellulose, cyanoethyl sucrose, Propiram, carboxymethyl cellulose, butadiene-styrene rubber, acrylonitrile-butadiene-styrene copolymer, polyimides and composition thereof.
In addition, described current-collector can have multiple recess.
Described multiple recess patterning or discontinuously patterning continuously at least one surface thereof.
Meanwhile, described first supporting layer can be perforated membrane or the nonwoven fabrics of mesh form.
Described first supporting layer can be made by being selected from following any one: high density polyethylene (HDPE), low density polyethylene (LDPE), LLDPE, ultra-high molecular weight polyethylene, polypropylene, PETG, polybutylene terephthalate (PBT), polyester, polyacetals, polyamide, Merlon, polyimides, polyether-ether-ketone, polyether sulfone, polyphenylene oxide, polyphenylene sulfide, PEN and composition thereof.
In addition, described first supporting layer can also comprise the conductive material coating with electric conducting material and adhesive in its surface.
In described conductive material coating, described electric conducting material and described adhesive can exist with the weight ratio of 80:20 ~ 99:1.
Described electric conducting material can comprise and is selected from following any one: carbon black, acetylene black, Ketjen black, carbon fiber, carbon nano-tube, Graphene and composition thereof.
Meanwhile, described porous polymeric nitride layer can have the aperture of 0.01 ~ 10 μm and the porosity of 5 ~ 95%.
Described porous polymeric nitride layer can comprise linear polymer, oxide-base linear polymer or its mixture with polarity.
The described linear polymer with polarity can be selected from: polyacrylonitrile, polyvinyl chloride, polyvinylidene fluoride (PVDF), polyvinylidene fluoride-altogether-hexafluoropropylene, polyvinylidene fluoride-altogether-trichloroethylene, polymine, polymethyl methacrylate, butyl polyacrylate, PVP, polyvinyl acetate, polyethylene-altogether-vinyl acetate, polyarylate, PPTA and composition thereof.
Described oxide-base linear polymer can be selected from: poly(ethylene oxide), PPOX, polyformaldehyde, dimethyl silicone polymer and composition thereof.
Meanwhile, described electrode for secondary battery can comprise porous coating further, and described porous coating is formed on the first porous support layer by the mixture of inorganic particulate and binder polymer.
In addition, described electrode for secondary battery can comprise the second supporting layer be formed on another surface of described current-collector further.
Described second supporting layer can be polymer film.Described polymer film can by making as follows: polyolefin, polyester, polyimides, polyamide and composition thereof.
Meanwhile, when described electrode for secondary battery is used as negative pole, described electrode active material layers can comprise and is selected from following active material: native graphite, Delanium or carbonaceous material; Lithium-titanium composite oxide (LTO), and the metal (Me) comprising Si, Sn, Li, Zn, Mg, Cd, Ce, Ni and Fe; The alloy of described metal; The oxide (MeOx) of described metal; The compound of described metal and carbon; And their mixture, and when described electrode for secondary battery is used as positive pole, described electrode active material layers can comprise and is selected from following active material: LiCoO 2, LiNiO 2, LiMn 2o 4, LiCoPO 4, LiFePO 4, LiNiMnCoO 2, LiNi 1-x-y-zco xm1 ym2 zo 2(wherein M1 and M2 is selected from independently of one another: Al, Ni, Co, Fe, Mn, V, Cr, Ti, W, Ta, Mg and Mo, and x, y and z are independently of one another for forming the atomic fraction of the element of oxide, wherein 0≤x<0.5,0≤y<0.5,0≤z<0.5, and x+y+z≤1) and composition thereof.
According to another aspect of the present invention, a kind of method preparing the electrode for secondary battery of sheet form is provided, comprise: the slurry containing electrode active material is coated on a surface of current-collector by (S1), dry subsequently, thus form electrode active material layers; (S2) polymer solution containing polymer is coated in described electrode active material layers; (S3) on polymer solution, the first porous support layer is formed; And (S4) compresses to form porous polymeric nitride layer to the obtained thing obtained in step (S3), described porous polymeric nitride layer is bonded between described electrode active material layers with described first porous support layer mutually integrated.
Described polymer solution can comprise adhesive ingredients.
Herein, in step (S3), before adhesive ingredients is cured, polymer solution can form the first porous support layer.
In addition, in step (S4), compress to form porous polymeric nitride layer to the obtained thing obtained in step (S3) by coating blade, described porous polymeric nitride layer is bonded between described electrode active material layers with described first porous support layer mutually integrated.
In addition, described method can be included in before step (S1) or after step (S4) further, forms the second supporting layer by carrying out on the surface compressing at another of current-collector.
In addition, according to also another aspect of the present invention, a kind of cable Type Rechargeable Battery is provided, comprises: interior electrode; Separator, its outer surface around described interior electrode is to prevent the short circuit between electrode; And external electrode, its by spirally to reel thus around described separator outer surface and formed, at least one in wherein said interior electrode and described external electrode above-mentionedly to be formed according to electrode for secondary battery of the present invention by using.
Herein, described external electrode can be formed with the strips of uniaxial extension.
In addition, described external electrode can spirally winding, thus not overlapping or overlapping on its width.
In addition, described interior electrode can centered by part be empty hollow structure.
Herein, described interior electrode can comprise one or more electrode for secondary battery spirally reeled.
Described interior electrode can be provided with the core of interior current-collector within it, and for supplying the core of lithium ion, it comprises electrolyte; Or the core of filling.
The described core for supplying lithium ion can comprise gel polymer electrolyte and support, or can comprise liquid electrolyte and porous carrier.
Describedly can be selected from for supplying the electrolyte used in the core of lithium ion: the nonaqueous electrolytic solution using ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate (VC), diethyl carbonate (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), methyl formate (MF), gamma-butyrolacton (γ-BL), sulfolane, methyl acetate (MA) or methyl propionate (MP); Use the gel polymer electrolyte of PEO, PVdF, PVdF-HFP, PMMA, PAN or PVAc; And the solid electrolyte of use PEO, PPOX (PPO), polymine (PEI, polyether imine), poly-ethyl sulfide (PES) or polyvinyl acetate (PVAc).
Described electrolyte also can comprise lithium salts, and described lithium salts can be selected from: LiCl, LiBr, LiI, LiClO 4, LiBF 4, LiB 10cl 10, LiPF 6, LiCF 3sO 3, LiCF 3cO 2, LiAsF 6, LiSbF 6, LiAlCl 4, CH 3sO 3li, CF 3sO 3li, (CF 3sO 2) 2nLi, chloroborane lithium, lower aliphatic lithium carbonate, tetraphenylboronic acid lithium and composition thereof.
Described interior electrode can be negative pole or positive pole, and described external electrode can be the negative or positive electrode corresponding with described interior electrode.
Meanwhile, described separator can be dielectric substrate or barrier film.
Described dielectric substrate can comprise and is selected from following electrolyte: the gel polymer electrolyte using PEO, PVdF, PMMA, PVdF-HFP, PAN or PVAc; With the solid electrolyte of use PEO, PPOX (PPO), polymine (PEI), poly-ethyl sulfide (PES) or polyvinyl acetate (PVAc).
Described dielectric substrate also can comprise lithium salts, and described lithium salts can be selected from: LiCl, LiBr, LiI, LiClO 4, LiBF 4, LiB 10cl 10, LiPF 6, LiCF 3sO 3, LiCF 3cO 2, LiAsF 6, LiSbF 6, LiAlCl 4, CH 3sO 3li, CF 3sO 3li, (CF 3sO 2) 2nLi, chloroborane lithium, lower aliphatic lithium carbonate, tetraphenylboronic acid lithium and composition thereof.
Described barrier film can be: the porous polymer matrix be made up of the polyolefin polymers being selected from Alathon, Noblen, ethylene-butene copolymer, ethylene-hexene co-polymers and ethylene-methyl acrylate copolymer; The porous polymer matrix be made up of the polymer being selected from polyester, polyacetals, polyamide, Merlon, polyimides, polyether-ether-ketone, polyether sulfone, polyphenylene oxide, polyphenylene sulfide and PEN; The porous substrate be made up of the mixture of inorganic particulate and binder polymer; Or as lower diaphragm plate, it has the porous coating be formed at least one surface of described porous polymer matrix, and comprises inorganic particulate and binder polymer.
In addition, according to an also aspect of the present invention, a kind of cable Type Rechargeable Battery is provided, comprises:
For supplying the core of lithium ion, it comprises electrolyte;
Interior electrode, it around the outer surface of the described core for supplying lithium ion, and comprises current-collector and electrode active material layers;
Separator, its outer surface around described interior electrode is to prevent the short circuit between electrode; With
External electrode, its by spirally to reel thus around described separator outer surface and formed, and comprising current-collector and electrode active material layers, at least one in wherein said interior electrode and described external electrode is use above-mentioned electrode for secondary battery according to the present invention to be formed.
In addition, according to an also aspect of the present invention, a kind of cable Type Rechargeable Battery is provided, comprises:
The plural interior electrode be arranged parallel to each other;
Separator, its outer surface around described interior electrode is to prevent the short circuit between electrode; And
External electrode, its by spirally to reel thus around described separator outer surface and formed, at least one in wherein said interior electrode and described external electrode is use above-mentioned electrode for secondary battery according to the present invention to be formed.
In addition, according to also another aspect of the present invention, provide a kind of cable Type Rechargeable Battery, comprise: the plural core for supplying lithium ion, it comprises electrolyte; The plural interior electrode be arranged parallel to each other, in each electrode around each for supplying the outer surface of the core of lithium ion and comprising current-collector and electrode active material layers; Separator, its outer surface around described interior electrode is to prevent the short circuit between electrode; And external electrode, its by spirally to reel thus around described separator outer surface and formed, and comprising current-collector and electrode active material layers, at least one in wherein said interior electrode and described external electrode is use above-mentioned electrode for secondary battery according to the present invention to be formed.
Herein, described interior electrode can comprise one or more electrode for secondary battery spirally reeled.
Thus, the electrode for secondary battery according to of the present invention form has supporting layer at least one surface thereof, thus shows the flexibility shockingly improved.
When applying strong external force to electrode, such as, in the completely folding period of electrode, described supporting layer serves as buffering, even if thus the amount of adhesive in electrode active material layers do not increase, the crackle that still can reduce in electrode active material layers produces.Thereby, it is possible to prevent electrode active material layers from coming off from current-collector.
Therefore, the electrode of sheet form can prevent battery capacity from declining and can improve the cycle life characteristics of battery.
In addition, the electrode of sheet form has porous polymeric nitride layer to make it possible to electrolyte to introduce well in electrode active material layers on the end face of its electrode active material layers, suppresses the resistance of electrode to raise thus.
In addition, owing to providing porous support layer, so electrolyte can to immerse in the hole of porous support layer to suppress the resistance of battery to raise, degradation of cell performance is prevented thus.
Accompanying drawing explanation
Drawings show the preferred embodiment of the present invention, and be used from foregoing invention content one and understand technology purport of the present invention further.But the present invention can not be interpreted as being limited to accompanying drawing.
Fig. 1 display is according to the cross section of the electrode for secondary battery of the sheet form of one embodiment of the present invention.
Fig. 2 display is according to the cross section of the electrode for secondary battery of the sheet form of another execution mode of the present invention.
Fig. 3 schematically shows the method for preparation according to the electrode for secondary battery of the sheet form of one embodiment of the present invention.
Fig. 4 display is according to the surface of the current-collector of the mesh form of one embodiment of the present invention.
Fig. 5 schematically shows the surface with the current-collector of multiple recess according to one embodiment of the present invention.
Fig. 6 schematically shows the surface with the current-collector of multiple recess according to another execution mode of the present invention.
Fig. 7 is the photo of the cross section of the porous polymeric nitride layer that display is obtained by an embodiment of the invention.
Fig. 8 schematically shows the interior electrode of sheet form, and described interior electrode roll is around the outer surface of the core for supplying lithium ion in cable Type Rechargeable Battery of the present invention.
Fig. 9 is the decomposition diagram of the inside of the cable Type Rechargeable Battery schematically shown according to one embodiment of the present invention.
Figure 10 schematically shows according to the cross section with the cable Type Rechargeable Battery of multiple interior electrode of the present invention.
< Reference numeral >
10: current-collector 20: electrode active material layers
30: porous polymeric nitride layer 30 ': polymer solution
40: the first supporting layer 50: the second supporting layers
60: coating blade
100,200: cable Type Rechargeable Battery
110,210: for supplying the core of lithium ion
120,220: interior current-collector
130,230: interior electrode active material layers
140,240: porous polymeric nitride layer
150,250: the first supporting layers
160,260: the second supporting layers
170,270: separator
180,280: external electrode active material layer
190,290: outer current-collector
195,295: protective finish
Embodiment
Hereinafter, with reference to accompanying drawing, the preferred embodiment of the present invention is described in detail.Before explanation, should understand, should not be by the terminological interpretation used in specification and appended claims book be limited to common with implication that is dictionary, but should can carry out suitably defining to carry out on the basis of principle of best illustrated to term making the present inventor, according to the implication corresponding with technical elements of the present invention and concept, described term is made an explanation.
Therefore, explanation proposed herein, just only for illustration of the preferred embodiment of property object, is not intended to limit the scope of the invention, thus should be understood that can complete other equivalents and variant to it under the condition not deviating from the spirit and scope of the invention.
Fig. 1 and 2 display is according to the cross section of the electrode for secondary battery of the sheet form of one embodiment of the present invention, and Fig. 3 schematically shows the method for optimizing of preparation according to the electrode for secondary battery of the sheet form of one embodiment of the present invention.
With reference to figure 1-3, the electrode for secondary battery according to of the present invention form comprises: current-collector 10; Be formed in the electrode active material layers 20 on a surface of described current-collector 10; Be formed in the porous polymeric nitride layer 30 in described electrode active material layers 20; With the first porous support layer 40 be formed on the end face of described porous polymeric nitride layer 30.
Further, the second supporting layer 50 be formed on described another surface of current-collector 10 can be comprised further according to the electrode for secondary battery of sheet form of the present invention.
In order to make battery have flexibility, enough flexibilities should be had for the electrode in battery.But, when the regular cable type battery as a flexible battery example, electrode active material layers is easy to the stress because causing the external force of change of shape to cause or its fast volume when using the high power capacity negative active core-shell material containing Si, Sn etc. during charging and discharging process expands and comes off.This capacity deteriorated cycle life characteristics that reduce battery of coming off of electrode active material layers.As the trial overcoming this problem, improve the amount of adhesive in electrode active material layers to bend or to provide flexible during distortion.
But the amount of binder improved in electrode active material layers causes electrode resistance to raise and deterioration.In addition, when applying strong external force, such as, when being folded completely by electrode, even if the quantitative change of adhesive is large, still can not prevent electrode active material layers from coming off.Therefore, the method is not enough to address this is that.
In order to overcome the problems referred to above, the present inventor is by comprising formation the first supporting layer 40 on its outer surface and the second supporting layer 50 of being optionally formed in further on another surface of current-collector 10 and devising the electrode for secondary battery of sheet form.
Namely, even if electrode is bending or is being subject to External Force Acting during distortion, first supporting layer 40 with porosity still serves as the buffering that can alleviate the external force being applied to electrode active material layers 20, thus prevents electrode active material layers 20 from coming off, and improves the flexibility of electrode thus.In addition, when being formed with the second supporting layer 50 further, the short circuit of current-collector 10 can be suppressed, improving the flexibility of electrode thus further.
In addition, electrode of the present invention comprises porous polymeric nitride layer 30 using as making its mutually integrated adhesive for bonding the first porous support layer 40 and electrode active material layers, and described porous polymeric nitride layer 30 obtains by carrying out drying to polymer solution.
If common adhesive is used as described adhesive, then it serves as the antagonist of electrode and deterioration.On the contrary, the porous polymeric nitride layer 30 with loose structure makes it possible to electrolyte to introduce well in electrode active material layers, suppresses the rising of electrode resistance thus.
Hereinafter, with reference to Fig. 1-3, the method for the electrode for secondary battery preparing sheet form is described.Although illustrated the first situation forming the second supporting layer 50 below current-collector 10, then form porous polymeric nitride layer in Fig. 3, this has been one embodiment of the present of invention.Therefore, as hereafter mentioned, porous polymeric nitride layer can be formed under the condition not forming the second supporting layer.
First, by applying the slurry containing electrode active material on a surface of current-collector 10, then dry, thus form electrode active material layers 20 (S1).
Described current-collector 10 can by making as follows: stainless steel, aluminium, nickel, titanium, sintered carbon or copper; In its surface with the stainless steel that carbon, nickel, titanium or silver processed; Aluminium-cadmium alloy; In its surface with the non-conductive polymer of electric conducting material process; Conducting polymer; Comprise the metal paste of the metal dust of Ni, Al, Au, Ag, Pd/Ag, Cr, Ta, Cu, Ba or ITO; Or comprise the carbon paste cream of the carbon dust of graphite, carbon black or carbon nano-tube.
As mentioned above, when secondary cell experiences external force because of bending or distortion, electrode active material layers may come off from current-collector.In view of this reason, a large amount of adhesive component is used in electrode active material layers to provide flexible in the electrodes.But a large amount of adhesive may be easy to peel off, deterioration thus because of cause swelling of electrolyte.
Therefore, in order to improve the adhesivity between electrode active material layers and current-collector, described current-collector 10 can also comprise the priming coat be made up of electric conducting material and adhesive.
Described electric conducting material can comprise and is selected from following any one: carbon black, acetylene black, Ketjen black, carbon fiber, carbon nano-tube, Graphene and composition thereof, but is not limited thereto.
Described adhesive can be selected from: polyvinylidene fluoride (PVDF), polyvinylidene fluoride-altogether-hexafluoropropylene, polyvinylidene fluoride-altogether-trichloroethylene, butyl polyacrylate, polymethyl methacrylate, polyacrylonitrile, PVP, polyvinyl acetate, polyethylene-altogether-vinyl acetate, poly(ethylene oxide), polyarylate, cellulose acetate, cellulose acetate-butyrate, cellulose-acetate propionate, cyanoethyl pullulan, cyanoethyl polyvinylalcohol, cyanethyl cellulose, cyanoethyl sucrose, Propiram, carboxymethyl cellulose, butadiene-styrene rubber, acrylonitrile-butadiene-styrene copolymer, polyimides and composition thereof, but be not limited thereto.
In addition, with reference to figure 4 ~ 6, described current-collector 10 can be the form of mesh, and can have multiple recess at least one surface thereof, thus improves its surface area further.Described recess can patterning or discontinuously patterning continuously.That is, continuous patterned recess can be formed with being spaced from each other in the vertical, or multiple hole can be formed with the form of intermittent pattern.Described multiple hole can be circular or polygon.
In the present invention, when described electrode for secondary battery is used as negative pole, electrode active material layers can comprise and is selected from following active material: native graphite, Delanium or carbonaceous material; Lithium-titanium composite oxide (LTO), and the metal (Me) comprising Si, Sn, Li, Zn, Mg, Cd, Ce, Ni and Fe; The alloy of described metal; The oxide (MeOx) of described metal; The compound of described metal and carbon; And their mixture, and when described electrode for secondary battery is used as positive pole, electrode active material layers can comprise and is selected from following active material: LiCoO 2, LiNiO 2, LiMn 2o 4, LiCoPO 4, LiFePO 4, LiNiMnCoO 2, LiNi 1-x-y-zco xm1 ym2 zo 2(wherein M1 and M2 is selected from independently of one another: Al, Ni, Co, Fe, Mn, V, Cr, Ti, W, Ta, Mg and Mo, and x, y and z are independently of one another for forming the atomic fraction of the element of oxide, wherein 0≤x<0.5,0≤y<0.5,0≤z<0.5, and x+y+z≤1) and composition thereof.
Then, the polymer solution 30 ' containing polymer is coated on (S2) in electrode active material layers 20.
Described polymer can for having the linear polymer of polarity, oxide-base linear polymer or its mixture.
The described linear polymer with polarity can be selected from: polyacrylonitrile, polyvinyl chloride, polyvinylidene fluoride (PVDF), polyvinylidene fluoride-altogether-hexafluoropropylene, polyvinylidene fluoride-altogether-trichloroethylene, polymine, polymethyl methacrylate, butyl polyacrylate, PVP, polyvinyl acetate, polyethylene-altogether-vinyl acetate, polyarylate, PPTA and composition thereof.
Described oxide-base linear polymer can be selected from: poly(ethylene oxide), PPOX, polyformaldehyde, dimethyl silicone polymer and composition thereof.
Then, at upper formation first porous support layer 40 (S3) of the polymer solution (30) applied.
Meanwhile, described first supporting layer 40 can be perforated membrane or the nonwoven fabrics of mesh form.This loose structure makes it possible to be introduced by electrolyte in electrode active material layers 20 well, and described first supporting layer 40 self has excellent electrolyte infiltration and provides good ionic conductance, prevents electrode resistance from raising and finally preventing degradation of cell performance thus.
Described first supporting layer 40 can be made by being selected from following any one: high density polyethylene (HDPE), low density polyethylene (LDPE), LLDPE, ultra-high molecular weight polyethylene, polypropylene, PETG, polybutylene terephthalate (PBT), polyester, polyacetals, polyamide, Merlon, polyimides, polyether-ether-ketone, polyether sulfone, polyphenylene oxide, polyphenylene sulfide, PEN and composition thereof.
In addition, described first supporting layer 40 can also comprise the conductive material coating with electric conducting material and adhesive on this first supporting layer 40.Described conductive material coating, for improving the conductivity of electrode active material layers and reducing electrode resistance, prevents degradation of cell performance thus.
Can be identical with adhesive for the electric conducting material in priming coat with above-mentioned with adhesive for the electric conducting material in conductive material coating.
This conductive material coating is more favourable when being applied in positive pole than when being applied in negative pole, strengthen because the conductivity of anode active material layer is low and raise by electrode resistance the performance degradation caused, and anode active material layer has relatively good conductivity, the impact thus by conductive material coating not quite shows the performance similar with conventional anode.
In described conductive material coating, electric conducting material and adhesive can exist with the weight ratio of 80:20 ~ 99:1.Use a large amount of adhesive can cause the serious rising of electrode resistance.Therefore, when meeting this number range, can prevent electrode resistance from seriously raising.In addition, as mentioned above, because the first supporting layer serves as the buffering that can prevent electrode active material layers from coming off, so use adhesive can not greatly affect electrode flexibility with relatively few amount.
Subsequently, compress to form porous polymeric nitride layer 30 to the obtained thing obtained in step (S3), described porous polymeric nitride layer 30 is bonded in mutual integrated (S4) between electrode active material layers 20 with the first supporting layer 40.
Porous polymeric nitride layer 30 can have loose structure to be introduced in electrode active material layers well by electrolyte, and has the aperture of 0.01 ~ 10 μm and the porosity of 5 ~ 95%.
Described porous coating can be formed in the mode by being separated of being caused by non-solvent or phase transformation during its preparation with loose structure.
Such as, using polyvinylidene fluoride-altogether-hexafluoropropylene in the acetone that polymer adds to as solvent to obtain having the solution of 10 % by weight solids.To in the solution obtained, the amount using 2 ~ 10 % by weight is added as the water of non-solvent or ethanol to prepare polymer solution.
During drying program after coating, phase transformation is carried out to this polymer solution, thus form the part that is separated of non-solvent and polymer.Wherein, described non-solvent portion becomes hole.Therefore, can according to non-solvent and the amount of structure adaptability degree and non-solvent the size of control hole.
Fig. 7 is the photo of the cross section of the porous polymeric nitride layer 30 that display is obtained by an embodiment of the invention.
Simultaneously, if by polymer solution (30 ') is coated on a surface of electrode active material layers 20, drying subsequently forms porous polymeric nitride layer 30, and then form the first supporting layer 40 thereon by lamination, then may solidify for the adhesive component in the polymer solution (30 ') of bonded-electrode active material layer 20 and the first supporting layer 40, thus make to be difficult between the two layers keep strong adhesion.
In addition, different from using the of the present invention preferred preparation method of the first porous support layer prepared in advance, if form porous support layer by being coated in porous polymeric nitride layer by polymer solution, then compared with the first porous support layer of the present invention, the mechanical performance of this porous support layer formed by coated polymeric solution is poorer, can not effectively prevent electrode active material layers from coming off thus.
On the contrary, according to preferred preparation method of the present invention, on the polymer solution (30 ') the first supporting layer 40 being placed on applying, then adhesive component solidification, in the situation utilizing coating blade 60 they to be coated with together afterwards, formed thus and be bonded in porous polymeric nitride layer 30 between electrode active material layers 20 with the first supporting layer 40 thus mutually integrated.
Meanwhile, before the step (S1) or after step (S4), form the second supporting layer 50 by carrying out on the surface compressing at another of current-collector.Described second supporting layer 50 can suppress the short circuit of current-collector 10, thus more improves the flexibility of electrode.
Described second supporting layer 50 can be polymer film, and described polymer film can be made by being selected from following any one: polyolefin, polyester, polyimides, polyamide and composition thereof.
In addition, the invention provides a kind of secondary cell, described secondary cell comprises: positive pole, negative pole, be arranged on barrier film between described positive pole and described negative pole and electrolyte, and at least one in wherein said positive pole and described negative pole is formed by above-mentioned electrode for secondary battery.
Secondary cell of the present invention can be stacking, winding or stacking/folding common form, and it also can be the special shape of cable-type.
In addition, the invention provides a kind of cable Type Rechargeable Battery, comprise: interior electrode; Separator, its outer surface around described interior electrode is to prevent the short circuit between electrode; And external electrode, its by spirally to reel thus around described separator outer surface and formed, at least one in wherein said interior electrode and described external electrode is formed according to electrode for secondary battery of the present invention by above-mentioned.
Herein, term " spirally " used refer to while movement in specific region place rotate spiral-shaped, comprise common form of springs.
Described external electrode can be the strips of uniaxial extension.
Described external electrode can spirally winding, thus not overlapping or overlapping on its width on its width.Such as, in order to prevent the deterioration of battery performance, the external electrode of sheet form can spirally reel at the interval in the double length of its width, thus makes it not overlapping.
Or, described external electrode can overlapping on its width while spirally reel.In this case, in order to suppress the excessive rising of battery internal resistance, described external electrode can within spirally winding thus the width of its overlapping part can be in 0.9 times of the width of external electrode self.
Described interior electrode can centered by part be empty hollow structure.
Described interior electrode can be provided with the core of interior current-collector within it.
The core of described interior current-collector can by making as follows: carbon nano-tube, stainless steel, aluminium, nickel, titanium, sintered carbon or copper; In its surface with the stainless steel that carbon, nickel, titanium or silver processed; Aluminium-cadmium alloy; In its surface with the non-conductive polymer of electric conducting material process; Conducting polymer.
Or described interior electrode can be provided with the core for supplying lithium ion within it, and it comprises electrolyte.
The described core for supplying lithium ion can comprise gel polymer electrolyte and support.
In addition, the described core for supplying lithium ion can comprise liquid electrolyte and porous carrier.
Or described interior electrode can be provided with the core of filling within it.
The core of described filling can be made up of some materials of the many performances improving cable-type battery, such as except the core of current-collector in being formed with for except the material of the core of supplying lithium ion, also can be made up of fluoropolymer resin, rubber and inorganic matter, and also can have the various forms comprising line, fiber, powder, mesh and foam.
Meanwhile, Fig. 8 schematically shows the cable Type Rechargeable Battery according to one embodiment of the present invention, wherein by the outer surface of electrode roll in sheet form around the core 110 for supplying lithium ion.The interior electrode of sheet form can be applied in cable Type Rechargeable Battery, and as shown in Figure 8, and the external electrode of sheet form can be wound on the outer surface of separator similarly.
This cable Type Rechargeable Battery according to one embodiment of the present invention comprises: for supplying the core of lithium ion, it comprises electrolyte; Interior electrode, its outer surface around the described core for supplying lithium ion also comprises current-collector and electrode active material layers; Separator, its outer surface around described interior electrode is to prevent the short circuit between electrode; And external electrode, its by spirally to reel thus around described separator outer surface and formed, and comprising current-collector and electrode active material layers, at least one in wherein said interior electrode and described external electrode is for by being formed according to above-mentioned electrode for secondary battery of the present invention.
The level cross-sectionn that cable Type Rechargeable Battery of the present invention has reservation shape, the linear structure extended in the vertical and flexibility, thus it freely can change shape.Term used herein ' reservation shape ' is not restricted to any F-SP, and refers to the arbitrary shape not damaging character of the present invention.
In the cable Type Rechargeable Battery that can be designed by the present invention, will wherein use above-mentioned electrode for secondary battery shown in Figure 9 as the cable Type Rechargeable Battery 100 of interior electrode.
With reference to figure 9, cable Type Rechargeable Battery 100 comprises: for supplying the core 110 of lithium ion, it comprises electrolyte, interior electrode, it is around the outer surface of the described core 110 for supplying lithium ion, separator 170, its outer surface around described interior electrode is to prevent the short circuit between electrode, and external electrode, its by spirally to reel thus around described separator 170 outer surface and formed, and comprise outer current-collector 190 and external electrode active material layer 180, wherein said interior electrode comprises interior current-collector 120, be formed in the interior electrode active material layers 130 on a surface of described interior current-collector 120, be formed in the porous polymeric nitride layer 140 on the end face of described interior electrode active material layers 130, be formed in the first porous support layer 150 on the end face of described porous polymeric nitride layer 140, and the second supporting layer 160 be formed on another surface of described interior current-collector 120.
As mentioned above, the electrode for secondary battery according to of the present invention form also can be used as external electrode but not interior electrode, maybe can be used as both it.
Core 110 for supplying lithium ion comprises electrolyte, and described electrolytical type is not particularly limited and can be selected from: the nonaqueous electrolytic solution using ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate (VC), diethyl carbonate (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), methyl formate (MF), gamma-butyrolacton (γ-BL), sulfolane, methyl acetate (MA) or methyl propionate (MP); Use the gel polymer electrolyte of PEO, PVdF, PVdF-HFP, PMMA, PAN or PVAc; And the solid electrolyte of use PEO, PPOX (PPO), polymine (PEI), poly-ethyl sulfide (PES) or polyvinyl acetate (PVAc).In addition, described electrolyte also can comprise lithium salts, and described lithium salts can be selected from: LiCl, LiBr, LiI, LiClO 4, LiBF 4, LiB 10cl 10, LiPF 6, LiCF 3sO 3, LiCF 3cO 2, LiAsF 6, LiSbF 6, LiAlCl 4, CH 3sO 3li, CF 3sO 3li, (CF 3sO 2) 2nLi, chloroborane lithium, lower aliphatic lithium carbonate, tetraphenylboronic acid lithium and composition thereof.Core 110 for supplying lithium ion can only be made up of electrolyte, especially, can form liquid electrolyte by using porous carrier.
In the present invention, interior electrode can be negative pole or positive pole, and external electrode can be the negative or positive electrode corresponding with described interior electrode.
The electrode active material that may be used in negative pole and positive pole is same as described above.
Meanwhile, separator can be dielectric substrate or barrier film.
The dielectric substrate serving as ion channel can by making as follows: the gel-type polymer electrolyte using PEO, PVdF, PVdF-HFP, PMMA, PAN or PVAc; Or the solid electrolyte of use PEO, PPOX (PPO), polymine (PEI), poly-ethyl sulfide (PES) or polyvinyl acetate (PVAc).Preferred use polymer or glass-ceramic form the matrix of solid electrolyte as skeleton.When typical polymer dielectric, even if when meeting ionic conductance, in reaction rate, ion is still slowly mobile.Therefore, compared with solid electrolyte, preferably use the gel-type polymer electrolyte contributing to ionic transfer.The bad mechanical property of gel-type polymer electrolyte, therefore can comprise support to improve poor mechanical performance, and described support can be support or the cross-linked polymer of loose structure.Dielectric substrate of the present invention can serve as barrier film, therefore can omit other barrier film.
In the present invention, dielectric substrate also can comprise lithium salts.Lithium salts can improve ionic conductance and response time.The limiting examples of lithium salts can comprise: LiCl, LiBr, LiI, LiClO 4, LiBF 4, LiB 10cl 10, LiPF 6, LiCF 3sO 3, LiCF 3cO 2, LiAsF 6, LiSbF 6, LiAlCl 4, CH 3sO 3li, CF 3sO 3li, (CF 3sO 2) 2nLi, chloroborane lithium, lower aliphatic lithium carbonate and tetraphenylboronic acid lithium.
The example of barrier film can include but not limited to: the porous polymer matrix be made up of the polyolefin polymers being selected from Alathon, Noblen, ethylene-butene copolymer, ethylene-hexene co-polymers and ethylene-methyl acrylate copolymer; The porous polymer matrix be made up of the polymer being selected from polyester, polyacetals, polyamide, Merlon, polyimides, polyether-ether-ketone, polyether sulfone, polyphenylene oxide, polyphenylene sulfide and PEN; The porous substrate be made up of the mixture of inorganic particulate and binder polymer; Or as lower diaphragm plate, it has the porous coating be formed at least one surface of described porous polymer matrix, and comprises inorganic particulate and binder polymer.
In the porous coating formed by inorganic particulate and binder polymer, (namely described inorganic particulate is be combined with each other by binder polymer, described binder polymer connects and fixes described inorganic particulate), and described porous coating is maintained by the state that binder polymer is combined with the first supporting layer.In this porous coating, described inorganic particulate is filled with contacting with each other, and forms interstitial volume thus between inorganic particulate.Interstitial volume between described inorganic particulate becomes empty space thus forms hole.
Wherein, in order to make the lithium ion transfer of the core for supplying lithium ion to external electrode, preferably use with by being selected from the corresponding nonwoven fabrics barrier film of porous polymer matrix that following polymer makes: polyester, polyacetals, polyamide, Merlon, polyimides, polyether-ether-ketone, polyether sulfone, polyphenylene oxide, polyphenylene sulfide and PEN.
In addition, cable Type Rechargeable Battery of the present invention has protective finish 195.Described protective finish 195 serves as insulator and to be formed around the mode of outer current-collector, guard electrode does not affect by the moisture in air and external impact thus.Protective finish can be made up of the conventional polymer resin with moisture blocking layer.Described moisture blocking layer can be made up of aluminium or the liquid crystal polymer with good water-resisting ability, and described fluoropolymer resin can be PET, PVC, HDPE or epoxy resin.
In addition, the invention provides a kind of cable Type Rechargeable Battery, there is electrode in two or more, comprise:
The plural interior electrode be arranged parallel to each other;
Separator, its outer surface around described interior electrode is to prevent the short circuit between electrode; And
External electrode, its by spirally to reel thus around described separator outer surface and formed, at least one in wherein said interior electrode and described external electrode is use above-mentioned electrode for secondary battery according to the present invention to be formed.
In addition, the invention provides a kind of cable Type Rechargeable Battery, have electrode in two or more, comprise: the plural core for supplying lithium ion, it comprises electrolyte; The plural interior electrode be arranged parallel to each other, in each electrode around each for supplying the outer surface of the core of lithium ion and comprising current-collector and electrode active material layers; Separator, its outer surface around described interior electrode is to prevent the short circuit between electrode; And external electrode, its by spirally to reel thus around described separator outer surface and formed, and comprising current-collector and electrode active material layers, at least one in wherein said interior electrode and described external electrode is use above-mentioned electrode for secondary battery according to the present invention to be formed.
Have in the cable Type Rechargeable Battery of electrode in two or more what can be designed by the present invention, will wherein use above-mentioned electrode for secondary battery shown in Figure 10 as the cable Type Rechargeable Battery 200 of interior electrode.
With reference to Figure 10, cable Type Rechargeable Battery 200 comprises: the plural core 210 for supplying lithium ion, and it comprises electrolyte, the plural interior electrode be arranged parallel to each other, in each electrode around each for supplying the outer surface of the core of lithium ion, separator 270, its outer surface around described interior electrode is to prevent the short circuit between electrode, and external electrode, its by spirally to reel thus around described separator 270 outer surface and formed, and comprise outer current-collector 290 and external electrode active material layer 280, wherein in each, electrode comprises interior current-collector 220, be formed in the interior electrode active material layers 230 on a surface of described interior current-collector 220, be formed in the porous polymeric nitride layer 240 on the end face of described interior electrode active material layers 230, be formed in the first porous support layer 250 on the end face of described porous polymeric nitride layer 240, and the second supporting layer 260 be formed on another surface of described interior current-collector 220.
As mentioned above, the electrode for secondary battery according to of the present invention form also can be used as external electrode but not interior electrode, maybe can be used as both it.
In the cable Type Rechargeable Battery 200 with multiple interior electrode, the number of adjustable interior electrode with the load capacity of control electrode active material layer and battery capacity, and can prevent the possibility of short circuit owing to there is multiple electrode.
Industrial applicability
To invention has been detailed description.But should understand, describe in detail and instantiation, although instruction the preferred embodiment of the present invention, only provide with illustrative object, because according to this detailed description, the variations and modifications in the spirit and scope of the invention will become apparent for those skilled in the art.

Claims (65)

1. an electrode for secondary battery for sheet form, comprises:
Current-collector;
Electrode active material layers, it is formed on a surface of described current-collector;
Porous polymeric nitride layer, it is formed in described electrode active material layers; With
First porous support layer, it is formed in described porous polymeric nitride layer.
2. electrode for secondary battery according to claim 1, wherein said current-collector is by making as follows: stainless steel, aluminium, nickel, titanium, sintered carbon or copper; In its surface with the stainless steel that carbon, nickel, titanium or silver processed; Aluminium-cadmium alloy; In its surface with the non-conductive polymer of electric conducting material process; Conducting polymer; Comprise the metal paste of the metal dust of Ni, Al, Au, Ag, Pd/Ag, Cr, Ta, Cu, Ba or ITO; Or comprise the carbon paste cream of the carbon dust of graphite, carbon black or carbon nano-tube.
3. electrode for secondary battery according to claim 1, wherein said current-collector is the form of mesh.
4. electrode for secondary battery according to claim 1, wherein said current-collector also comprises the priming coat be made up of electric conducting material and adhesive.
5. electrode for secondary battery according to claim 4, wherein said electric conducting material comprises and is selected from following any one: carbon black, acetylene black, Ketjen black, carbon fiber, carbon nano-tube, Graphene and composition thereof.
6. electrode for secondary battery according to claim 4, wherein said adhesive is selected from polyvinylidene fluoride (PVDF), polyvinylidene fluoride-altogether-hexafluoropropylene, polyvinylidene fluoride-altogether-trichloroethylene, butyl polyacrylate, polymethyl methacrylate, polyacrylonitrile, PVP, polyvinyl acetate, polyethylene-altogether-vinyl acetate, poly(ethylene oxide), polyarylate, cellulose acetate, cellulose acetate-butyrate, cellulose-acetate propionate, cyanoethyl pullulan, cyanoethyl polyvinylalcohol, cyanethyl cellulose, cyanoethyl sucrose, Propiram, carboxymethyl cellulose, butadiene-styrene rubber, acrylonitrile-butadiene-styrene copolymer, polyimides and composition thereof.
7. electrode for secondary battery according to claim 1, wherein said current-collector has multiple recess at least one surface thereof.
8. electrode for secondary battery according to claim 7, wherein said multiple recess is patterning or patterning discontinuously continuously.
9. electrode for secondary battery according to claim 8, the recess of wherein said patterning is continuously formed with being spaced from each other in the vertical.
10. electrode for secondary battery according to claim 8, the recess of wherein said patterning is discontinuously formed by multiple hole.
11. electrode for secondary battery according to claim 10, wherein said multiple hole is circular or polygon.
12. electrode for secondary battery according to claim 1, wherein said first supporting layer is perforated membrane or the nonwoven fabrics of mesh form.
13. electrode for secondary battery according to claim 1, wherein said first supporting layer is made by being selected from following any one: high density polyethylene (HDPE), low density polyethylene (LDPE), LLDPE, ultra-high molecular weight polyethylene, polypropylene, PETG, polybutylene terephthalate (PBT), polyester, polyacetals, polyamide, Merlon, polyimides, polyether-ether-ketone, polyether sulfone, polyphenylene oxide, polyphenylene sulfide, PEN and composition thereof.
14. electrode for secondary battery according to claim 1, wherein also comprise the conductive material coating with electric conducting material and adhesive on the first supporting layer.
15. electrode for secondary battery according to claim 14, wherein in described conductive material coating, described electric conducting material and described adhesive exist with the weight ratio of 80:20 ~ 99:1.
16. electrode for secondary battery according to claim 14, wherein said electric conducting material comprises and is selected from following any one: carbon black, acetylene black, Ketjen black, carbon fiber, carbon nano-tube, Graphene and composition thereof.
17. electrode for secondary battery according to claim 14, wherein said adhesive is selected from polyvinylidene fluoride (PVDF), polyvinylidene fluoride-altogether-hexafluoropropylene, polyvinylidene fluoride-altogether-trichloroethylene, butyl polyacrylate, polymethyl methacrylate, polyacrylonitrile, PVP, polyvinyl acetate, polyethylene-altogether-vinyl acetate, poly(ethylene oxide), polyarylate, cellulose acetate, cellulose acetate-butyrate, cellulose-acetate propionate, cyanoethyl pullulan, cyanoethyl polyvinylalcohol, cyanethyl cellulose, cyanoethyl sucrose, Propiram, carboxymethyl cellulose, butadiene-styrene rubber, acrylonitrile-butadiene-styrene copolymer, polyimides and composition thereof.
18. electrode for secondary battery according to claim 1, wherein said porous polymeric nitride layer has the aperture of 0.01 ~ 10 μm and the porosity of 5 ~ 95%.
19. electrode for secondary battery according to claim 1, wherein said porous polymeric nitride layer comprises linear polymer, oxide-base linear polymer or its mixture with polarity.
20. electrode for secondary battery according to claim 19, the wherein said linear polymer with polarity is selected from: polyacrylonitrile, polyvinyl chloride, polyvinylidene fluoride (PVDF), polyvinylidene fluoride-altogether-hexafluoropropylene, polyvinylidene fluoride-altogether-trichloroethylene, polymine, polymethyl methacrylate, butyl polyacrylate, PVP, polyvinyl acetate, polyethylene-altogether-vinyl acetate, polyarylate, PPTA and composition thereof.
21. electrode for secondary battery according to claim 19, wherein said oxide-base linear polymer is selected from: poly(ethylene oxide), PPOX, polyformaldehyde, dimethyl silicone polymer and composition thereof.
22. electrode for secondary battery according to claim 1, it comprises porous coating further, and described porous coating is formed on the first supporting layer by the mixture of inorganic particulate and binder polymer.
23. electrode for secondary battery according to claim 1, it comprises the second supporting layer be formed on another surface of described current-collector further.
24. electrode for secondary battery according to claim 23, wherein said second supporting layer is polymer film.
25. electrode for secondary battery according to claim 24, wherein said polymer film is made by being selected from following any one: polyolefin, polyester, polyimides, polyamide and composition thereof.
26. electrode for secondary battery according to claim 1, wherein when described electrode for secondary battery is used as negative pole, described electrode active material layers comprises and is selected from following active material: native graphite, Delanium or carbonaceous material; Lithium-titanium composite oxide (LTO), and the metal (Me) comprising Si, Sn, Li, Zn, Mg, Cd, Ce, Ni and Fe; The alloy of described metal; The oxide (MeOx) of described metal; The compound of described metal and carbon; And their mixture, and
When described electrode for secondary battery is used as positive pole, described electrode active material layers comprises and is selected from following active material: LiCoO 2, LiNiO 2, LiMn 2o 4, LiCoPO 4, LiFePO 4, LiNiMnCoO 2, LiNi 1-x-y-zco xm1 ym2 zo 2(wherein M1 and M2 is selected from independently of one another: Al, Ni, Co, Fe, Mn, V, Cr, Ti, W, Ta, Mg and Mo, and x, y and z are independently of one another for forming the atomic fraction of the element of oxide, wherein 0≤x<0.5,0≤y<0.5,0≤z<0.5, and x+y+z≤1) and composition thereof.
27. 1 kinds of methods preparing the electrode for secondary battery of sheet form, comprising:
(S1) slurry containing electrode active material is coated on a surface of current-collector, dry subsequently, thus form electrode active material layers;
(S2) polymer solution containing polymer is coated in described electrode active material layers;
(S3) on polymer solution, the first porous support layer is formed; And
(S4) compress to form porous polymeric nitride layer to the obtained thing obtained in step (S3), described porous polymeric nitride layer is bonded between described electrode active material layers with described first porous support layer mutually integrated.
28. methods preparing the electrode for secondary battery of sheet form according to claim 27, wherein said polymer solution comprises adhesive ingredients.
29. methods preparing the electrode for secondary battery of sheet form according to claim 28, wherein in step (S3), before adhesive ingredients is cured, polymer solution form the first porous support layer.
30. methods preparing the electrode for secondary battery of sheet form according to claim 28, wherein in step (S4), compress to form porous polymeric nitride layer to the obtained thing obtained in step (S3) by coating blade, described porous polymeric nitride layer is bonded between described electrode active material layers with described first porous support layer mutually integrated.
31. methods preparing the electrode for secondary battery of sheet form according to claim 27, it is included in before step (S1) or after step (S4) further, forms the second supporting layer by carrying out on the surface compressing at another of current-collector.
32. 1 kinds of secondary cells, described secondary cell comprises: positive pole, negative pole, be arranged on barrier film between described positive pole and described negative pole and nonaqueous electrolytic solution,
The electrode for secondary battery of at least one any one of claim 1 ~ 26 in wherein said positive pole and described negative pole.
33. according to the secondary cell of claim 32, and wherein said secondary cell is the form of stacking, winding, stacking/folding or cable-type.
34. 1 kinds of cable Type Rechargeable Batteries, comprise:
Interior electrode;
Separator, its outer surface around described interior electrode is to prevent the short circuit between electrode; And
External electrode, its outer surface around described separator also passes through spirally reel and formed,
At least one in wherein said interior electrode and described external electrode is formed by using the electrode for secondary battery any one of claim 1 to 26.
35. according to the cable Type Rechargeable Battery of claim 34, the strips of wherein said dispatch from foreign news agency very uniaxial extension.
36. according to the cable Type Rechargeable Battery of claim 34, and wherein said external electrode spirally reels, thus not overlapping on its width.
37. according to the cable Type Rechargeable Battery of claim 36, and wherein said external electrode spirally reels with the interval in the double length of its width, thus makes it not overlapping.
38. according to the cable Type Rechargeable Battery of claim 34, and wherein said external electrode spirally reels, thus overlapping on its width.
39. according to the cable Type Rechargeable Battery of claim 38, and wherein said external electrode spirally reels, thus within the width of its overlapping part is in 0.9 times of the width of external electrode self.
40. according to the cable Type Rechargeable Battery of claim 34, and centered by wherein said interior electrode, part is empty hollow structure.
41. according to the cable Type Rechargeable Battery of claim 40, and wherein said interior electrode comprises one or more electrode for secondary battery spirally reeled.
42. according to the cable Type Rechargeable Battery of claim 40, and wherein said interior electrode is provided with the core of interior current-collector within it, and for supplying the core of lithium ion, it comprises electrolyte; Or the core of filling.
43. according to the cable Type Rechargeable Battery of claim 42, and the core of wherein said interior current-collector is by making as follows: carbon nano-tube, stainless steel, aluminium, nickel, titanium, sintered carbon or copper; In its surface with the stainless steel that carbon, nickel, titanium or silver processed; Aluminium-cadmium alloy; In its surface with the non-conductive polymer of electric conducting material process; Conducting polymer.
44. according to the cable Type Rechargeable Battery of claim 42, and the wherein said core for supplying lithium ion comprises gel polymer electrolyte and support.
45. according to the cable Type Rechargeable Battery of claim 42, and the wherein said core for supplying lithium ion comprises liquid electrolyte and porous carrier.
46. according to the cable Type Rechargeable Battery of claim 42, and wherein said electrolyte is selected from: the nonaqueous electrolytic solution using ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate (VC), diethyl carbonate (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), methyl formate (MF), gamma-butyrolacton (γ-BL), sulfolane, methyl acetate (MA) or methyl propionate (MP); Use the gel polymer electrolyte of PEO, PVdF, PVdF-HFP, PMMA, PAN or PVAc; And the solid electrolyte of use PEO, PPOX (PPO), polymine (PEI), poly-ethyl sulfide (PES) or polyvinyl acetate (PVAc).
47. according to the cable Type Rechargeable Battery of claim 42, and wherein said electrolyte also comprises lithium salts.
48. according to the cable Type Rechargeable Battery of claim 47, and wherein said lithium salts is selected from: LiCl, LiBr, LiI, LiClO 4, LiBF 4, LiB 10cl 10, LiPF 6, LiCF 3sO 3, LiCF 3cO 2, LiAsF 6, LiSbF 6, LiAlCl 4, CH 3sO 3li, CF 3sO 3li, (CF 3sO 2) 2nLi, chloroborane lithium, lower aliphatic lithium carbonate, tetraphenylboronic acid lithium and composition thereof.
49. according to the cable Type Rechargeable Battery of claim 42, and the core of wherein said filling is made up with the form of line, fiber, powder, mesh and foam of fluoropolymer resin, rubber and inorganic matter.
50. according to the cable Type Rechargeable Battery of claim 34, and wherein said interior electrode is negative pole or positive pole, and the negative or positive electrode that described dispatch from foreign news agency is very corresponding with described interior electrode.
51. according to the cable Type Rechargeable Battery of claim 34, and wherein said separator is dielectric substrate or barrier film.
52. according to the cable Type Rechargeable Battery of claim 51, and wherein said dielectric substrate comprises and is selected from following electrolyte: the gel polymer electrolyte using PEO, PVdF, PMMA, PVdF-HFP, PAN or PVAc; With the solid electrolyte of use PEO, PPOX (PPO), polymine (PEI), poly-ethyl sulfide (PES) or polyvinyl acetate (PVAc).
53. according to the cable Type Rechargeable Battery of claim 51, and wherein said dielectric substrate also comprises lithium salts.
54. according to the cable Type Rechargeable Battery of claim 53, and wherein said lithium salts is selected from: LiCl, LiBr, LiI, LiClO 4, LiBF 4, LiB 10cl 10, LiPF 6, LiCF 3sO 3, LiCF 3cO 2, LiAsF 6, LiSbF 6, LiAlCl 4, CH 3sO 3li, CF 3sO 3li, (CF 3sO 2) 2nLi, chloroborane lithium, lower aliphatic lithium carbonate, tetraphenylboronic acid lithium and composition thereof.
55. according to the cable Type Rechargeable Battery of claim 51, and wherein said barrier film is: the porous polymer matrix be made up of the polyolefin polymers being selected from Alathon, Noblen, ethylene-butene copolymer, ethylene-hexene co-polymers and ethylene-methyl acrylate copolymer; The porous polymer matrix be made up of the polymer being selected from polyester, polyacetals, polyamide, Merlon, polyimides, polyether-ether-ketone, polyether sulfone, polyphenylene oxide, polyphenylene sulfide and PEN; The porous substrate be made up of the mixture of inorganic particulate and binder polymer; Or as lower diaphragm plate, it has the porous coating be formed at least one surface of described porous polymer matrix, and comprises inorganic particulate and binder polymer.
56. according to the cable Type Rechargeable Battery of claim 55, and wherein said porous polymer matrix is porous polymer film base material or porous non-woven cloth base material.
57. according to the cable Type Rechargeable Battery of claim 34, and it comprises protective finish further, and described protective finish is around the outer surface of described external electrode.
58. according to the cable Type Rechargeable Battery of claim 57, and wherein said protective finish is made up of fluoropolymer resin.
59. according to the cable Type Rechargeable Battery of claim 58, and wherein said fluoropolymer resin comprises any one that be selected from PET, PVC, HDPE, epoxy resin and composition thereof.
60. according to the cable Type Rechargeable Battery of claim 58, and wherein said protective finish comprises moisture blocking layer further.
61. according to the cable Type Rechargeable Battery of claim 60, and wherein said moisture blocking layer is made up of aluminium or liquid crystal polymer.
62. 1 kinds of cable Type Rechargeable Batteries, comprise:
For supplying the core of lithium ion, it comprises electrolyte;
Interior electrode, it around the outer surface of the described core for supplying lithium ion, and comprises current-collector and electrode active material layers;
Separator, its outer surface around described interior electrode is to prevent the short circuit between electrode; With
External electrode, its by spirally to reel thus around described separator outer surface and formed, and comprise current-collector and electrode active material layers,
At least one in wherein said interior electrode and described external electrode is formed for using the electrode for secondary battery any one of claim 1 to 26.
63. 1 kinds of cable Type Rechargeable Batteries, comprise:
The plural interior electrode be arranged parallel to each other;
Separator, its outer surface around described interior electrode is to prevent the short circuit between electrode; And
External electrode, its outer surface around described separator also passes through spirally reel and formed,
At least one in wherein said interior electrode and described external electrode is formed for using the electrode for secondary battery any one of claim 1 to 26.
64. 1 kinds of cable Type Rechargeable Batteries, comprise:
The plural core for supplying lithium ion, it comprises electrolyte;
The plural interior electrode be arranged parallel to each other, in each electrode around each for supplying the outer surface of the core of lithium ion and comprising current-collector and electrode active material layers;
Separator, its outer surface around described interior electrode is to prevent the short circuit between electrode; And
External electrode, its by spirally to reel thus around described separator outer surface and formed, and comprise current-collector and electrode active material layers, wherein
At least one in described interior electrode and described external electrode is formed for using the electrode for secondary battery any one of claim 1 to 26.
65. according to the cable Type Rechargeable Battery of claim 64, and wherein said interior electrode comprises one or more electrode for secondary battery spirally reeled.
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