CN104393231B - Electrode for secondary battery, it prepares and includes its secondary cell and cable Type Rechargeable Battery - Google Patents

Electrode for secondary battery, it prepares and includes its secondary cell and cable Type Rechargeable Battery Download PDF

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Publication number
CN104393231B
CN104393231B CN201410191341.1A CN201410191341A CN104393231B CN 104393231 B CN104393231 B CN 104393231B CN 201410191341 A CN201410191341 A CN 201410191341A CN 104393231 B CN104393231 B CN 104393231B
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electrode
secondary battery
cable type
rechargeable battery
type rechargeable
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CN201410191341.1A
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CN104393231A (en
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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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    • H01M10/0422—Cells or battery with cylindrical casing
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Abstract

The present invention relates to electrode for secondary battery, its preparation and include its secondary cell and cable Type Rechargeable Battery.The electrode for secondary battery includes：Current-collector；Electrode active material layers, it is formed on a surface of the current-collector；Porous polymeric nitride layer, it is formed in the electrode active material layers；And first porous support layer, it is formed in the porous polymeric nitride layer.Support layer is had according to the electrode for secondary battery of the sheet form of the present invention at least one surface, so as to show the flexibility that shockingly improves and even if applying strong external force to the electrode, it still is able to prevent electrode active material layers from coming off from current-collector, thus prevents battery capacity from declining and improve the cycle life characteristics of battery.

Description

Electrode for secondary battery, it is prepared and the secondary cell comprising it and cable-type two Primary cell
The cross reference of related application
This application claims the excellent of the korean patent application 10-2013-0051566 submitted on May 7th, 2013 in South Korea First weigh, by reference to its content is incorporated herein.
Technical field
The present invention relates to a kind of electrode for secondary battery, relates more specifically to prevent electrode active material layers from coming off simultaneously Flexible electrode for secondary battery with improvement, the method for preparing the electrode and the secondary cell for including the electrode And cable Type Rechargeable Battery.
Background technology
Secondary cell is that energy and the device that can change into electric energy when needed to generate electricity can be stored with chemical species. Also secondary cell is referred to as rechargeable battery, because it can be recharged repeatedly.Common secondary cell include lead accumulator, NiCd batteries, NiMH batteries, Li ion batteries, Li ion polymer cells etc..It is secondary when compared with disposable galvanic cell Battery is not only more economically effectively, and be more environmentally friendly.
Secondary cell is used to needing the application of low electric power at present, for example, for make the equipment of vehicle launch, mobile device, Instrument, uninterrupted power source etc..Recently, cause the popularization of mobile device with the development of wireless communication technology, and even result in more The mobile of kind conventional equipment, is sharply increased to the demand of secondary cell.Secondary cell is also used for the environment-friendly next generation To reduce cost and weight and increase the service life of vehicle in vehicle such as motor vehicle driven by mixed power and electric vehicle.
Generally, secondary cell has cylindrical, prismatic or pouch-shaped.This is related to the manufacture method of secondary cell, in institute State in method and the electrode assemblie being made up of negative pole, positive pole and barrier film is arranged on cylinder or prismatic metal shell or aluminium lamination pressure In the pouch-shaped case of piece, and the shell is filled using electrolyte.Because it is used for the predetermined installing space of electrode assemblie in the method It is necessary, so cylindrical, the prismatic or pouch-shaped of secondary cell is a kind of limit when developing variously-shaped mobile device System.Therefore the secondary cell for the new construction being readily adapted to accommodate it is necessary to have shape.
In order to meet this needs, it has been proposed that the exploitation length cable-type electricity very big to the ratio between cross-sectional diameter Pond.The cable-type battery is prone to change in shape while stress is undergone due to causing the external force of change in shape.This Outside, the electrode active material layers of cable-type battery may come off because of the fast volume expansion during charging and discharging process.Root According to these reasons, the capacity of battery can decline and its cycle life characteristics can deteriorate.
It is flexible to be provided during bending or distortion by improving the amount of the adhesive used in electrode active material layers, Can solve this problem to a certain extent.However, the amount of binder improved in electrode active material layers causes electrode resistance liter High and deterioration.In addition, when applying strong external force, for example, in the case of electrode is folded completely, even if viscous The quantitative change of mixture is big, can not still prevent coming off for electrode active material layers.Therefore, this method is not enough to solve this problem.
The content of the invention
The present invention is devised in order to solve the problems, such as correlation technique, therefore use the present invention relates to a kind of secondary cell is provided Electrode, the method for preparing the electrode and secondary cell and cable Type Rechargeable Battery comprising the electrode, the secondary electricity The crackle that pond electrode can mitigate in the electrode active material layers as caused by external force produces, and even if in the presence of serious crackle It still is able to prevent electrode active material layers from coming off from current-collector.
According to an aspect of the present invention, there is provided a kind of electrode for secondary battery of sheet form, comprising：Current-collector；Electrode Active material layer, it is formed on a surface of the current-collector；Porous polymeric nitride layer, it is formed in the electrode activity material On the bed of material；First porous support layer, it is formed in the porous polymeric nitride layer.
The current-collector can be by being made as follows：Stainless steel, aluminium, nickel, titanium, sintering carbon or copper；In its surface with carbon, The stainless steel that nickel, titanium or silver treat；Aluminium-cadmium alloy；The non-conductive polymer treated in its surface with conductive material；Lead Electric polymer；The metal paste of metal dust comprising Ni, Al, Au, Ag, Pd/Ag, Cr, Ta, Cu, Ba or ITO；Or comprising The carbon paste cream of the carbon dust of graphite, carbon black or CNT.
In addition, the current-collector can be the form of mesh.
In addition, the current-collector can be also comprising the priming coat being made up of conductive material and adhesive.
The conductive material can be included selected from as follows any：Carbon black, acetylene black, Ketjen black, carbon fiber, carbon nanometer Pipe, graphene and its mixture.
Described adhesive can be selected from polyvinylidene fluoride (PVDF), polyvinylidene fluoride -co- hexafluoropropene, poly- inclined two It is PVF -co- trichloro ethylene, butyl polyacrylate, polymethyl methacrylate, polyacrylonitrile, PVP, poly- Vinyl acetate, polyethylene -co- vinyl acetate, PEO, polyarylate, cellulose acetate, cellulose acetate-butyrate, Cellulose-acetate propionate, cyanoethyl pullulan, cyanoethyl polyvinylalcohol, cyanethyl cellulose, cyanoethyl sucrose, Propiram, carboxylic Methylcellulose, butadiene-styrene rubber, acrylonitrile-butadiene-styrene copolymer, polyimides and its mixture.
In addition, the current-collector can have multiple recesses.
The multiple recess at least one surface thereof continuous pattern or interruption pattern.
Meanwhile first porous support layer can be the perforated membrane or non-woven fabrics of mesh form.
First porous support layer can be by being made selected from any one following：High density polyethylene (HDPE), low-density are gathered Ethene, LLDPE, ultra-high molecular weight polyethylene, polypropylene, polyethylene terephthalate, poly- terephthaldehyde Sour butanediol ester, polyester, polyacetals, polyamide, makrolon, polyimides, polyether-ether-ketone, polyether sulfone, polyphenylene oxide, polyphenylene sulfide Ether, PEN and its mixture.
In addition, first porous support layer can also include the conduction with conductive material and adhesive in its surface Material coating.
In the conductive material coating, the conductive material and described adhesive can be with 80:20~99:1 weight Than existing.
The conductive material can be included selected from any one following：Carbon black, acetylene black, Ketjen black, carbon fiber, carbon are received Mitron, graphene and its mixture.
Meanwhile the porous polymeric nitride layer can be with 0.01~10 μm of aperture and 5~95% porosity.
The porous polymeric nitride layer can include with the linear polymer of polarity, oxide-base linear polymer or it is mixed Compound.
The linear polymer with polarity can be selected from：Polyacrylonitrile, polyvinyl chloride, polyvinylidene fluoride (PVDF), polyvinylidene fluoride -co- hexafluoropropene, polyvinylidene fluoride -co- trichloro ethylene, polyethyleneimine, poly- methyl-prop E pioic acid methyl ester, butyl polyacrylate, PVP, polyvinyl acetate, polyethylene -co- vinyl acetate, poly- virtue Ester, PPTA and its mixture.
The oxide-base linear polymer can be selected from：PEO, PPOX, polyformaldehyde, poly dimethyl Siloxanes and its mixture.
Meanwhile the electrode for secondary battery can further include porous coating, the porous coating by inorganic particulate with The mixture of binder polymer is formed on the first porous support layer.
In addition, the electrode for secondary battery can further include second be formed on another surface of the current-collector Hold layer.
Second support layer can be polymer film.The polymer film can be by being made as follows：Polyolefin, polyester, Polyimides, polyamide and its mixture.
Meanwhile when the electrode for secondary battery is used as into negative pole, the electrode active material layers can be included and are selected from Following active material：Native graphite, Delanium or carbonaceous material；Lithium-titanium composite oxide (LTO), and including Si, Sn, Li, Zn, Mg, Cd, Ce, Ni and Fe metal (Me)；The alloy of the metal；The oxide (MeOx) of the metal；The gold The compound of category and carbon；And their mixture, and when the electrode for secondary battery is used as into positive pole, the electrode active Property material layer can include be selected from following active material：LiCoO2、LiNiO2、LiMn2O4、LiCoPO4、LiFePO4、 LiNiMnCoO2、LiNi1-x-y-zCoxM1yM2zO2(wherein M1 and M2 are each independently selected from：Al、Ni、Co、Fe、Mn、V、Cr、 Ti, W, Ta, Mg and Mo, and x, y and z are each independently the atomic fraction for the element to form oxide, wherein 0≤x<0.5,0 ≤y<0.5,0≤z<0.5, and x+y+z≤1) and its mixture.
According to another aspect of the present invention, there is provided a kind of method for the electrode for secondary battery for preparing sheet form, including： (S1) slurry containing electrode active material is coated on a surface of current-collector, be subsequently dried, so as to form electrode activity Material layer；(S2) polymer solution containing polymer is coated in the electrode active material layers；(S3) in polymer solution The first porous support layer of upper formation；And (S4) is compressed to form porous polymeric to the obtained thing obtained in step (S3) Nitride layer, the porous polymeric nitride layer be bonded between the electrode active material layers and first porous support layer and mutual one Body.
The polymer solution can include adhesive ingredients.
Herein, in step (S3), it is porous that first can be formed on polymer solution before adhesive ingredients is cured Support layer.
In addition, in step (S4), the obtained thing obtained in step (S3) can be compressed by coating blade with Porous polymeric nitride layer is formed, the porous polymeric nitride layer is bonded in the electrode active material layers and first porous support layer Between and mutually integration.
In addition, methods described can further comprise before step (S1) or after step (S4), by current-collector Another surface on be compressed and form the second support layer.
In addition, the further aspect according to the present invention, there is provided a kind of cable Type Rechargeable Battery, comprising：Interior electrode；Isolation Layer, it surrounds the outer surface of the interior electrode to prevent the short circuit between electrode；And external electrode, it is by spirally winding So as to be formed around the outer surface of the separation layer, wherein at least one of the interior electrode and described external electrode are to pass through Formed using the above-mentioned electrode for secondary battery according to the present invention.
Herein, the external electrode can be formed with the strips of uniaxial extension.
In addition, the external electrode can be with spirally winding, so as to not overlapping or overlapping on its width.
In addition, the interior electrode can be partly empty hollow structure centered on.
Herein, the interior electrode can include one or more electrode for secondary battery spirally wound.
The interior electrode can be provided with the core of interior current-collector in it, and for supplying the core of lithium ion, it includes electrolyte； Or the core of filling.
The core for being used to supply lithium ion can include gel polymer electrolyte and support, or can include liquid electric Solve matter and porous carrier.
The electrolyte for supplying used in the core of lithium ion can be selected from：Use ethylene carbonate (EC), carbon The sub- propyl ester (PC) of acid, 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) nonaqueous electrolytic solution；Use PEO, PVdF, PVdF-HFP, PMMA, PAN or PVAc gel polymer electrolyte；And Use PEO, PPOX (PPO), polyethyleneimine (PEI, polyether imine), poly- ethyl sulfide (PES) or poly- acetic acid The solid electrolyte of vinyl acetate (PVAc).
The electrolyte can also include lithium salts, and the lithium salts can be selected from：LiCl、LiBr、LiI、LiClO4、 LiBF4、LiB10Cl10、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、CF3SO3Li、 (CF3SO2)2NLi, chloroborane lithium, lower aliphatic lithium carbonate, tetraphenylboronic acid lithium and its mixture.
The interior electrode can be negative pole or positive pole, and the external electrode can be the positive pole corresponding with the interior electrode Or negative pole.
Meanwhile the separation layer can be dielectric substrate or barrier film.
The dielectric substrate can include and be selected from following electrolyte：Using PEO, PVdF, PMMA, PVdF-HFP, PAN or PVAc gel polymer electrolyte；With use PEO, PPOX (PPO), polyethyleneimine (PEI), poly- ethyl sulfide (PES) or polyvinyl acetate (PVAc) solid electrolyte.
The dielectric substrate can also include lithium salts, and the lithium salts can be selected from：LiCl、LiBr、LiI、LiClO4、 LiBF4、LiB10Cl10、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、CF3SO3Li、 (CF3SO2)2NLi, chloroborane lithium, lower aliphatic lithium carbonate, tetraphenylboronic acid lithium and its mixture.
The barrier film can be：By selected from Alathon, Noblen, ethylene-butene copolymer, polyethylene-hexene Porous polymer matrix made of polyolefin polymers in copolymer and ethylene-methyl acrylate copolymer；By selected from Polyester, polyacetals, polyamide, makrolon, polyimides, polyether-ether-ketone, polyether sulfone, polyphenylene oxide, polyphenylene sulfide and poly- naphthalene two Porous polymer matrix made of polymer in formic acid glycol ester；By the mixture system of inorganic particulate and binder polymer Into porous substrate；Or such as lower diaphragm plate, it is more at least one surface of the porous polymer matrix with being formed at Hole coating, and include inorganic particulate and binder polymer.
In addition, the still another aspect according to the present invention, there is provided a kind of cable Type Rechargeable Battery, comprising：
For supplying the core of lithium ion, it includes electrolyte；
Interior electrode, it includes current-collector and electrode activity material around the outer surface for being used to supply the core of lithium ion The bed of material；
Separation layer, it surrounds the outer surface of the interior electrode to prevent the short circuit between electrode；With
External electrode, it is formed by spirally winding around the outer surface of the separation layer, and includes current collection Device and electrode active material layers, wherein at least one of the interior electrode and described external electrode are using according to the upper of the present invention State electrode for secondary battery and formed.
In addition, the still another aspect according to the present invention, there is provided a kind of cable Type Rechargeable Battery, comprising：
The more than two interior electrodes being arranged parallel to each other；
Separation layer, it surrounds the outer surface of the interior electrode to prevent the short circuit between electrode；And
External electrode, it is formed by spirally winding around the outer surface of the separation layer, wherein in described At least one of electrode and the external electrode are to be formed using the above-mentioned electrode for secondary battery according to the present invention.
In addition, the further aspect according to the present invention, there is provided a kind of cable Type Rechargeable Battery, comprising：It is more than two For supplying the core of lithium ion, it includes electrolyte；The more than two interior electrodes being arranged parallel to each other, each interior electrode surround It is each to be used to supply the outer surface of the core of lithium ion and comprising current-collector and electrode active material layers；Separation layer, it is around described The outer surface of interior electrode is to prevent the short circuit between electrode；And external electrode, it is by spirally winding so as to around described The outer surface of separation layer and formed, and comprising current-collector and electrode active material layers, wherein the interior electrode and the external electrode At least one of be using according to the present invention above-mentioned electrode for secondary battery and formed.
Herein, the interior electrode can include one or more electrode for secondary battery spirally wound.
Thus, support layer is had according to the electrode for secondary battery of the sheet form of the present invention at least one surface thereof, So as to show the flexibility shockingly improved.
When applying strong external force to electrode, such as during the complete folding of electrode, the support layer serves as buffering, So as to which even if amount of the adhesive in electrode active material layers does not increase, remain to reduce the crackle production in electrode active material layers It is raw.Thereby, it is possible to prevent electrode active material layers from being come 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 there is porous polymeric nitride layer on the top surface of its electrode active material layers so that can be with Electrolyte is introduced into electrode active material layers well, thus suppresses the resistance rise of electrode.
Further, since porous support layer is provided, so electrolyte can be immersed in the hole of porous support layer to suppress battery Resistance rise, thus prevent degradation of cell performance.
Brief description of the drawings
Accompanying drawing shows the preferred embodiment of the present invention, and for further understanding this hair together with foregoing invention content Bright technology purport.However, the present invention is not construed as limited to accompanying drawing.
Fig. 1 shows the cross section of the electrode for secondary battery of the sheet form according to one embodiment of the present invention.
Fig. 2 shows the cross section of the electrode for secondary battery of the sheet form according to another embodiment of the invention.
Fig. 3 schematically shows the side for the electrode for secondary battery for preparing the sheet form according to one embodiment of the present invention Method.
Fig. 4 shows the surface of the current-collector of the mesh form according to one embodiment of the present invention.
Fig. 5 schematically shows the surface of the current-collector with multiple recesses according to one embodiment of the present invention.
Fig. 6 schematically shows the surface of the current-collector with multiple recesses according to another embodiment of the invention.
Fig. 7 is the photo for the cross section for showing the porous polymeric nitride layer obtained by an embodiment of the invention.
Fig. 8 schematically shows the interior electrode of sheet form, and the interior electrode is wound in cable Type Rechargeable Battery of the present invention For the outer surface for the core for supplying lithium ion.
Fig. 9 is the exploded perspective for the inside for schematically showing the cable Type Rechargeable Battery according to one embodiment of the present invention Figure.
Figure 10 schematically shows the cross section of the cable Type Rechargeable Battery with multiple interior electrodes according to the present invention.
<Reference>
10：Current-collector 20：Electrode active material layers
30：Porous polymeric nitride layer 30 '：Polymer solution
40：First porous support layer 50：Second support layer
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：First porous support layer
160、260：Second support layer
170、270：Separation layer
180、280：External electrode active material layer
190、290：Outer current-collector
195、295：Protective coating
Embodiment
Hereinafter, the preferred embodiment of the present invention is described in detail refer to the attached drawing.Before explanation, Ying Li The term used in specification and appended claims, should not be construed as limited to common and dictionary implication by solution, But should cause the present inventor can to term carry out suitably define to carry out the principle of best illustrated on the basis of, according to The corresponding implication of the technical elements of invention and concept explain to the term.
Therefore, explanation presented herein is the preferred embodiment of being merely to illustrate property purpose, it is not intended to limits this hair Bright scope, it should be understood that it can be completed under conditions of without departing substantially from the spirit and scope of the invention other equivalents and Variant.
Figures 1 and 2 show that according to the cross section of the electrode for secondary battery of the sheet form of one embodiment of the present invention, and scheme 3 schematically show the method for optimizing for the electrode for secondary battery for preparing the sheet form according to one embodiment of the present invention.
With reference to figure 1-3, included according to the electrode for secondary battery of the sheet form of the present invention：Current-collector 10；Formed described Electrode active material layers 20 on one surface of current-collector 10；Form the porous polymeric in the electrode active material layers 20 Nitride layer 30；With first porous support layer 40 of the formation on the top surface of the porous polymeric nitride layer 30.
Also, can further include according to the electrode for secondary battery of sheet form of the present invention to be formed it is another in the current-collector 10 The second support layer 50 on one surface.
In order that battery has flexibility, there should be enough flexibilities for the electrode in battery.However, as flexible electrical In the case of the regular cable type battery of one, pond example, electrode active material layers are easy to the external force of change in shape caused by and made Into stress or when using high power capacity negative active core-shell material containing Si, Sn etc. during charging and discharging process its is fast Fast volumetric expansion and come off.This come off of electrode active material layers reduces the capacity of battery and deteriorates cycle life characteristics.Make To overcome the trial of this problem, amount of the adhesive in electrode active material layers has been improved with during bending or distortion There is provided flexible.
However, the amount of binder improved in electrode active material layers causes electrode resistance to raise and deterioration.This Outside, when applying strong external force, such as in the case of electrode is folded completely, even if the quantitative change of adhesive is big, still can not Prevent electrode active material layers from coming off.Therefore, this method is not enough to solve this problem.
In order to overcome above mentioned problem, the present inventor is by including the He of the first porous support layer 40 formed on its outer surface The second support layer 50 for being optionally further formed on another surface of current-collector 10 and devise the secondary electricity of sheet form Pond electrode.
That is, even if electrode is acted on during bending or distortion by external force, there is the first porous support layer 40 of porosity Still function as to mitigate and apply to the buffering of the external force of electrode active material layers 20, so as to prevent that electrode active material layers 20 are de- Fall, thus improve the flexibility of electrode.In addition, when being formed further with the second support layer 50, the short of current-collector 10 can be suppressed Road, thus further improve the flexibility of electrode.
In addition, the electrode of the present invention includes porous polymeric nitride layer 30 using as bonding the first porous support layer 40 and electricity Pole active material layer and make its mutually integration adhesive, the porous polymeric nitride layer 30 to polymer solution by doing It is dry and obtain.
If common adhesive is used as into the adhesive, it serves as the resistance thing of electrode and deterioration. On the contrary, the porous polymeric nitride layer 30 with loose structure allows to electrolyte being introduced into electrode active material layers well, Thus the rise of electrode resistance is suppressed.
Hereinafter, the method for preparing the electrode for secondary battery of sheet form will be illustrated with reference to figure 1-3.Although Fig. 3 In show first current-collector 10 be formed below the second support layer 50 then formed porous polymeric nitride layer a situation, but this Simply one embodiment of the present of invention.Therefore, as mentioned below, can be formed under conditions of the second support layer is not formed porous poly- Compound layer.
First, by slurry of the application containing electrode active material on a surface of current-collector 10, then dry, so as to Form electrode active material layers 20 (S1).
The current-collector 10 can be by being made as follows：Stainless steel, aluminium, nickel, titanium, sintering carbon or copper；In its surface with carbon, The stainless steel that nickel, titanium or silver treat；Aluminium-cadmium alloy；The non-conductive polymer treated in its surface with conductive material；Lead Electric polymer；The metal paste of metal dust comprising Ni, Al, Au, Ag, Pd/Ag, Cr, Ta, Cu, Ba or ITO；Or comprising The carbon paste cream of the carbon dust of graphite, carbon black or CNT.
As described above, when secondary cell undergoes external force because bending or distorting, electrode active material layers may be from current collection Device comes off.In view of the reason, a large amount of adhesive components is used in electrode active material layers to provide flexibility in the electrodes.So And a large amount of adhesives may be susceptible to peel off because of the swelling caused by electrolyte, thus deterioration.
Therefore, in order to improve the adhesivity between electrode active material layers and current-collector, the current-collector 10 can be wrapped also Containing the priming coat being made up of conductive material and adhesive.
The conductive material can be included selected from any one following：Carbon black, acetylene black, Ketjen black, carbon fiber, carbon are received Mitron, graphene and its mixture, but not limited to this.
Described adhesive can be selected from：Polyvinylidene fluoride (PVDF), polyvinylidene fluoride -co- hexafluoropropene, poly- inclined two It is PVF -co- trichloro ethylene, butyl polyacrylate, polymethyl methacrylate, polyacrylonitrile, PVP, poly- Vinyl acetate, polyethylene -co- vinyl acetate, PEO, polyarylate, cellulose acetate, cellulose acetate-butyrate, Cellulose-acetate propionate, cyanoethyl pullulan, cyanoethyl polyvinylalcohol, cyanethyl cellulose, cyanoethyl sucrose, Propiram, carboxylic Methylcellulose, butadiene-styrene rubber, acrylonitrile-butadiene-styrene copolymer, polyimides and its mixture, but not limited to this.
In addition, with reference to figure 4~6, the current-collector 10 can be the form of mesh, and can be at least one surface thereof With multiple recesses, so as to further improve its surface area.The recess can continuously pattern or interruption pattern. I.e., it is possible to form continuous patterned recess with being spaced from each other in the vertical, or can be formed in the form of intermittent pattern multiple Hole.The multiple hole can be circular or polygon.
In the present invention, when the electrode for secondary battery is used as into negative pole, electrode active material layers can include choosing From following active material：Native graphite, Delanium or carbonaceous material；Lithium-titanium composite oxide (LTO), and including Si, Sn, Li, Zn, Mg, Cd, Ce, Ni and Fe metal (Me)；The alloy of the metal；The oxide (MeOx) of the metal；It is described The compound of metal and carbon；And their mixture, and when the electrode for secondary battery is used as into positive pole, electrode activity Material layer can include and be selected from following active material：LiCoO2、LiNiO2、LiMn2O4、LiCoPO4、LiFePO4、 LiNiMnCoO2、LiNi1-x-y-zCoxM1yM2zO2(wherein M1 and M2 are each independently selected from：Al、Ni、Co、Fe、Mn、V、Cr、 Ti, W, Ta, Mg and Mo, and x, y and z are each independently the atomic fraction for the element to form oxide, wherein 0≤x<0.5,0 ≤y<0.5,0≤z<0.5, and x+y+z≤1) and its mixture.
Then, the polymer solution 30 ' containing polymer is coated in electrode active material layers 20 (S2).
The polymer can be the linear polymer with polarity, oxide-base linear polymer or its mixture.
The linear polymer with polarity can be selected from：Polyacrylonitrile, polyvinyl chloride, polyvinylidene fluoride (PVDF), polyvinylidene fluoride -co- hexafluoropropene, polyvinylidene fluoride -co- trichloro ethylene, polyethyleneimine, poly- methyl-prop E pioic acid methyl ester, butyl polyacrylate, PVP, polyvinyl acetate, polyethylene -co- vinyl acetate, poly- virtue Ester, PPTA and its mixture.
The oxide-base linear polymer can be selected from：PEO, PPOX, polyformaldehyde, poly dimethyl Siloxanes and its mixture.
Then, the first porous support layer 40 (S3) is formed on the polymer solution (30) of application.
Meanwhile first porous support layer 40 can be the perforated membrane or non-woven fabrics of mesh form.This loose structure Allow to electrolyte being introduced into well in electrode active material layers 20, and first porous support layer 40 has itself Excellent electrolyte infiltrates and provides good ionic conductance, thus prevents electrode resistance from raising and finally prevents battery performance Deterioration.
First porous support layer 40 can be by being made selected from any one following：High density polyethylene (HDPE), low-density It is polyethylene, LLDPE, ultra-high molecular weight polyethylene, polypropylene, polyethylene terephthalate, poly- to benzene two Formic acid butanediol ester, polyester, polyacetals, polyamide, makrolon, polyimides, polyether-ether-ketone, polyether sulfone, polyphenylene oxide, polyphenyl Thioether, PEN and its mixture.
In addition, first porous support layer 40 can also include on first porous support layer 40 has conductive material With the conductive material coating of adhesive.The conductive material coating is used to improve the electric conductivity of electrode active material layers and reduces electricity Electrode resistance, thus prevent degradation of cell performance.
Can be with the above-mentioned conductive material being used in priming coat for the conductive material in conductive material coating and adhesive It is identical with adhesive.
This conductive material coating in applied to positive pole when ratio when in applied to negative pole it is more favourable because positive-active The electric conductivity of material layer is low and strengthens the performance degradation as caused by raising electrode resistance, and anode active material layer is with relatively good Good electric conductivity, thus influenceed less to show the performance similar with conventional anode by conductive material coating.
In the conductive material coating, conductive material and adhesive can be with 80:20~99:1 weight ratio is present.Make The serious rise of electrode resistance can be caused with a large amount of adhesives.Therefore, when meeting this number range, it can prevent that electrode is electric The serious rise of resistance.In addition, as noted previously, as the first porous support layer serves as can prevent electrode active material layers from coming off slow Punching, so electrode flexibility will not be largely effected on using adhesive with relatively little of amount.
Then, the obtained thing obtained in step (S3) is compressed to form porous polymeric nitride layer 30, it is described porous Polymeric layer 30 be bonded between electrode active material layers 20 and the first porous support layer 40 and mutually integrated (S4).
Porous polymeric nitride layer 30 can have loose structure so that electrolyte is introduced into electrode active material layers well, and Porosity with 0.01~10 μm of aperture and 5~95%.
The porous coating can be more to have during its preparation by the phase separation caused by non-solvent or phase transformation The mode of pore structure is formed.
For example, it is added to using polyvinylidene fluoride -co- hexafluoropropene as polymer in the acetone as solvent to obtain Solution with 10 weight % solids.Into obtained solution, the water or second of non-solvent are used as using 2~10 weight % amount addition Alcohol is to prepare polymer solution.
Phase transformation is carried out to this polymer solution during drying program after coating, so as to form non-solvent and polymerization The phase separation part of thing.Wherein, the non-solvent portion is changed into hole.Therefore, can be according to the solubility of non-solvent and polymer With the amount of non-solvent and the size of control hole.
Fig. 7 is the photo for the cross section for showing the porous polymeric nitride layer 30 obtained by an embodiment of the invention.
Meanwhile if by the way that polymer solution (30 ') is coated on a surface of electrode active material layers 20, then Dry to form porous polymeric nitride layer 30, and then form the first porous support layer 40 by being laminated onto, be then used to glue Composite electrode active material layer 20 may solidify with the adhesive component in the polymer solution (30 ') of the first porous support layer 40, So that it is difficult to keep strong adhesion between the two layers.
In addition, it is different from the preferred preparation method of the invention using the first porous support layer prepared in advance, if logical Cross and polymer solution be coated in porous polymeric nitride layer and forms porous support layer, then with the present invention the first porous support layer Compare, the mechanical performance of this porous support layer formed by coated polymeric solution is worse, thus can not effectively prevent electricity Pole active material layer comes off.
On the contrary, according to the preferred preparation method of the present invention, the first porous support layer 40 is being placed on to the polymer of application On solution (30 '), then adhesive component solidifies, in the case of they are coated with together using coating blade 60 afterwards, by This formation is bonded between electrode active material layers 20 and the first porous support layer 40 so as to mutually integrated porous polymer Layer 30.
Meanwhile before step (S1) or after step (S4), can be by being carried out on another surface of current-collector Compress and form the second support layer 50.Second support layer 50 can suppress the short circuit of current-collector 10, so as to more improve electrode Flexibility.
Second support layer 50 can be polymer film, and the polymer film can be by selected from any one following system Into：Polyolefin, polyester, polyimides, polyamide and its mixture.
In addition, the present invention provides a kind of secondary cell, the secondary cell includes：Positive pole, negative pole, it is arranged on the positive pole Barrier film and electrolyte between the negative pole, wherein at least one of the positive pole and described negative pole are by above-mentioned What electrode for secondary battery was formed.
The secondary cell of the present invention can be the common form of stacking, winding or stacking/folding, and it can also be cable-type Special shape.
In addition, the present invention provides a kind of cable Type Rechargeable Battery, comprising：Interior electrode；Separation layer, it surrounds the interior electrode Outer surface to prevent the short circuit between electrode；And external electrode, it is by spirally winding so as to surround the separation layer Outer surface and formed, wherein at least one of the interior electrode and described external electrode be by it is above-mentioned according to the present invention two Primary cell electrode and formed.
Herein, term used " spirally " refers to rotate at specific region mobile while spiral-shaped, Including common form of springs.
The external electrode can be the strips of uniaxial extension.
The external electrode can be with spirally winding, so as to not overlap on its width or be overlapped on its width.For example, it is The deterioration of battery performance is prevented, the external electrode of sheet form can spirally be wound with the interval in the double length of its width, So that it is not overlapped.
Or the external electrode can spirally be wound while being overlapped on its width.In this case, in order to press down The excessive rise of battery internal resistance processed, the external electrode can be at dispatch from foreign news agency with spirally winding so as to the width of its overlapping part Within 0.9 times of the width of pole itself.
The interior electrode can be partly empty hollow structure centered on.
The interior electrode can be provided with the core of interior current-collector in it.
The core of the interior current-collector can be by being made as follows：CNT, stainless steel, aluminium, nickel, titanium, sintering carbon or copper；At it The stainless steel treated on surface with carbon, nickel, titanium or silver；Aluminium-cadmium alloy；Do not led with what conductive material treated in its surface Electric polymer；Conducting polymer.
Or the interior electrode can be provided with the core for supplying lithium ion in it, it includes electrolyte.
The core for being used to supply lithium ion can include gel polymer electrolyte and support.
In addition, the core for being used to supply lithium ion can include liquid electrolyte and porous carrier.
Or the interior electrode can be provided with the core of filling in it.
The core of the filling can be made up of some materials of many performances of raising cable-type battery, such as except collecting in formation Beyond the material of the core of electrical equipment and the core for supplying lithium ion, it can be also made up of fluoropolymer resin, rubber and inorganic matter, and There can also be the various forms for including 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 sheet form Interior electrode wound on the outer surface of the core 110 for supplying lithium ion.The interior electrode of sheet form can apply to cable-type In secondary cell, as shown in Figure 8, and the external electrode of sheet form can be similarly on the outer surface of separation layer.
Included according to this cable Type Rechargeable Battery of one embodiment of the present invention：For supplying the core of lithium ion, its Include electrolyte；Interior electrode, it is used to supply the outer surface of the core of lithium ion and comprising current-collector and electrode activity around described Material layer；Separation layer, it surrounds the outer surface of the interior electrode to prevent the short circuit between electrode；And external electrode, it passes through Spirally winding is around the outer surface of the separation layer so as to form, and comprising current-collector and electrode active material layers, its Described at least one of interior electrode and the external electrode be by according to the present invention above-mentioned electrode for secondary battery and shape Into.
The cable Type Rechargeable Battery of the present invention has the level cross-sectionn of predetermined shape, the linear structure extended in the vertical And it is flexible, so as to which it can freely change shape.Term ' predetermined shape ' used herein is not limited to any special shape Shape, and refer to the arbitrary shape for not damaging property of the present invention.
In the cable Type Rechargeable Battery that can be designed by the present invention, wherein it will be made using above-mentioned electrode for secondary battery It is shown in Figure 9 for the cable Type Rechargeable Battery 100 of interior electrode.
With reference to figure 9, cable Type Rechargeable Battery 100 includes：For supplying the core 110 of lithium ion, it includes electrolyte；Interior electricity Pole, it is around the outer surface for being used to supply the core 110 of lithium ion；Separation layer 170, it surrounds the outer surface of the interior electrode To prevent the short circuit between electrode；And external electrode, it is by spirally winding so as to around the appearance of the separation layer 170 Face and formed, and comprising outer current-collector 190 and external electrode active material layer 180, wherein the interior electrode includes interior current-collector 120th, interior electrode active material layers 130 on a surface of the interior current-collector 120 are formed, are formed in the interior electrode active Property material layer 130 top surface on porous polymeric nitride layer 140, formed on the top surface of the porous polymeric nitride layer 140 first The second support layer 160 of porous support layer 150 and formation on another surface of the interior current-collector 120.
It is as already mentioned above, external electrode is also used as according to the electrode for secondary battery of the sheet form of the present invention and Non- interior electrode, or may be used as both.
Core 110 for supplying lithium ion includes electrolyte, and the type of the electrolyte is not particularly limited and can selected From：Use ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate (VC), carbonic acid diethyl Ester (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), methyl formate (MF), gamma-butyrolacton (γ-BL), sulfolane, The nonaqueous electrolytic solution of methyl acetate (MA) or methyl propionate (MP)；Use PEO, PVdF, PVdF-HFP, PMMA, PAN or PVAc Gel polymer electrolyte；And using PEO, PPOX (PPO), polyethyleneimine (PEI), poly- ethyl sulfide (PES) or The solid electrolyte of polyvinyl acetate (PVAc).In addition, the electrolyte can also include lithium salts, the lithium salts can select From：LiCl、LiBr、LiI、LiClO4、LiBF4、LiB10Cl10、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、 LiAlCl4、CH3SO3Li、CF3SO3Li、(CF3SO2)2NLi, chloroborane lithium, lower aliphatic lithium carbonate, tetraphenylboronic acid lithium and its Mixture.Core 110 for supplying lithium ion only can be made up of electrolyte, especially, can be by using porous carrier shape Into liquid electrolyte.
In the present invention, interior electrode can be negative pole or positive pole, and external electrode can be corresponding with the interior electrode Negative or positive electrode.
It can be used for negative pole and the electrode active material in positive pole be same as described above.
Meanwhile separation layer can be dielectric substrate or barrier film.
The dielectric substrate for serving as ion channel can be by being made as follows：Using PEO, PVdF, PVdF-HFP, PMMA, PAN or PVAc gel-type polymer electrolyte；Or use PEO, PPOX (PPO), polyethyleneimine (PEI), poly- ethyl sulfide (PES) or polyvinyl acetate (PVAc) solid electrolyte.It is preferred that formed using polymer or glass-ceramic as skeleton solid The matrix of body electrolyte.In the case of typical polymer dielectric, even if when meeting ionic conductance, in reaction rate Aspect ion still very slowly moves.Therefore, compared with solid electrolyte, preferably using the gel-type for contributing to ion to move Polymer dielectric.The bad mechanical property of gel-type polymer electrolyte, therefore support can be included to improve the mechanicalness of difference Can, the support can be the support or cross-linked polymer of loose structure.The dielectric substrate of the present invention potentially acts as barrier film, Therefore other barrier film can be omitted.
In the present invention, dielectric substrate can also include lithium salts.Lithium salts can improve ionic conductance and response time.Lithium salts Non-limiting examples can include：LiCl、LiBr、LiI、LiClO4、LiBF4、LiB10Cl10、LiPF6、LiCF3SO3、 LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、CF3SO3Li、(CF3SO2)2NLi, chloroborane lithium, lower aliphatic carbon Sour lithium and tetraphenylboronic acid lithium.
The example of barrier film may include but be not limited to：By selected from Alathon, Noblen, ethylene-butene copolymer, Porous polymer matrix made of polyolefin polymers in ethylene-hexene co-polymers and ethylene-methyl acrylate copolymer Material；By selected from polyester, polyacetals, polyamide, makrolon, polyimides, polyether-ether-ketone, polyether sulfone, polyphenylene oxide, polyphenylene sulfide With the polymer in PEN made of porous polymer matrix；By inorganic particulate and binder polymer Porous substrate made of mixture；Or such as lower diaphragm plate, it has at least one table for being formed at the porous polymer matrix Porous coating on face, and include inorganic particulate and binder polymer.
In the porous coating formed by inorganic particulate and binder polymer, the inorganic particulate is by binder polymer And be combined with each other (that is, described adhesive polymer connects and fixes the inorganic particulate), and the porous coating keeps logical Cross the state that binder polymer is combined with the first porous support layer.In the porous coating, the inorganic particulate contacts with each other Ground is filled, and interstitial volume is thus formed between inorganic particulate.Interstitial volume between the inorganic particulate is changed into empty sky Between so as to forming hole.
Wherein, in order that must be used to supplying the lithium ion transfer of the core of lithium ion to external electrode, preferably use with by selected from The corresponding nonwoven cloth diaphragm of porous polymer matrix made of following polymer：Polyester, polyacetals, polyamide, poly- carbonic acid Ester, polyimides, polyether-ether-ketone, polyether sulfone, polyphenylene oxide, polyphenylene sulfide and PEN.
In addition, the cable Type Rechargeable Battery of the present invention has protective coating 195.The protective coating 195 serves as insulator And formed in a manner of around outer current-collector, thus the moisture in by air and external impact are not influenceed guard electrode.Protection applies Layer can be made up of the conventional polymer resin with moisture blocking layer.The moisture blocking layer can be by aluminium or with well blocking water The liquid crystal polymer of ability is made, and the fluoropolymer resin can be PET, PVC, HDPE or epoxy resin.
In addition, the present invention provides a kind of cable Type Rechargeable Battery, there is electrode in two or more, comprising：
The more than two interior electrodes being arranged parallel to each other；
Separation layer, it surrounds the outer surface of the interior electrode to prevent the short circuit between electrode；And
External electrode, it is formed by spirally winding around the outer surface of the separation layer, wherein in described At least one of electrode and the external electrode are to be formed using the above-mentioned electrode for secondary battery according to the present invention.
In addition, the present invention provides a kind of cable Type Rechargeable Battery, there is electrode in two or more, comprising：It is more than two For supplying the core of lithium ion, it includes electrolyte；The more than two interior electrodes being arranged parallel to each other, each interior electrode surround It is each to be used to supply the outer surface of the core of lithium ion and comprising current-collector and electrode active material layers；Separation layer, it is around described The outer surface of interior electrode is to prevent the short circuit between electrode；And external electrode, it is by spirally winding so as to around described The outer surface of separation layer and formed, and comprising current-collector and electrode active material layers, wherein the interior electrode and the external electrode At least one of be using according to the present invention above-mentioned electrode for secondary battery and formed.
In the cable Type Rechargeable Battery with electrode in two or more that can be designed by the present invention, will wherein it use Above-mentioned electrode for secondary battery is shown in Figure 10 as the cable Type Rechargeable Battery 200 of interior electrode.
With reference to figure 10, cable Type Rechargeable Battery 200 includes：More than two cores 210 for being used to supply lithium ion, it is included Electrolyte；The more than two interior electrodes being arranged parallel to each other, each interior electrode is around each core for being used to supply lithium ion Outer surface；Separation layer 270, it surrounds the outer surface of the interior electrode to prevent the short circuit between electrode；And external electrode, it is logical Cross spirally winding to be formed so as to surround the outer surface of the separation layer 270, and include outer current-collector 290 and external electrode work Property material layer 280, wherein each interior electrode include interior current-collector 220, formed on a surface of the interior current-collector 220 Interior electrode active material layers 230, porous polymeric nitride layer 240, the shape formed on the top surface of the interior electrode active material layers 230 Into the first porous support layer 250 on the top surface in the porous polymeric nitride layer 240 and formed in the interior current-collector 220 Another surface on the second support layer 260.
It is as already mentioned above, external electrode is also used as according to the electrode for secondary battery of the sheet form of the present invention and Non- interior electrode, or may be used as both.
In the cable Type Rechargeable Battery 200 with multiple interior electrodes, the number of adjustable interior electrode is lived with coordination electrode The load capacity and battery capacity of property material layer, and can prevent short circuit due to there is a possibility that multiple electrodes.
Industrial applicability
The present invention has been described in detail.It should be understood, however, that detailed description and instantiation, although indicating this hair Bright preferred embodiment, but only provided with illustrative purpose, because according to the detailed description, in the spirit and scope of the invention Interior variations and modifications will become apparent for those skilled in the art.

Claims (68)

1. a kind of electrode for secondary battery of sheet form, comprising：
Current-collector；
Electrode active material layers, it is formed on a surface of the current-collector；
Porous polymeric nitride layer, it is formed in the electrode active material layers；With
First porous support layer, it is formed in the porous polymeric nitride layer,
Wherein described electrode for secondary battery have it is spiral-shaped,
Wherein described first porous support layer selected from any one following by being made：High density polyethylene (HDPE), low density polyethylene (LDPE), It is ultra-high molecular weight polyethylene, polypropylene, polyester, polyacetals, polyamide, polyimides, polyether-ether-ketone, polyether sulfone, polyphenylene oxide, poly- Diphenyl sulfide and its mixture.
2. electrode for secondary battery according to claim 1, wherein the current-collector by being made as follows：Stainless steel, aluminium, nickel, titanium, Sinter carbon or copper；Aluminium-cadmium alloy；The non-conductive polymer treated in its surface with conductive material；Conducting polymer；Comprising The metal paste of Ni, Al, Au, Ag, Pd/Ag, Cr, Ta, Cu, Ba or ITO metal dust；Or include graphite, carbon black or carbon The carbon paste cream of the carbon dust of nanotube.
3. electrode for secondary battery according to claim 1, wherein the current-collector is the form of mesh.
4. electrode for secondary battery according to claim 1, wherein the current-collector is also included by conductive material and adhesive group Into priming coat.
5. electrode for secondary battery according to claim 4, wherein the conductive material is included selected from as follows any：Charcoal Black, carbon fiber, CNT, graphene and its mixture.
6. electrode for secondary battery according to claim 4, wherein described adhesive are selected from polyvinylidene fluoride (PVDF), gathered partially Difluoroethylene -co- hexafluoropropene, polyvinylidene fluoride -co- trichloro ethylene, butyl polyacrylate, polymethyl methacrylate, Polyacrylonitrile, PVP, polyvinyl acetate, polyethylene -co- vinyl acetate, PEO, poly- virtue Ester, cellulose acetate, cellulose acetate-butyrate, cellulose-acetate propionate, cyanoethyl pullulan, cyanoethyl polyvinylalcohol, cyanogen second Base cellulose, cyanoethyl sucrose, Propiram, carboxymethyl cellulose, butadiene-styrene rubber, acrylonitrile-butadiene-styrene copolymer, Polyimides and its mixture.
7. electrode for secondary battery according to claim 1, wherein the current-collector is at least one surface thereof with multiple Recess.
8. electrode for secondary battery according to claim 7, wherein the continuous pattern of the multiple recess or discontinuously pattern Change.
9. electrode for secondary battery according to claim 8, wherein the recess continuously patterned in the vertical mutually every Turn up the soil to be formed.
10. electrode for secondary battery according to claim 8, wherein the recess discontinuously patterned passes through multiple hole shapes Into.
11. electrode for secondary battery according to claim 10, wherein the multiple hole is circular or polygon.
12. electrode for secondary battery according to claim 1, wherein first porous support layer is the perforated membrane of mesh form Or non-woven fabrics.
13. electrode for secondary battery according to claim 2, wherein the stainless steel is to use carbon, nickel, titanium or silver in its surface Treated stainless steel.
14. electrode for secondary battery according to claim 1, wherein also being included on the first porous support layer has conductive material With the conductive material coating of adhesive.
15. electrode for secondary battery according to claim 14, wherein in the conductive material coating, the conductive material and Described adhesive is with 80:20~99:1 weight ratio is present.
16. electrode for secondary battery according to claim 14, wherein the conductive material is included selected from any one following： Carbon black, carbon fiber, CNT, graphene and its mixture.
17. electrode for secondary battery according to claim 14, wherein described adhesive are selected from polyvinylidene fluoride (PVDF), gathered Vinylidene fluoride -co- hexafluoropropene, polyvinylidene fluoride -co- trichloro ethylene, butyl polyacrylate, poly-methyl methacrylate It is ester, polyacrylonitrile, PVP, polyvinyl acetate, polyethylene -co- vinyl acetate, PEO, poly- Aromatic ester, cellulose acetate, cellulose acetate-butyrate, cellulose-acetate propionate, cyanoethyl pullulan, cyanoethyl polyvinylalcohol, cyanogen Ethyl cellulose, cyanoethyl sucrose, Propiram, carboxymethyl cellulose, butadiene-styrene rubber, acrylonitrile-styrene-butadiene copolymer Thing, polyimides and its mixture.
18. electrode for secondary battery according to claim 1, wherein the porous polymer layer has 0.01~10 μm of aperture With 5~95% porosity.
19. electrode for secondary battery according to claim 1, wherein the porous polymer layer includes linearly gathering with polarity Compound, oxide-base linear polymer or its mixture.
20. electrode for secondary battery according to claim 19, wherein the linear polymer with polarity is selected from：Polypropylene Nitrile, polyvinyl chloride, polyvinylidene fluoride (PVDF), polyvinylidene fluoride -co- hexafluoropropene, polyvinylidene fluoride -co- trichlorine Ethene, polyethyleneimine, polymethyl methacrylate, butyl polyacrylate, PVP, polyvinyl acetate, Polyethylene -co- vinyl acetate, polyarylate, PPTA and its mixture.
21. electrode for secondary battery according to claim 19, wherein the oxide-base linear polymer is selected from：Polycyclic oxygen second Alkane, PPOX, polyformaldehyde, dimethyl silicone polymer and its mixture.
22. electrode for secondary battery according to claim 1, it further includes porous coating, and the porous coating is by inorganic The mixture of particle and binder polymer is formed on the first porous support layer.
23. electrode for secondary battery according to claim 1, it further includes and is formed on another surface of the current-collector Second support layer.
24. electrode for secondary battery according to claim 23, wherein second support layer is polymer film.
25. electrode for secondary battery according to claim 24, wherein the polymer film selected from following by any being made： Polyolefin, polyester, polyimides, polyamide and its mixture.
26. electrode for secondary battery according to claim 1, wherein when the electrode for secondary battery is used as into negative pole, institute State electrode active material layers include be selected from following active material：Carbonaceous material；Lithium-titanium composite oxide, and including Si, Sn, Li, Zn, Mg, Cd, Ce, Ni and Fe metal；The alloy of the metal；The oxide of the metal；The metal and carbon are answered Compound；And their mixture, and
When the electrode for secondary battery is used as into positive pole, the electrode active material layers are included selected from following active material Material：LiCoO2；LiNiO2；LiMn2O4；LiCoPO4；LiFePO4；LiNiMnCoO2；LiNi1-x-y-zCoxM1yM2zO2, wherein M1 and M2 is each independently selected from Al, Ni, Co, Fe, Mn, V, Cr, Ti, W, Ta, Mg and Mo, and x, y and z are each independently to form oxygen The atomic fraction of the element of compound, wherein 0≤x<0.5,0≤y<0.5,0≤z<0.5, and x+y+z≤1；And its mixture.
27. according to the electrode for secondary battery of claim 5 or 16, wherein the carbon black is acetylene black or Ketjen black.
28. electrode for secondary battery according to claim 1, wherein the low density polyethylene (LDPE) is LLDPE, And the polyester is polyethylene terephthalate, polybutylene terephthalate (PBT), makrolon or poly- naphthalenedicarboxylic acid second Diol ester.
29. a kind of method for the electrode for secondary battery for preparing sheet form as claimed in claim 1, including：
(S1) slurry containing electrode active material is coated on a surface of current-collector, be subsequently dried, so as to form electrode Active material layer；
(S2) polymer solution containing polymer is coated in the electrode active material layers；
(S3) the first porous support layer is formed on polymer solution；And
(S4) the obtained thing obtained in step (S3) is compressed to form porous polymeric nitride layer, the porous polymeric nitride layer Be bonded between the electrode active material layers and first porous support layer and mutually it is integrated.
30. the method for the electrode for secondary battery according to claim 29 for preparing sheet form, wherein the polymer solution bag Containing adhesive ingredients.
31. the method for the electrode for secondary battery according to claim 30 for preparing sheet form, wherein in step (S3), viscous Before mixture composition is cured, the first porous support layer is formed on polymer solution.
32. the method for the electrode for secondary battery according to claim 30 for preparing sheet form, wherein in step (S4), passes through Coating blade is compressed to the obtained thing obtained in step (S3) to form porous polymeric nitride layer, the porous polymeric nitride layer Be bonded between the electrode active material layers and first porous support layer and mutually it is integrated.
33. the method for the electrode for secondary battery according to claim 29 for preparing sheet form, it further comprises in step (S1) before or after step (S4), the second support layer is formed by being compressed on another surface of current-collector.
34. a kind of secondary cell, the secondary cell includes：Positive pole, negative pole, it is arranged between the positive pole and the negative pole Barrier film and nonaqueous electrolytic solution,
At least one of wherein described positive pole and the negative pole are the secondary cell electricity consumption of any one of claim 1~28 Pole.
35. according to the secondary cell of claim 34, wherein the secondary cell is the form of cable-type.
36. a kind of cable Type Rechargeable Battery, comprising：
Interior electrode；
Separation layer, it surrounds the outer surface of the interior electrode to prevent the short circuit between electrode；And
External electrode, it is formed around the outer surface of the separation layer and by spirally winding,
At least one of wherein described interior electrode and the external electrode are by using according to any one of claim 1 to 28 Electrode for secondary battery and formed.
37. according to the cable Type Rechargeable Battery of claim 36, wherein the external electrode is the strips of uniaxial extension.
38. according to the cable Type Rechargeable Battery of claim 36, wherein the external electrode is spirally wound, so as in its width On do not overlap.
39. according to the cable Type Rechargeable Battery of claim 38, wherein the external electrode is between in the double length of its width Every spirally winding, so that it is not overlapped.
40. according to the cable Type Rechargeable Battery of claim 36, wherein the external electrode is spirally wound, so as in its width It is upper overlapping.
41. according to the cable Type Rechargeable Battery of claim 40, wherein the external electrode is spirally wound, so as to its overlap Within 0.9 times of the width that the width divided is in external electrode itself.
42. according to the cable Type Rechargeable Battery of claim 36, wherein being partly empty hollow structure centered on the interior electrode.
43. according to the cable Type Rechargeable Battery of claim 42, spirally rolled up wherein the interior electrode includes one or more Around electrode for secondary battery.
44. according to the cable Type Rechargeable Battery of claim 42, wherein the interior electrode is provided with the core of interior current-collector in it, For supplying the core of lithium ion, it includes electrolyte；Or the core of filling.
45. according to the cable Type Rechargeable Battery of claim 44, wherein the core of the interior current-collector by being made as follows：Carbon nanometer Pipe, stainless steel, aluminium, nickel, titanium, sintering carbon or copper；Aluminium-cadmium alloy；Treated in its surface with conductive material non-conductive poly- Compound；Conducting polymer.
46. according to the cable Type Rechargeable Battery of claim 45, wherein the stainless steel in its surface with carbon, nickel, titanium or The treated stainless steel of silver.
47. according to the cable Type Rechargeable Battery of claim 44, wherein the core for being used to supply lithium ion includes gel polymerisation Thing electrolyte and support.
48. according to the cable Type Rechargeable Battery of claim 44, wherein the core for being used to supply lithium ion includes liquid electrolytic Matter and porous carrier.
49. according to the cable Type Rechargeable Battery of claim 44, wherein the electrolyte is selected from：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 propionic acid The nonaqueous electrolytic solution of methyl esters (MP)；Use PEO, PVdF, PVdF-HFP, PMMA, PAN or PVAc gel polymer electrolyte； And use PEO, PPOX (PPO), polyethyleneimine (PEI), poly- ethyl sulfide (PES) or polyvinyl acetate (PVAc) Solid electrolyte.
50. according to the cable Type Rechargeable Battery of claim 44, wherein the electrolyte also includes lithium salts.
51. according to the cable Type Rechargeable Battery of claim 50, wherein the lithium salts is selected from：LiCl、LiBr、LiI、LiClO4、 LiBF4、LiB10Cl10、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、CF3SO3Li、 (CF3SO2)2NLi, chloroborane lithium, lower aliphatic lithium carbonate, tetraphenylboronic acid lithium and its mixture.
52. according to the cable Type Rechargeable Battery of claim 44, wherein the core of the filling is by fluoropolymer resin, rubber and inorganic Thing is made in the form of line, fiber, powder, mesh and foam.
53. according to the cable Type Rechargeable Battery of claim 36, wherein the interior electrode is negative pole or positive pole, and the external electrode For the negative or positive electrode corresponding with the interior electrode.
54. according to the cable Type Rechargeable Battery of claim 36, wherein the separation layer is dielectric substrate or barrier film.
55. according to the cable Type Rechargeable Battery of claim 54, wherein the dielectric substrate, which includes, is selected from following electrolyte：Make With PEO, PVdF, PMMA, PVdF-HFP, PAN or PVAc gel polymer electrolyte；With use PEO, PPOX (PPO), the solid electrolyte of polyethyleneimine (PEI), poly- ethyl sulfide (PES) or polyvinyl acetate (PVAc).
56. according to the cable Type Rechargeable Battery of claim 54, wherein the dielectric substrate also includes lithium salts.
57. according to the cable Type Rechargeable Battery of claim 56, wherein the lithium salts is selected from：LiCl、LiBr、LiI、LiClO4、 LiBF4、LiB10Cl10、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、CF3SO3Li、 (CF3SO2)2NLi, chloroborane lithium, lower aliphatic lithium carbonate, tetraphenylboronic acid lithium and its mixture.
58. according to the cable Type Rechargeable Battery of claim 54, wherein the barrier film is：By equal selected from Alathon, propylene TPO polymerization in polymers, ethylene-butene copolymer, ethylene-hexene co-polymers and ethylene-methyl acrylate copolymer Porous polymer matrix made of thing；By selected from polyester, polyacetals, polyamide, makrolon, polyimides, polyether-ether-ketone, poly- Porous polymer matrix made of polymer in ether sulfone, polyphenylene oxide, polyphenylene sulfide and PEN；By inorganic Porous substrate made of the mixture of particle and binder polymer；Or such as lower diaphragm plate, it is described porous poly- with being formed at Porous coating at least one surface of compound base material, and include inorganic particulate and binder polymer.
59. according to the cable Type Rechargeable Battery of claim 58, wherein the porous polymer matrix is apertured polymeric film base Material or porous non-woven cloth base material.
60. according to the cable Type Rechargeable Battery of claim 36, it further includes protective coating, and the protective coating surrounds institute State the outer surface of external electrode.
61. according to the cable Type Rechargeable Battery of claim 60, wherein the protective coating is made up of fluoropolymer resin.
62. according to the cable Type Rechargeable Battery of claim 61, wherein the fluoropolymer resin include selected from PET, PVC, HDPE, Epoxy resin and its mixture it is any.
63. according to the cable Type Rechargeable Battery of claim 61, wherein the protective coating further includes moisture blocking layer.
64. according to the cable Type Rechargeable Battery of claim 63, wherein the moisture blocking layer is made up of aluminium or liquid crystal polymer.
65. a kind of cable Type Rechargeable Battery, comprising：
For supplying the core of lithium ion, it includes electrolyte；
Interior electrode, it includes current-collector and electrode active material layers around the outer surface for being used to supply the core of lithium ion；
Separation layer, it surrounds the outer surface of the interior electrode to prevent the short circuit between electrode；With
External electrode, its by spirally winding so as to which the outer surface around the separation layer is formed, and comprising current-collector and Electrode active material layers,
At least one of wherein described interior electrode and the external electrode are using according to the two of any one of claim 1 to 28 Primary cell electrode and formed.
66. a kind of cable Type Rechargeable Battery, comprising：
The more than two interior electrodes being arranged parallel to each other；
Separation layer, it surrounds the outer surface of the interior electrode to prevent the short circuit between electrode；And
External electrode, it is formed around the outer surface of the separation layer and by spirally winding,
At least one of wherein described interior electrode and the external electrode are using according to the two of any one of claim 1 to 28 Primary cell electrode and formed.
67. a kind of cable Type Rechargeable Battery, comprising：
More than two cores for being used to supply lithium ion, it includes electrolyte；
The more than two interior electrodes being arranged parallel to each other, each interior electrode is around each appearance for being used to supply the core of lithium ion Face simultaneously includes current-collector and electrode active material layers；
Separation layer, it surrounds the outer surface of the interior electrode to prevent the short circuit between electrode；And
External electrode, its by spirally winding so as to which the outer surface around the separation layer is formed, and comprising current-collector and Electrode active material layers, wherein
At least one of the interior electrode and the external electrode are using the secondary electricity according to any one of claim 1 to 28 Pond electrode and formed.
68. according to the cable Type Rechargeable Battery of claim 67, spirally rolled up wherein the interior electrode includes one or more Around electrode for secondary battery.
CN201410191341.1A 2013-05-07 2014-05-07 Electrode for secondary battery, it prepares and includes its secondary cell and cable Type Rechargeable Battery Active CN104393231B (en)

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