CN104993150A - Flexible device and preparation method thereof - Google Patents
Flexible device and preparation method thereof Download PDFInfo
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- CN104993150A CN104993150A CN201510394861.7A CN201510394861A CN104993150A CN 104993150 A CN104993150 A CN 104993150A CN 201510394861 A CN201510394861 A CN 201510394861A CN 104993150 A CN104993150 A CN 104993150A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention belongs to the technical field of flexible devices, and particularly relates to a flexible device. The flexible device comprises a positive plate, a negative plate and an isolating membrane, the negative plate is composed of negative active materials and a negative current collector which is composed of a porous structural layer and a matrix layer, the porous structural layer comprises a pore structural region and a non-pore region, the sizes of the pore structural region and the non-pore region are V1 and V2 respectively, and V1/(V1+V2) >= 10%; the negative active materials are distributed in pore structures of the porous structural layer or on the surface of the non-pore region of the porous structural layer, the mass of the active materials which are distributed in the pore structures of the porous structural layer is W1, the mass of the active materials which are distributed on the surface of the non-pore region of the porous structural layer is W2, and W1/(W1+W2) >= 10%. According to the flexible device and a preparation method thereof, the porous current collector is adopted, the bonding force between the current collector and the active materials can be increased, tight bonding of interfaces of the flexible device in the bending process is guaranteed, and therefore the prepared flexible device is more excellent in flexibility and electro-chemical performance.
Description
Technical field
The invention belongs to flexible device technical field, particularly a kind of flexible device and preparation method thereof.
Background technology
1991, the creationary employing Carbon Materials of Sony corporation of Japan as lithium ion battery anode material, for field of lithium ion battery brings revolutionary change; Since then, lithium ion battery technology fast development, uses in a large number on mobile phone, video camera, notebook computer and other portable electronics.Lithium ion battery has plurality of advantages, such as voltage is high, volume is little, quality is light, memory-less effect higher than ability, pollution-free, self discharge is little, have extended cycle life, and is 21st century desirable movable electrical appliances power supply, electric car power supply and electricity storage station electrical storage device.
But along with electronic device is towards personalized future development, a large amount of creative electronic product emerges in large numbers rapidly: as the wearable devices such as intelligent watch, intelligent glasses, Intelligent bracelet in succession occur and obtain the accreditation of consumers in general within a few years time.Different from conditional electronic product, this electronic product has the features such as profile is irregular, flexible, therefore proposes new requirement to the power supply part (i.e. battery) of these electronic products: irregular, flexible etc.
For flexible device, in bending process back and forth, device inside interface will be subject to stern challenge; And electrochemical device, interfacial reaction is one of deciding factor affecting its performance; Therefore to ensure that flexible device has excellent chemical property, must guarantee that this device has excellent interface cohesive force.
The U.S. Patent Application Publication No. 2013/0171490A1 announced July 4 in 2013 discloses a kind of flexible battery group, by upper and lower lamination by a series of battery-arrangements, and battery is isolated upper and lower adhesion layer bonding by the adhesive between battery, thus prepare flexible battery group.But the flexible battery group of this design is when bending, due to top layers and bottom layer rigid comparatively strong, affected by force, bending degree and the fatigue resistance of flexible battery group are very restricted, and affect the performance of flexible battery group performance; Binding agent is after certain angle of bend and number of bends, and adhesive strength can decline, and causes its fixing to be deteriorated, and easy produces fatigue in the adhesive free region close with binding agent because active force is inconsistent, risky to the security performance of flexible battery group.And the method needs to control the adhesive strength of adhesive and the homogeneous of each region use amount, and the difficulty of volume production is very large.
In view of this, necessaryly provide a kind of new flexible device, make it have excellent interface cohesive force, even if still closely bond after repeatedly bending, thus prepare the flexible device of function admirable.
Summary of the invention
The object of the invention is to: for the deficiencies in the prior art, and a kind of electrochemical energy storing device provided: comprise a slice positive plate, a slice negative plate and barrier film, described negative plate is made up of negative electrode active material and negative current collector; Described negative current collector is made up of porous structure layer and base layer, and described porous structure layer is attached to described base layer surface; Described porous structure layer comprises pore structure district and non-porose area, and the volume of described pore structure district and non-porose area is respectively V1, V2, and V1/ (V1+V2) >=10%, now contain enough holes in collector, provide the space storing active material; Described negative electrode active material is distributed in the pore structure of described porous structure layer or the surface of non-porose area of described porous structure layer, the quality being distributed in the active material in the pore structure of described porous structure layer is W1, the quality being distributed in the active material on the non-porose area surface of described porous structure layer is W2, and W1/ (W1+W2) >=10%, now active substance part or whole inserting in the hole of described porous current collector.The present invention adopts porous current collector, and active material is embedded in the pore structure of porous current collector wholly or in part, thus increases the bonding force between collector and active material, guarantees that flexible device closely bonds in bending process median surface; Therefore the flexible device prepared has more excellent flexibility and chemical property.
In order to achieve the above object, the present invention adopts following technical scheme:
A kind of flexible device, comprise a slice positive plate, a slice negative plate and barrier film, described negative plate is made up of negative electrode active material and negative current collector, it is characterized in that:
Described negative current collector is made up of porous structure layer and base layer, and described porous structure layer is attached to described base layer surface;
Described porous structure layer comprises pore structure district and non-porose area, and the volume of described pore structure district and non-porose area is respectively V1, V2, and V1/ (V1+V2) >=10%, now contain enough holes in collector, provide the space storing active material;
Described negative electrode active material is distributed in the pore structure of described porous structure layer or the surface of non-porose area of described porous structure layer, the quality being distributed in the active material in the pore structure of described porous structure layer is W1, the quality being distributed in the active material on the non-porose area surface of described porous structure layer is W2, and W1/ (W1+W2) >=10%, now active substance part or whole inserting in the hole of described porous current collector.
One as flexible device of the present invention is improved, it is at least one in metal simple-substance, metal and metal alloy, metal and non-metal alloy that described base layer has conductive capability and water proof ability concurrently, or be the composite material that metal simple-substance or its alloy and other materials are formed, and the thickness of described base layer is h, and h is more than or equal to 1 μm, collector is enough thick, just with obtain the hole with certain depth, for carrying active substance.
One as flexible device of the present invention is improved, and the thickness of the porous structure layer of described collector is a, and 5 μm≤a≤1000 μm, when loose structure layer thickness is excessive, ion diffuse path can be increased, the high rate performance of battery is deteriorated; The hole equivalent diameter of described loose structure structure sheaf is that d is (when equivalent aperture diameter refers to and hole area is converted into an area of a circle, described diameter of a circle), and 0.1 μm≤d≤2cm, equivalent diameter is too small, enough active materials cannot be filled, equivalent diameter is excessive, cannot represent the fixation of pore structure to active material fully, and can affect the electronic conductance of electrode; The pore wall thickness of described porous structure layer is b, and 0.01 μm≤b≤1cm; The hole length of described porous structure layer is L, and L≤4a, when hole depth is excessive, the ion transfer path being filled in active material in pore structure must be increased, thus affect the high rate performance of battery; Described porous structure layer is at least one in metal simple-substance, metal and the metal alloy, the alloy of metal and nonmetal formation and the conducting polymer that are formed, or is the composite material that metal simple-substance, alloy, conducting polymer and other materials are formed.
One as flexible device of the present invention is improved, 10 μm≤h≤100 μm, 20 μm≤a≤500 μm, 0.6 μm≤d≤1cm, 0.05 μm≤b≤10mm, L≤2a; The hole shape of described porous structure layer is at least one in circle, ellipse, polygon, non-regular shape (as the hole etc. that line segment and camber line are formed).
One as flexible device of the present invention is improved, V1/ (V1+V2) >=50%; W1/ (W1+W2) >=50%.
One as flexible device of the present invention is improved, and also contains conductive agent or/and bonding agent in described negative electrode active material; Described porous structure layer has conductive capability, and the hole in described pore structure district runs through whole described porous structure layer; Be provided with conductive adhesion layer between described porous structure layer and described base layer, and the thickness of described conductive adhesion layer is c, c≤1 μm.
One as flexible device of the present invention is improved, and described metal comprises at least one in Mg, Ca, Sr, Ba, Ra, Al, Ga, In, Ge, Sn, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, La, W, Pt, Au, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; Describedly nonmetally comprise at least one in H, B, C, N, O, Si, P, S, As, Se, Te, F, Cl, Br, I; Described other materials is polymer composite, described polymer composite is the organic substance of molecular weight more than 200 formed by described nonmetalloid, comprises at least one in polypyrrole (PPy), polyaniline (PANi), polyacrylonitrile (PAN), Polyglycolic acid fibre (PEDOT), poly(ethylene oxide) (PEO) and polyethylene glycol (PEG).
One as flexible device of the present invention is improved, and described conducting polymer comprises at least one in polythiophene and derivative, polypyrrole and derivative thereof, Polyaniline and its derivative, polyacetylene, conducting resinl.
One as flexible device of the present invention is improved, and described negative electrode active material comprises at least one in material with carbon element (graphite, disordered carbon), carbon compound (B ~ C ~ N series, C ~ Si ~ O series), non-carbon material (metal oxide, lithium ~ transition metal nitride, lithium alloy); Described conductive agent comprises at least one in conductive carbon black, super conductive carbon, carbon nano-tube, Ketjen black, Graphene; Described bonding agent comprises at least one in copolymer tetrafluoroethylene, all polytetrafluoroethylene, butadiene-styrene rubber, sodium carboxymethylcellulose, polyacrylic acid, polypropylene cyanogen, polyvinyl alcohol, polyolefin, Viton, Polyurethane.
The present invention also comprises a kind of preparation method of flexible device, mainly comprises the steps:
Step 1, prepared by porous current collector: prepare porous structure layer, be arranged in substrate surface, make porous structure layer be attached to substrate surface and electronic conduction, obtain porous current collector;
Step 2, prepared by negative plate: porous structure layer side negative electrode active material being arranged in porous current collector described in step 1, obtains negative plate;
Step 3, flexible device is assembled: above-mentioned negative plate and barrier film, positive plate are assembled, change into, shaping obtains flexible device.
One as the preparation method of flexible device of the present invention is improved, it is characterized in that, porous structure layer described in step 1 obtains porous structure layer for directly preparing (namely prepare in forming process at collector and just form loose structure), or pore-free material prepares porous structure layer by etching; Described etching comprises at least one in laser ablation, chemical etching, quantum bombardment; The collector of the positive plate described in step 3 can be porous current collector.
In addition, in order to increase flexible device wear resistance of the present invention, can also increase one layer of polymeric layer on the collector top layer as encapsulating material, as polyethylene, nylon layer etc., this protective layer can also play the object of isolated electronics simultaneously.
Compared with prior art, flexible device of the present invention and preparation method thereof tool has the following advantages:
1. use the hole storage area negative electrode active material of porous current collector, the active matter quality being coated on collection liquid surface can be reduced, thus reduce surface reactive material coating layer thickness, increase the adhesive force of face coat and collector;
2. use porous current collector, the contact area of electrode coating and collector can be increased, thus increase the bonding force between collector and coating;
3. use porous current collector, the active material on the active material in hole and collector top layer forms an organic whole, forms falcon fourth of the twelve Earthly Branches structure between itself and collector, can increase the adhesive strength between two kinds greatly;
4., because this porous current collector is divided into porous structure layer and base layer, when preparing porous layer, preparation technology is very simple, and the hole uniformity obtained is good; And base layer can play the double action of battery packaging material and collector, intercept while aqueous vapor enters inside battery and carry out electronic conductance and electron collection; Collector after two kinds of compounds has more excellent performance.
Embodiment
Below in conjunction with embodiment, the present invention and beneficial effect thereof are described in detail, but embodiments of the present invention are not limited thereto.
Comparative example 1
Prepared by collector: selection thickness is the Copper Foil of 100 μm is that collector is stand-by.
Prepared by negative plate: with silicon-carbon compound (silicone content is for 30%), PVDF is bonding agent, Supper-P is conductive agent (three's mass ratio is 94:3:3), NMP is solvent configuration slurry; Be coated in a surface of above-mentioned collector afterwards, dry, cold pressing, to cut into monolithic (all around for empty foil district, centre is coating region) stand-by.
Battery is assembled: positive plate (one side coating is all around empty foil district, and middle is coating region), barrier film (containing pvdf coating) are cut into the size matched with above-mentioned positive plate; Dry, then spray in positive pole coating electrolyte obtain infiltrate after positive plate; Adhesive linkage is arranged in empty foil (coating homonymy) district of negative current collector surrounding, according to the mode of negative plate, barrier film, positive plate stacking (both positive and negative polarity active matter is all towards barrier film), after heat compound positive pole, barrier film, negative pole are closely bonded, positive/negative plate closely bonds together by the adhesive linkage being simultaneously arranged in negative current collector surrounding, and plays the object of sealing surrounding; Through changing into, shaping obtains flexible device.
Embodiment 1
The preparation of porous current collector: select thickness to be that the Copper Foil of 1 μm is as base layer; Selection thickness is the Copper Foil of 100 μm, adopt the mode of laser drilling afterwards, this Copper Foil is punched thus obtain hole shape for circular, bore dia be 2 μm, the hole that pitch of holes (two bore edges) is 1 μm, hole depth is 100 μm, thus obtain the porous structure layer of porous current collector; Above-mentioned porous structure layer and collective's layer are cut, uses conduction rubber cement porous structure layer to be adhered to afterwards base layer to obtain porous current collector stand-by;
Prepared by negative plate: with silicon-carbon compound (silicone content is for 30%) for negative electrode active material, PVDF is bonding agent, Supper-P is conductive agent (three's mass ratio is 94:3:3), NMP is solvent configuration slurry; Be coated in afterwards above-mentioned porous current collector contain pore structure side surface (during coating control applied thickness, make W1/ (W1+W2)=50%), dry, cold pressing, to cut into monolithic (all around for empty foil district, centre is coating region) stand-by.
Battery is assembled: with comparative example 1;
Embodiment 2
Difference from Example 1 is, comprises the steps:
The preparation of porous current collector: select thickness to be that the Copper Foil of 10 μm is as base layer.
All the other are identical with embodiment 1, repeat no more.
Embodiment 3
Difference from Example 1 is, comprises the steps:
The preparation of porous current collector: select thickness to be that the Copper Foil of 15 μm is as base layer; Selection thickness is the Copper Foil of 100 μm, adopt the mode of laser drilling afterwards, this Copper Foil is punched thus obtain hole shape for circular, bore dia be 1 μm, the hole that pitch of holes (two bore edges) is 2.8 μm, hole depth is 100 μm, thus obtain the porous structure layer of porous current collector; Above-mentioned porous structure layer and collective's layer are cut, uses conduction rubber cement porous structure layer to be adhered to afterwards base layer to obtain porous current collector stand-by;
Prepared by negative plate: with silicon-carbon compound (silicone content is for 30%) for negative electrode active material, PVDF is bonding agent, Supper-P is conductive agent (three's mass ratio is 94:3:3), NMP is solvent configuration slurry; Be coated in afterwards above-mentioned porous current collector contain pore structure side surface (during coating control applied thickness, make W1/ (W1+W2)=10%), dry, cold pressing, to cut into monolithic (all around for empty foil district, centre is coating region) stand-by.
All the other are identical with embodiment 1, repeat no more.
Embodiment 4
Difference from Example 1 is, comprises the steps:
The preparation of porous current collector: select thickness to be that the Copper Foil of 20 μm is as base layer; Selection thickness is the Copper Foil of 150 μm, adopt the mode of laser drilling afterwards, this Copper Foil is punched thus obtain hole shape for circular, bore dia be 0.1 μm, the hole that pitch of holes (two bore edges) is 0.05 μm, hole depth is 150 μm, thus obtain the porous structure layer of porous current collector; Above-mentioned porous structure layer and collective's layer are cut, uses conduction rubber cement porous structure layer to be adhered to afterwards base layer to obtain porous current collector stand-by;
Prepared by negative plate: take silicon as negative electrode active material, silicon nanoparticle is inserted in the pore structure of porous current collector, now, active material silicon is all restricted to (i.e. W1/ (W1+W2)=100%) in the pore structure of porous current collector, and after cooling, namely taking-up obtains positive plate;
All the other are identical with embodiment 1, repeat no more.
Embodiment 5
Difference from Example 4 is, comprises the steps:
The preparation of porous current collector: in porous structure layer, bore dia is 0.6 μm, and pitch of holes (two bore edges) is 0.05 μm
All the other are identical with embodiment 1, repeat no more.
Embodiment 6
Difference from Example 4 is, comprises the steps:
The preparation of porous current collector: in porous structure layer, bore dia is 2 μm, and pitch of holes (two bore edges) is 0.05 μm;
All the other are identical with embodiment 4, repeat no more.
Embodiment 7
The preparation of porous current collector: select thickness to be that the Copper Foil of 100 μm is as base layer; Selection thickness is the Copper Foil of 1000 μm, adopt the mode of laser drilling, chemical corrosion afterwards, punch to this Copper Foil thus to obtain hole shape be equivalent diameter that is square, hole is 2cm, pitch of holes (two bore edges) obtains the porous structure layer of porous current collector for 1cm's; Above-mentioned porous structure layer and collective's layer are cut, use conduction rubber cement porous structure layer to be adhered to afterwards base layer to obtain porous current collector stand-by, now obtained hole depth is 1500 μm;
Prepared by negative plate: take lithium titanate as negative electrode active material, PVDF is bonding agent, Supper-P is conductive agent (three's mass ratio is 94:3:3), NMP is solvent configuration slurry; Be coated in afterwards above-mentioned porous current collector contain pore structure side surface (during coating control applied thickness, make W1/ (W1+W2)=90%), dry, cold pressing, to cut into monolithic (all around for empty foil district, centre is coating region) stand-by.
Battery is assembled: with comparative example 1;
Embodiment 8
Difference from Example 7 is, comprises the steps:
The preparation of porous current collector: select thickness to be that the Copper Foil of 100 μm is as base layer; Select thickness to be the Copper Foil of 300 μm, adopt the mode of laser drilling, chemical corrosion afterwards, this Copper Foil to be punched thus to obtain hole shape be equivalent diameter that is square, hole is 1cm, the porous structure layer that pitch of holes (two bore edges) is 10mm; Above-mentioned porous structure layer and collective's layer are cut, use conduction rubber cement porous structure layer to be adhered to afterwards base layer to obtain porous current collector stand-by, now obtained hole depth is 360 μm;
All the other are identical with embodiment 7, repeat no more.
Embodiment 9
Difference from Example 7 is, comprises the steps:
The preparation of porous current collector: select thickness to be that the Copper Foil of 100 μm is as base layer; Select thickness to be the Copper Foil of 300 μm, adopt the mode of laser drilling, chemical corrosion afterwards, to punch thus to obtain hole shape be square, hole equivalent diameter is 200 μm to this Copper Foil, pitch of holes (two bore edges) is the porous structure layer of 5 μm; Above-mentioned porous structure layer and collective's layer are cut, use conduction rubber cement porous structure layer to be adhered to afterwards base layer to obtain porous current collector stand-by, now obtained hole depth is 600 μm;
All the other are identical with embodiment 7, repeat no more.
Embodiment 10
Difference from Example 7 is, comprises the steps:
The preparation of porous current collector: select thickness to be that the Copper Foil of 100 μm is as base layer; Select thickness to be the Copper Foil of 300 μm, adopt the mode of laser drilling, chemical corrosion afterwards, to punch thus to obtain hole shape be square, hole equivalent diameter is 200 μm to this Copper Foil, pitch of holes (two bore edges) is the porous structure layer of 5 μm; Above-mentioned porous structure layer and collective's layer are cut, use conduction rubber cement porous structure layer to be adhered to afterwards base layer to obtain porous current collector stand-by, now obtained hole depth is 1200 μm;
All the other are identical with embodiment 7, repeat no more.
Embodiment 11
Difference from Example 7 is, comprises the steps:
Porous current collector base layer material is nickel; Porous structure layer material is polypyrrole, and thickness is 500 μm, and the porous current collector hole depth finally obtained is 750 μm, and negative electrode active material is graphite.
All the other are identical with embodiment 7, repeat no more.
Embodiment 12
Difference from Example 7 is, comprises the steps:
Porous current collector base layer material is rustless steel; Porous structure layer material is polyaniline, and negative electrode active material is manganese bioxide material.
All the other are identical with embodiment 7, repeat no more.
Embodiment 13
Difference from Example 1 is, the present embodiment comprises the steps:
The preparation of porous current collector: select thickness to be that the Copper Foil of 1 μm is as base layer; Selection thickness is the Copper Foil of 5 μm, adopt the mode of laser drilling afterwards, this Copper Foil is punched thus obtain hole shape for circular, bore dia be 2 μm, the hole that pitch of holes (two bore edges) is 1 μm, hole depth is 5 μm, thus the porous structure layer obtaining porous current collector; Above-mentioned porous structure layer and collective's layer are cut, uses conduction rubber cement porous structure layer to be adhered to afterwards base layer to obtain porous current collector stand-by;
All the other are identical with embodiment 1, repeat no more.
Embodiment 14
Difference from Example 1 is, the present embodiment comprises the steps:
The preparation of porous current collector: select thickness to be that the Copper Foil of 1 μm is as base layer; Selection thickness is the Copper Foil of 20 μm, adopt the mode of laser drilling afterwards, this Copper Foil is punched thus obtain hole shape for circular, bore dia be 2 μm, the hole that pitch of holes (two bore edges) is 1 μm, hole depth is 20 μm, thus obtain the porous structure layer of porous current collector; Above-mentioned porous structure layer and collective's layer are cut, uses conduction rubber cement porous structure layer to be adhered to afterwards base layer to obtain porous current collector stand-by;
All the other are identical with embodiment 1, repeat no more.
Embodiment 15
Difference from Example 1 is, the present embodiment comprises the steps:
The preparation of porous current collector: select thickness to be that the Copper Foil of 1 μm is as base layer; Selection thickness is the Copper Foil of 50 μm, adopt the mode of laser drilling afterwards, this Copper Foil is punched thus obtain hole shape for circular, bore dia be 2 μm, the hole that pitch of holes (two bore edges) is 1 μm, hole depth is 50 μm, thus obtain the porous structure layer of porous current collector; Above-mentioned porous structure layer and collective's layer are cut, uses conduction rubber cement porous structure layer to be adhered to afterwards base layer to obtain porous current collector stand-by;
All the other are identical with embodiment 1, repeat no more.
Volume test: carry out volume test by the battery core of following flow process to comparative example and each embodiment in 35 DEG C of environment: leave standstill 3min; 0.5C constant current charge is to 4.2V, and constant voltage charge is to 0.05C; Leave standstill 3min; 0.5C constant-current discharge obtains discharge capacity D0 first to 3.0V; Volume test is completed after leaving standstill 3min; Acquired results is in table 1.
Bending: flexible battery core in comparative example and each embodiment is carried out 0 degree ~ 180 degree bendings, bending number of times 500 times; According to above-mentioned flow process, volume test is carried out to comparative example and each embodiment respectively afterwards.
Battery core high rate performance test (after getting volume test battery core): multiplying power test is carried out to the lithium ion battery that comparative example and each embodiment prepare.Battery core is carried out multiplying power test in 35 DEG C of environment, and flow process is: leave standstill 3min; 0.5C constant current charge is to 4.2V, and constant voltage charge is to 0.05C; Leave standstill 3min; 0.2C constant-current discharge obtains discharge capacity D0 first to 3.0V.Leave standstill 3min; 0.5C constant current charge is to 4.2V, and constant voltage charge is to 0.05C; Leave standstill 3min; 2C constant-current discharge obtains discharge capacity D1 first to 3.0V.High rate performance Rate=D1/D0, acquired results is in table 1.
Table 1, the electrical property table of the energy storage device of comparative example and embodiment
By table 1, comparative examples 1, embodiment 1 ~ 6 can obtain, and use flexible battery prepared by the present invention, after bending 500 times, battery capacity conservation rate is higher, illustrates that battery of the present invention has better combination property.
Flexible battery core prepared by embodiment 1,2 is placed in 60 DEG C, 20 days are stored in the environment of 95% humidity, find the flexible battery core flatulence of embodiment 1, the battery core of embodiment 2 is intact, this is the not perforated thickness h of porous current collector too little (1 μm) due to embodiment 1, cannot play the effect of intact obstruct aqueous vapor, therefore in hot and humid environment, aqueous vapor penetrates into battery core inside and causes battery core aerogenesis.
Comparative example's 4 ~ embodiment 6 finds, effective aperture along with porous current collector becomes large gradually, the high rate performance of the flexible device prepared is poorer, this be due to porous current collector hole less time, collector can serve as electronic conductor, increase the electric conductivity of silicon electrode, thus prepare the excellent flexible battery of high rate performance; But when effective aperture is larger, the electronics on collector is difficult to conduct to the silicon active material place being positioned at center, hole, therefore can affect the high rate performance of flexible device.And effective aperture less time, be also conducive to the constraint of pore structure to volumetric expansion after the embedding lithium of silicon materials, reduce electrode expansion absolute value, be conducive to the structural stability improving electrode, improve the cycle performance of flexible battery.
Comparative example's 8 ~ embodiment 10 can find, along with the increase of porous current collector hole length, the high rate performance of the flexible device prepared reduces gradually, this is due to the increase along with porous current collector hole length, the ion diffuse path of silicon active material in charge and discharge process be filled in pore structure is longer, and therefore the high rate performance of battery is poorer.
Can be obtained by each embodiment, the present invention has universality, to collector, the different negative electrode active materials of unlike material, is all applicable to the present invention.
The announcement of book and instruction according to the above description, those skilled in the art in the invention can also change above-mentioned execution mode and revise.Therefore, the present invention is not limited to above-mentioned embodiment, and any apparent improvement of every those skilled in the art done by basis of the present invention, replacement or modification all belong to protection scope of the present invention.In addition, although employ some specific terms in this specification, these terms just for convenience of description, do not form any restriction to the present invention.
Claims (10)
1. a flexible device, comprise a slice positive plate, a slice negative plate and barrier film, described negative plate is made up of negative electrode active material and negative current collector, it is characterized in that:
Described negative current collector is made up of porous structure layer and base layer, and described porous structure layer is attached to described base layer surface;
Described porous structure layer comprises pore structure district and non-porose area, and the volume of described pore structure district and non-porose area is respectively V1, V2, and V1/ (V1+V2) >=10%;
Described negative electrode active material is distributed in the pore structure of described porous structure layer or the surface of non-porose area of described porous structure layer, the quality being distributed in the active material in the pore structure of described porous structure layer is W1, the quality being distributed in the active material on the non-porose area surface of described porous structure layer is W2, and W1/ (W1+W2) >=10%.
2. a flexible device according to claim 1, it is characterized in that, described base layer is at least one in metal simple-substance, metal and metal alloy, metal and non-metal alloy, or be the composite material that metal simple-substance or its alloy and other materials are formed, and the thickness of described base layer is h, and h is more than or equal to 1 μm.
3. a flexible device according to claim 1, is characterized in that, the thickness of the porous structure layer of described collector is a, and 5 μm≤a≤1000 μm; The hole equivalent diameter of described loose structure structure sheaf is d, and 0.1 μm≤d≤2cm; The pore wall thickness of described porous structure layer is b, and 0.01 μm≤b≤1cm; The hole length of described porous structure layer is L, and L≤4a; Described porous structure layer is at least one in metal simple-substance, metal and the metal alloy, the alloy of metal and nonmetal formation and the conducting polymer that are formed, or is the composite material that metal simple-substance, alloy, conducting polymer and other materials are formed.
4. a flexible device according to claim 3, is characterized in that, 10 μm≤h≤100 μm, 20 μm≤a≤500 μm, 0.6 μm≤d≤1cm, 0.05 μm≤b≤10mm, L≤2a; The hole shape of described porous structure layer is at least one in circle, ellipse, polygon.
5. the flexible device described in any one of Claims 1 to 4, is characterized in that, V1/ (V1+V2) >=50%; W1/ (W1+W2) >=50%.
6. a flexible device according to claim 1, is characterized in that, also contains conductive agent or/and bonding agent in described negative electrode active material; Described porous structure layer has conductive capability, and the hole in described pore structure district runs through whole described porous structure layer; Be provided with conductive adhesion layer between described porous structure layer and described base layer, and the thickness of described conductive adhesion layer is c, c≤1 μm.
7. the flexible device described in a Claims 2 or 3, it is characterized in that, described metal comprises at least one in Mg, Ca, Sr, Ba, Ra, Al, Ga, In, Ge, Sn, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, La, W, Pt, Au, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; Describedly nonmetally comprise at least one in H, B, C, N, O, Si, P, S, As, Se, Te, F, Cl, Br, I; Described other materials is polymer composite, and described polymer composite comprises at least one in polypyrrole (PPy), polyaniline (PANi), polyacrylonitrile (PAN), Polyglycolic acid fibre (PEDOT), poly(ethylene oxide) (PEO) and polyethylene glycol (PEG).
8. a flexible device according to claim 3, is characterized in that, described conducting polymer comprises at least one in polythiophene and derivative, polypyrrole and derivative thereof, Polyaniline and its derivative, polyacetylene, conducting resinl.
9. a preparation method for flexible device described in claim 1, is characterized in that, mainly comprises the steps:
Step 1, prepared by porous current collector: prepare porous structure layer, be arranged in substrate surface, make porous structure layer be attached to substrate surface and electronic conduction, obtain porous current collector;
Step 2, prepared by negative plate: porous structure layer side negative electrode active material being arranged in porous current collector described in step 1, obtains negative plate;
Step 3, flexible device is assembled: above-mentioned negative plate and barrier film, positive plate are assembled, change into, shaping obtains flexible device.
10. a preparation method for flexible device according to claim 9, is characterized in that, the porous structure layer described in step 1 is for directly to prepare porous structure layer, or pore-free material prepares porous structure layer by etching; Described etching comprises at least one in laser ablation, chemical etching, quantum bombardment.
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| CN111048787A (en) * | 2019-12-11 | 2020-04-21 | 合肥国轩高科动力能源有限公司 | Manufacturing method of flexible composite current collector |
| CN111063860A (en) * | 2019-12-19 | 2020-04-24 | 深圳市倍特力电池有限公司 | Electrode plate, preparation method thereof and battery |
| CN111342053A (en) * | 2020-03-02 | 2020-06-26 | 太仓中科赛诺新能源科技有限公司 | Flexible integrated electrode plate and preparation method and application thereof |
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