CN109216703A - A kind of flexible, porous collector and preparation method thereof - Google Patents
A kind of flexible, porous collector and preparation method thereof Download PDFInfo
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- CN109216703A CN109216703A CN201811039741.5A CN201811039741A CN109216703A CN 109216703 A CN109216703 A CN 109216703A CN 201811039741 A CN201811039741 A CN 201811039741A CN 109216703 A CN109216703 A CN 109216703A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A kind of flexible, porous collector and preparation method thereof, belongs to battery afflux liquid field of material technology.The collector includes flexible, porous conductive substrates and the ultra-thin conductive metal layer for being plated in flexible, porous conductive substrates surface；The flexible, porous conductive substrates are the evenly dispersed perforated membrane formed in the polymeric material of conductive powder material.The method is as follows: it is first that polymer and conductive powder material melting mixing is uniform, flexible, porous conductive substrates are prepared using the double daraf(reciprocals of farad) of dry method in lithium battery diaphragm production equipment；One layer of ultra-thin conductive metal layer is plated on flexible, porous conductive substrates surface using vacuum evaporation or electro-plating method again, obtains flexible, porous collector.The invention has the advantages that since the base material is that conductive powder body and polymer are uniformly compound, have the characteristics that flexible, tensile strength is high, electric conductivity is high, low density, can further improve its electric conductivity and tensile strength after plating one layer of ultra-thin conductive metal layer on this substrate.
Description
Technical field
The invention belongs to battery afflux liquid field of material technology, and in particular to a kind of flexible, porous collector and its preparation side
Method.
Background technique
With the development of wearable device, flexible super capacitor, flexible lithium-ion capacitor, flexible lithium ion battery etc.
The demand of flexible energy storage device is increasing.Wherein, flexible current-collecting body is the critical material for restricting flexible energy storage device development.It is existing
The collectors such as the collector of some batteries such as copper foil, aluminium foil, stainless steel foil, foam copper, nickel foam have certain flexibility, still
It is used as flexible battery collector and still shows toughness deficiency, the disadvantage of bending resistance difference.
The thinking of one solution is using metal wire knitted networking or fabric, such as copper mesh, stainless (steel) wire, nickel screen etc.
Metal mesh, the flexibility and bending resistance of collector can be obviously improved by doing collector really using metal mesh.However, using metal mesh
New problem can be brought by doing collector, if will lead to its thickness using thicker metal wire knitted networking and surface density be higher,
Reduce the energy density of entire battery；If will lead to cost using superfine metal wire knitted networking and steeply rise.In addition have
A kind of resolving ideas is or to be woven into carbon cloth, or be prepared into graphite using conductive materials such as carbon fiber, graphene, carbon nanotubes
The problem of flexible substrates such as alkene paper, carbon paper, this thinking is the lower influence battery processing of its intensity, and is difficult to be prepared into ultra-thin
Collector, battery energy density will receive limitation.In addition have a kind of thinking be using ITO electro-conductive glass, this electro-conductive glass at
This is higher, though and glass it is flexible flexible, bending resistance is still poor.In addition having a kind of thinking is to use conducting polymer for example
Polyaniline, polyacetylene, polypyrrole, polythiophene etc. are used as collector, and conducting polymer materials especially large area conduction is poly- at present
The preparation and more difficult, the higher cost of processing of compound film, greatly limit its application.In addition there are also some on such thinking basis
On make the new method of improvement and innovation.
The Chinese invention patent application of Publication No. CN108258334A uses carbon cloth, nickel cloth or copper cloth as flexible collection
Fluid.The Chinese invention patent application of Publication No. CN107104003A uses carbon cloth and ITO electro-conductive glass does collector.It is public
The Chinese invention patent that the number of opening is CN104900422A in dacron surface hydroiodic acid redox graphene by preparing
Graphene/dacron electrode.The Chinese invention patent application of Publication No. CN106898729A will by electric plating method
Conductive coating (one or more of Cu, Al, Ni, Au, Ag, Zn, Fe metal) is coated on the fibre of nonconducting textile substrate
(polyester fiber, Fypro, polyacrylonitrile fibre, polyolefine fiber, vinal, polyurethane fiber, viscose in dimension
One or more of fiber, copper ammonia fiber, acetate fiber, cotton, fiber crops, wool, silk), since fibres for fabrics is non-conductive therefore
The electric conductivity of the flexible current-collecting body is bad.The Chinese invention of Publication No. CN101071860 recall patent disclose it is a kind of soft
Property collector, is made of, supporting layer is the organic film material that can be wound, with a thickness of 10 ~ 100 μm supporting layer/conductive layer；It is conductive
Layer is 1 ~ 500 layer of conductive film material, with a thickness of 10nm ~ 10 μm；The conductive of flexible current-collecting body be nickel, platinum, gold, ruthenium,
Cobalt or manganese Metal thin-film material；RuO2、NiO、TiO2、SnO2、ZrO2、V2O5Or MnO2Transition metal oxide film material；It is poly-
Aniline, polypyrrole or polythiophene conductive polymer thin-film material, since supporting layer is nonconducting organic film therefore flexibility
The electric conductivity of collector is bad.The Chinese invention patent application of Publication No. CN106654285A uses polyvinyl chloride, poly- second
The conduct of one of alkene, polypropylene, polystyrene, polyethylene terephthalate, dimethyl silicone polymer and polyimides
Basal layer uses the method for vacuum coating to plate one of one layer of Cu, Al, Ni, Au and Ag as conductive layer in substrate surface, then
At least one of electrically conductive graphite, graphene, carbon nanotube and carbon nano-fiber are coated in conductive layer surface, since basal layer is
The electric conductivity of nonconducting organic film therefore the flexible current-collecting body is still bad.The middle promulgated by the State Council of Publication No. CN105140047A
Bright granted patent discloses a kind of flexible current-collecting body, including (polypropylene, gathers polyethylene terephthalate flexible base layer
At least one of vinyl chloride, polyethylene, polyethylene naphthalate, polymethyl methacrylate, polycarbonate), setting
Flexible substrate layer surface adhesive layer and be arranged in bonding layer surface flexible conductive layer (from electrically conductive graphite paper remove lead
Graphite layer or at least one of the conductive carbon layer removed from conductive carbon paper), electric conductivity is poor.Publication No.
The Chinese invention granted patent of CN103903876A is by conductive graphene suspension spray in polyethylene terephthalate, poly-
Flexible current-collecting body, electric conductivity are formed in the flexible substrates such as (ethylene naphthalate), polymethyl methacrylate or polycarbonate
It is poor.
The problem of summarizing the above method is to guarantee the intensity of collector how while improving collector flexibility, lead
Electrically, ultra-thin and ultra-light performance.
Summary of the invention
The purpose of the present invention is to solve existing collector it is flexible it is poor, intensity is low, poorly conductive, ultra-thin and ultra-light performance
The problem of difference provides a kind of flexible, porous collector and preparation method thereof, and the collector of preparation has strong electric conductivity, strong bend resistance
Performance, high intensity, easy processing, conductivity > 1*103S/m, tensile strength are 50 ~ 200 MPa, the bending of 1cm bendable bilge radius
10000 times or more, while its ultra-thin and ultra-light performance can be kept, energy density can be improved for battery.
To achieve the above object, the technical solution adopted by the present invention is as follows:
A kind of flexible, porous collector, the collector include flexible, porous conductive substrates and are plated in flexible, porous conductive substrates
The ultra-thin conductive metal layer on surface；The flexible, porous conductive substrates are that conductive powder material is dispersed in polymer material
The perforated membrane of middle formation.
A kind of preparation method of above-mentioned flexible, porous collector, specific step is as follows for the method:
It is first that polymer and conductive powder material melting mixing is uniform, wherein the mass fraction of conductive powder material be 0.01 ~
50%, flexible, porous conductive substrates are prepared using the double daraf(reciprocals of farad) of dry method in lithium battery diaphragm production equipment；Vacuum evaporation is used again
Or electro-plating method plates the ultra-thin conductive metal layer that a layer thickness is 0.01 ~ 3 μm on flexible, porous conductive substrates surface, obtains flexibility
Porous current collector.
The beneficial effect of the present invention compared with the existing technology is: since the base material is that conductive powder body and polymer are uniform
It is compound, there is flexible, tensile strength high (10 MPa of tensile strength >), electric conductivity height (conductivity > 1*102S/m), density
Low (surface density < 8mg/cm2) the characteristics of, it can further improve its conduction after plating one layer of ultra-thin conductive metal layer on this substrate
Performance (conductivity > 1*103) and tensile strength s/m.It is simple to be provided simultaneously with preparation method, it is at low cost, easy large-scale production
Feature.The porous structure of the collector can also guarantee that electrode front and back sides are linked together, and the high rate performance for improving electrode (can be supported
5C or more rate charge-discharge), the mechanism of action is similar to the laser pore-creating copper foil current collector released currently on the market.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of flexible, porous collector of the present invention, wherein 1 is conductive powder material, and 2 be polymer,
3 be flexible, porous conductive substrates, and 4 be ultra-thin conductive metal layer, and 5 be the hole of flexible, porous conductive substrates.Hole in figure is straight hole,
But the shape of actual conditions lower opening and irregular.
Specific embodiment
Further description of the technical solution of the present invention with reference to the accompanying drawings and examples, and however, it is not limited to this,
All to be modified to technical solution of the present invention or equivalent replacement, range without departing from the spirit of the technical scheme of the invention should all
Cover within the protection scope of the present invention.The material and instrument arrived used in the present invention such as not special explanation, be
Conventional material and conventional instrument, it is commercially available.
Specific embodiment 1: present embodiment record is a kind of flexible, porous collector, the collector includes
Flexible, porous conductive substrates 3 and the ultra-thin conductive metal layer 4 for being plated in flexible, porous conductive substrates surface；The flexible, porous is led
Electric substrate 3 is that conductive powder material 1 is dispersed in the perforated membrane formed in 2 material of polymer.
Specific embodiment 2: a kind of flexible, porous collector, the flexible, porous described in specific embodiment one
Conductive substrates with a thickness of 1 ~ 100 μm, porosity is 0.01 ~ 80%.
Specific embodiment 3: a kind of flexible, porous collector, the conductive powder body described in specific embodiment one
Material be carbon black, carbon nanotube, graphene, carbon fiber, copper nanoparticle, nanometer aluminium powder, nano-nickel powder, nano-silver powder, phthalocyanine blue,
Zinc oxide or the stannic oxide for adulterating Sb element.
Specific embodiment 4: a kind of flexible, porous collector described in specific embodiment three, the doping Sb member
The content of Sb element is 0.1 ~ 50wt% in the stannic oxide of element.
Specific embodiment 5: a kind of flexible, porous collector, the polymer described in specific embodiment one are
Polyethylene, polypropylene, polystyrene, polyethylene terephthalate or polycarbonate.
Specific embodiment 6: a kind of flexible, porous collector, the ultra-thin conductive described in specific embodiment one
Metal layer is one or more of Cu, Al, In, Ni, Au, Ag, Zn or Fe, with a thickness of 0.01 ~ 3 μm.
Specific embodiment 7: flexible, porous collection described in a kind of any specific embodiment of specific embodiment one to six
The preparation method of fluid, specific step is as follows for the method:
As shown in Figure 1, first that polymer 2 and 1 melting mixing of conductive powder material is uniform, wherein the quality of conductive powder material
Score is 0.01 ~ 50%, prepares flexible, porous conductive base using the double daraf(reciprocals of farad) of well known dry method in lithium battery diaphragm production equipment
Bottom 3；Vacuum evaporation or electro-plating method is used on 3 surface of flexible, porous conductive substrates to plate a layer thickness again ultra-thin for 0.01 ~ 3 μm
Conductive metal layer 4 obtains flexible, porous collector.
Embodiment 1:
It is first that polypropylene and carbon black (carbon black mass percentage composition is 0.5%) melting mixing is uniform, in lithium battery diaphragm production equipment
On the perforated membranes of 3 μm of porositys 39% of thickness is prepared using the double daraf(reciprocals of farad) of well known dry method.Again using vacuum vapour deposition in perforated membrane
The metallic aluminium (1 μ m-thick metallic aluminium is coated in perforated membrane upper and lower surface and hole) that a layer thickness is 1 μm is plated on surface, obtains flexibility
Porous current collector.
Embodiment 2:
It is first that polyethylene and graphene (graphene mass percentage is 0.1%) melting mixing is uniform, it is produced in lithium battery diaphragm
The perforated membrane of 1 μm of porosity 0.1% of thickness is prepared in equipment using the double daraf(reciprocals of farad) of well known dry method.Again using galvanoplastic porous
Film surface plates the metal Au(perforated membrane upper and lower surface that a layer thickness is 0.01 μm and is coated with 0.01 μm of metal Au in hole),
Obtain flexible, porous collector.
Embodiment 3:
It is first that polyethylene and carbon nanotube (carbon nanotube mass percentage composition is 8%) melting mixing is uniform, it is raw in lithium battery diaphragm
It produces and the double daraf(reciprocals of farad) of well known dry method is used to prepare 100 μm of porositys of thickness as 80% perforated membrane in equipment.Existed again using galvanoplastic
Porous film surface plates the metallic silver (3 μm of metallic silver is coated in perforated membrane upper and lower surface and hole) that a layer thickness is 3 μm, obtains
To flexible, porous collector.
Embodiment 4:
It is first that PET and phthalocyanine blue (phthalocyanine blue mass percentage is 50%) melting mixing is uniform, in lithium battery diaphragm production equipment
On use the double daraf(reciprocals of farad) of well known dry method to prepare 12 μm of porositys of thickness as 25% perforated membrane.Again using galvanoplastic in perforated membrane
The metallic copper (0.1 μ m-thick metallic copper is coated in perforated membrane upper and lower surface and hole) that a layer thickness is 0.1 μm is plated on surface, obtains
Flexible, porous collector.
Embodiment 5:
It is first that polystyrene and carbon fiber (carbon fiber mass percentage is 25%) melting mixing is uniform, it is raw in lithium battery diaphragm
It produces and the double daraf(reciprocals of farad) of well known dry method is used to prepare 20 μm of porositys of thickness as 28% perforated membrane in equipment.Vacuum evaporation is used again
Method plates the indium metal that a layer thickness is 0.5 μm in porous film surface and (is coated with 0.5 μ m-thick gold in perforated membrane upper and lower surface and hole
Belong to indium), obtain flexible, porous collector.
Embodiment 6:
It is first that polycarbonate and nano-silver powder (carbon black mass percentage composition is 30%) melting mixing is uniform, it is raw in lithium battery diaphragm
It produces and the double daraf(reciprocals of farad) of well known dry method is used to prepare 8 μm of porositys of thickness as 15% perforated membrane in equipment.Vacuum vapour deposition is used again
(2 μ m-thicks are coated in perforated membrane upper and lower surface and hole in the mixture that porous film surface plates aluminium and indium that a layer thickness is 2 μm
The mixture of aluminium and indium), obtain flexible, porous collector.
Comparative example 1:
The flexible current-collecting that 2 μm of copper obtains is plated using 50 μ m-thick polyester fiber cloths of the method preparation in patent CN106898729A
Body.
Comparative example 2:
2 μm of copper 2 μm of graphene layers of re-coating are plated using 50 μm of polyethylene films of the method preparation in patent CN106654285A to obtain
The flexible current-collecting body arrived.
Comparative example 3:
2 μm of graphite are coated using 50 μm of pet films of the method preparation in patent CN103903876A
The flexible current-collecting body that alkene obtains.
Flexible, porous collector prepared by embodiment 1 ~ 6 is tested with the flexible current-collecting body in comparative example 1 ~ 3 and is bent with 1cm
Radius bends 180 ° of numbers, conductivity, tensile strength and surface density, in addition does collector using these collectors and is prepared into capacity
The lithium ion battery (positive ternary material, cathode lithium titanate material) of 1Ah simultaneously tests its internal resistance and 10C charge-discharge magnification performance,
The results are shown in Table 1.
Table 1
As can be known from the results of Table 1, the flexible, porous collector prepared using the method for the present invention, compared to the flexible current-collecting of comparative example
Body, electric conductivity is more preferable (showing as higher conductivity), and flexible higher (showing as more bend resistance numbers), tensile strength is bright
It is aobvious to improve, maintain lower surface density.It is (flexible battery, soft that the flexible, porous collector is used for flexible electronic device
Property supercapacitor etc.), can be improved flex capability (flex life), improve energy density, improve electrical property (reduce internal resistance,
Improve high rate performance).
Claims (7)
1. a kind of flexible, porous collector, it is characterised in that: the collector includes flexible, porous conductive substrates (3) and is plated in
The ultra-thin conductive metal layer (4) on flexible, porous conductive substrates surface；The flexible, porous conductive substrates (3) are conductive powder body material
Material (1) is dispersed in the perforated membrane formed in polymer (2) material.
2. a kind of flexible, porous collector according to claim 1, it is characterised in that: the flexible, porous conductive substrates
(3) with a thickness of 1 ~ 100 μm, porosity is 0.01 ~ 80%.
3. a kind of flexible, porous collector according to claim 1, it is characterised in that: the conductive powder material (1)
For carbon black, carbon nanotube, graphene, carbon fiber, copper nanoparticle, nanometer aluminium powder, nano-nickel powder, nano-silver powder, phthalocyanine blue, oxidation
Zinc or the stannic oxide for adulterating Sb element.
4. a kind of flexible, porous collector according to claim 3, it is characterised in that: the dioxy of the doping Sb element
The content for changing Sb element in tin is 0.1 ~ 50wt%.
5. a kind of flexible, porous collector according to claim 1, it is characterised in that: the polymer be polyethylene,
Polypropylene, polystyrene, polyethylene terephthalate or polycarbonate.
6. a kind of flexible, porous collector according to claim 1, it is characterised in that: the ultra-thin conductive metal layer
It (4) is one or more of Cu, Al, In, Ni, Au, Ag, Zn or Fe, ultra-thin conductive metal layer (4) is with a thickness of 0.01 ~ 3 μm.
7. a kind of preparation method of flexible, porous collector described in claim 1 ~ 6 any claim, it is characterised in that: institute
Stating method, specific step is as follows:
It is first that polymer (2) and conductive powder material (1) melting mixing is uniform, wherein the mass fraction of conductive powder material (1)
It is 0.01 ~ 50%, prepares flexible, porous conductive substrates (3) using the double daraf(reciprocals of farad) of dry method in lithium battery diaphragm production equipment；It adopts again
The ultra-thin conductive gold that a layer thickness is 0.01 ~ 3 μm is plated on flexible, porous conductive substrates (3) surface with vacuum evaporation or electro-plating method
Belong to layer (4), obtains flexible, porous collector.
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