CN105186006A - Composite porous current collector, and preparation method and application thereof - Google Patents
Composite porous current collector, and preparation method and application thereof Download PDFInfo
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- CN105186006A CN105186006A CN201410270417.XA CN201410270417A CN105186006A CN 105186006 A CN105186006 A CN 105186006A CN 201410270417 A CN201410270417 A CN 201410270417A CN 105186006 A CN105186006 A CN 105186006A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
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- 238000004080 punching Methods 0.000 claims abstract description 18
- 238000002955 isolation Methods 0.000 claims abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 3
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- 239000003513 alkali Substances 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
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- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
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Classifications
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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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Cell Electrode Carriers And Collectors (AREA)
- Cell Separators (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a composite porous current collector, and a preparation method and an application thereof. The composite porous current collector comprises a porous electron conducting layer with through holes and an electron insulating layer with through holes, wherein the porosity of the through holes of porous electron conducting layer is not less than the porosity of the through holes of the electron insulating layer, a position of the porous electron conducting layer corresponding to the position of the through hole of the electron insulating layer is a through hole, and a position of the porous electron conducting layer corresponding to the position of the non-through hole of the electron insulating layer can be a through hole, and also can be a blind hole or a rough surface. The electron insulating layer is adjacent to an isolation layer, so puncture of precipitated lithium dendrite to a diaphragm is prevented, direct contact of the electron conducting layer is avoided, and the safety of a battery is improved; the above corresponding through hole structure is in favor of transferring lithium ions, so the internal resistance of the battery is reduced; the hole structure of the porous electron conducting layer and the homogeneous rough surface are in favor of full contact of an electrode active substance with the current collector, the current is uniformly distributed, and the current collection effect is improved; and the preparation method adopting airflow punching has the advantages of simplicity, easy implementation, cleanness, energy saving, combination of other various enforcement modes, and convenience for production and application.
Description
Technical field
The invention belongs to lithium ion flow battery technical field, relate generally to a kind of compound porous collector for lithium ion flow battery and preparation method thereof and application.
Background technology
Lithium ion flow battery is a kind of chemical cell technology that latest development is got up, and it combines the advantage of lithium ion battery and flow battery, is a kind of power output and stored energy capacitance is independent of one another, energy density is large, lower-cost novel chargeable battery.Cell reaction chamber is the important component part of lithium ion flow battery reactor.Conventional lithium ion flow battery forms cell reaction chamber by the gap between current collector layer and separator, because cell reaction chamber spacing is too large, the conduction distance of electronics and ion in electrode suspension can be increased, battery polarization internal resistance is increased, discharge and recharge conversion efficiency reduces, so need to reduce reaction chamber spacing as far as possible, but the electrode suspension of lithium ion flow battery is relatively sticky, and flowing for making electrode suspension then needs to increase cell reaction chamber spacing smoothly.Therefore, this is a contradiction.
Chinese patent (CN201410027599.8) discloses a kind of new type lithium ion flow battery for this reason, the anode collection layer of porous and the negative pole currect collecting layer of porous are placed in respectively separator both sides and with separator close contact, form sandwich composite construction layer by mechanical press or other method, then form cell reaction chamber by the gap between adjacent sandwich composite construction layer.Such structural design makes the size in cell reaction chamber can not increase the polarization resistance of battery according to the viscosity flexible of electrode suspension, solves above-mentioned contradiction.But, this design also brings new problem: due to close contact between porous current collector layer and separator, when battery over multiple cycles or super-charge super-discharge, likely Li dendrite can be formed in the porous current collector layer of negative pole and separator close contact side, pierce through separator and cause internal short-circuit of battery, affect the security performance of battery, especially when separator is the low-intensity materials such as collosol and gel, this problem is more outstanding.
Summary of the invention
For solving the problem, the invention provides a kind of compound porous collector, this compound porous collector be the porous current collector layer of conducting electricity in above-mentioned sandwich composite construction layer side compound one or more layers contain the electric insulators of through hole, wherein the side of composite electron insulating barrier is the side of porous current collector layer and separator close contact, form the compound porous collector of an electron conduction and another side electronic isolation, compound porous collector is placed in both positive and negative polarity reaction chamber as compound porous plus plate current-collecting body and compound porous negative current collector, and the electric insulators of described porous current collector is directly contacted with separator, thus the porous current collector layer avoiding conduction contacts with the direct of separator, direct contact short circuit between the porous both positive and negative polarity current collector layer that can prevent Li dendrite from continuing in the one side of the adjacent separator of porous negative pole currect collecting layer to separate out and conduct electricity like this, improve the security performance of sandwich composite construction layer.
An object of the present invention is to provide a kind of compound porous collector for lithium ion flow battery, it is characterized in that: described compound porous collector is made up of porous electron conducting layer and electric insulators; Electric insulators has through hole and is closely compounded in the one side of porous electron conducting layer; Porous electron conducting layer has through hole, blind hole and rough surface; The through hole of porous electron conducting layer and electric insulators has following corresponding relation: porous electron conducting layer corresponds to electric insulators lead to the hole site place one and is decided to be through hole, can be through hole corresponding to electric insulators non through hole position, also can be blind hole or rough surface; The through hole porosity of porous electron conducting layer is not less than the through hole porosity of electric insulators.
Due to the electronic isolation that compound porous negative current collector and separator directly contact, therefore in the process of battery over multiple cycles and super-charge super-discharge, the one side that lithium ion directly can not contact at compound porous negative current collector and separator obtains electronics, thus prevent Li dendrite compound porous negative current collector and separator directly contact one side separate out; The electric insulators being compound positive/negative porous current collector simultaneously owing to directly contacting with separator, the electron conducting layer avoiding compound positive/negative porous current collector directly contacts and short circuit.
According to the present invention, described compound porous collector is the coating of electric insulators substrate one side or is bonded with porous electron conducting layer and forms.
Described electric insulators is that Eo+ window is wide, align negative active core-shell material and electrolyte to stablize, the polymeric material that lithium ion passes can be shielded, as one or more materials in polyvinyl chloride, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, PETG, polyamide, polyimides, polyethers nitrile, polymethyl acrylate, Kynoar, polyurethane, polyacrylonitrile, butadiene-styrene rubber, improved polyalkene are blended without hole site.
Described electric insulators has through-hole structure, and thickness is 5 ~ 300 μm, and through hole porosity is 30% ~ 90%, and pore diameter range is between 0.1 ~ 2mm.
Described electron conducting layer is the porous mixture of conductive filler and binding agent, and wherein, the mass fraction of conductive filler is not less than 70%, described conductive filler is titanium valve, copper powder, aluminium powder, silver powder, rich lithium silica flour, rich lithium glass putty metalloid alloy conductive particle, or described conductive filler is one or more in carbon black, carbon nano-tube, carbon fiber, Graphene, described binding agent is polyvinyl chloride, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, PETG, polyamide, polyimides, polyethers nitrile, polymethyl acrylate, Kynoar, polyurethane, polyacrylonitrile, butadiene-styrene rubber, sodium carboxymethylcellulose, improved polyalkene, polyacetylene, polypyrrole and derivative thereof, polythiophene and derivative thereof, Polyaniline and its derivative, poly-phenylene vinylene (ppv) and derivative thereof, poly-to benzene and its derivative, one or more in polyfluorene and derivative thereof.
The thickness of described porous electron conducting layer is at 10 ~ 1000 μm, and through hole porosity is equal to or greater than the through hole porosity of described electric insulators, and pore diameter range is at 10nm ~ 2mm.
Or according to the present invention, described compound porous collector is applied by porous electron conducting layer substrate one side or is bonded with electric insulators and forms.
According to the present invention, described porous electron conducting layer is the metal conducting layer with through-hole structure.Described metal conducting layer is that wire or surface form with the metal wire knitted of conductive carbon material coating, and mesh is square, rhombus or rectangle; Or described metal conducting layer is the porous foam metal layer with through-hole structure; Or described metal conducting layer is that expanded metal or metal forming form through mechanical stamping or chemical corrosion, mesh is circular, oval, semicircle, square, hexagon, triangle, rhombus, trapezoidal or not specification polygon.Described expanded metal or metal forming, for being aluminium, alloy aluminum, stainless steel or titanium during anode collection layer, are preferably aluminium; Described expanded metal or metal forming, for being copper, stainless steel, nickel, titanium, tin, tin-coated copper, nickel-clad copper or silver-plated copper during negative pole currect collecting layer, are preferably nickel plating stainless steel; Further, the surface-coated of described metallic plate or metal forming has conductive carbon material coating.
Or described porous electron conducting layer is one or more in Polyester Porous silk conductive fabric, electric conduction of carbon fiber cloth, wire and organic fiber silk hybrid conductive cloth; Or, described porous electron conducting layer is porous organic conductive material, be that porous organic material surface-coated conductive carbon layer or plating or impregnated carbon slurry form, described porous organic material comprises the organic substance that natural linen-cotton, aramid fiber, nylon, polypropylene, polyethylene, polytetrafluoroethylene, PETG and other electrolyte resistance can be good.
Or described porous electron conducting layer is the above-mentioned composition of two or more compounds arbitrarily.
Described porous electron conducting layer has through-hole structure; For increasing the contact area of porous electron conducting layer and electrode suspension, collect better and conduction current, the non through hole region of porous electron conducting layer arranges blind hole or rough surface.
The thickness of described porous electron conducting layer is at 10 ~ 1000 μm, and through hole porosity is 30% ~ 90%, and pore diameter range is at 10nm ~ 2mm.
According to the present invention, described electric insulators is that Eo+ window is wide, align negative active core-shell material and electrolyte to stablize, the film of the organic or inorganic insulating material formation that lithium ion passes can be shielded, can be polyvinyl chloride, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, PETG, polyamide, polyimides, polyethers nitrile, polymethyl acrylate, Kynoar, polyurethane, polyacrylonitrile, butadiene-styrene rubber, improved polyalkene, one or more in pottery, metal oxide, metal hydroxides.
Described electric insulators has through-hole structure; The thickness of described electric insulators is at 0.01 ~ 300 μm, and through hole porosity is less than or equal to the through hole porosity of described electron conducting layer, and pore diameter range is not more than the pore diameter range of described electron conducting layer.
Formed in the one side of the adjacent separator of porous electron conducting layer for preventing Li dendrite, porous electron conducting layer is avoided to contact with the direct of separator, increase the fail safe of battery, retain the electronic conductivity of porous electron conducting layer again to greatest extent simultaneously, ensure catchment effect, reduce the impact of electric insulators covering on lithium ion movement in electrode suspension, described compound porous collector has following structure: electric insulators has through hole and fits tightly at porous electron conducting layer one side, porous electron conducting layer corresponds to electric insulators lead to the hole site place one and is decided to be through hole, can be that through hole also can for blind hole or rough surface corresponding to electric insulators non through hole position, the through hole porosity of porous electron conducting layer is not less than the through hole porosity of electric insulators.
Described shape of through holes can be one or more in circular, square, rhombus, rectangle.Described structure be by the CVD (Chemical Vapor Deposition) method such as vacuum evaporation, ion plating, sputtering, plasma CVD or melt impregnation cooling, solution impregnation solvent flashing method porous electron conducting layer substrate one side coating or bonding electric insulators, or obtain in the coating of electric insulators substrate one side or bonding porous electron conducting layer, or obtained by the method for machinery or air-flow punching after coating or bonding electric insulators and porous electron conducting layer.Because mechanical hole fabrication is difficult to the preparation realizing micron order hole, and air-flow punching have cost low, neatly do not hinder matrix without oil stain, otch, be convenient to the advantage of micro molding, in conjunction with the method for melt/solution coating in the present invention, the mode of air-flow punching is adopted to prepare compound porous collector.
The preparation method of compound porous collector provided by the invention is as follows:
1) preliminary treatment, specifically comprises:
A. cleaning and dry: within the scope of 20 ~ 60 DEG C, with organic solvent to porous electron conducting layer or/and electric insulators cleaning 3 ~ 10 minutes, to remove greasy dirt and the dust on surface; Spray can be adopted, soak or the method for wiping; Described organic solvent is one or more in the low boiling volatile liquids such as ethanol, acetone, gasoline; By drying under the hot blast of 60 ~ 90 DEG C 30 ~ 120 minutes after cleaning.
B. surface treatment: for increasing the bond strength between porous electron conducting layer and electric insulators, improve interface performance, to the porous electron conducting layer after cleaning-drying or/and electric insulators carries out surface treatment.The surface treatment method of the number of chemical such as alkali leaching, pickling, gamma-ray irradiation, ultra-violet radiation, plasma treatment and physics can be adopted.
2) compound: as long as can make to form good interfacial adhesion between electric insulators and porous electron conducting layer, the materials and methods of compound can variation.If compound porous collector is the coating of electric insulators substrate one side or bonding porous electron conducting layer, then on electric insulators, cast coat can form the electrocondution slurry of porous electron conducting layer, the porous electron conduction layer thickness that distance between control coater head and electric insulators makes curtain coating obtain is 10 ~ 1000 μm, and in cast coat process, the temperature of heating plate and warm-up mill controls at 80 ~ 300 DEG C; If compound porous collector is the coating of porous electron conducting layer substrate one side or bonding electric insulators, can on porous electron conducting layer the melt of cast coat electric insulators or solution, the distance controlled between coater head and porous electron conducting layer makes the electronic isolation layer thickness of curtain coating be 0.01 ~ 300 μm, and in cast coat process, the temperature of heating plate and warm-up mill controls at 80 ~ 300 DEG C; If compound porous collector is the coating of porous electron conducting layer substrate one side or bonding electric insulators and electric insulators is insulating organic polymer film, then porous electron conducting layer and electric insulators one side are overlaped, through heating roll-in compound, according to the difference of different polymer melting temperature, the temperature of warm-up mill controls at 80 ~ 300 DEG C.Which kind of method finally all obtains the one side composite material of electric insulators and porous electron conducting layer.
3) air-flow punching: the one side composite material of electric insulators and porous electron conducting layer is drawn between the upper and lower mould to air-flow hole punched device, composite electron insulating barrier one facing to cope match-plate pattern, the high-pressure inert gas of heat is caused in patrix air inlet chamber while matched moulds, utilize hot high pressure air-flow to wash the electron conducting layer at electric insulators lead to the hole site place open, electron conducting layer forms the through hole corresponding with electric insulators through hole; Or utilize hot high pressure air-flow to wash the electric insulators at porous electron conducting layer lead to the hole site place open, electric insulators forms the through hole corresponding with porous electron conducting layer through hole; The temperature of thermal current controls at 80 ~ 250 DEG C; Described inert gas pressure is at 0.5 ~ 5MPa.
4) reprocessing: mainly comprise and blow drying, rear scouring or polishing to the one side composite material of electric insulators after punching and porous electron conducting layer, finally obtains the compound porous collector being applicable to being applied to lithium ion flow battery.
The present invention also provides a kind of sandwich composite construction layer being applied to lithium ion flow battery utilizing compound porous collector to assemble.
Described sandwich composite construction layer is made up of compound porous plus plate current-collecting body, separator and compound porous negative current collector, it is characterized in that: separator is between compound porous plus plate current-collecting body and compound porous negative current collector, and the electric insulators side of compound porous plus plate current-collecting body and compound porous negative current collector contacts with separator.Described separator is polyethylene, polypropylene, Kynoar or the nonconducting porous polymer material of other electronics; Or described separator is the composite porous material of glass fibre non-woven, non-woven fabrics of synthetic fiber, ceramic fiber paper or the nonconducting Inorganic Non-metallic Materials of other electronics and organic polymer; Or the material of separator adopts the gel polymer electrolyte composite material of the nonconducting polymeric matrix of electronics, liquid organic plasticizers and lithium salts three part compound formation.Described compound porous plus plate current-collecting body and compound porous negative current collector are the compound porous collector in the present invention.Compound porous plus plate current-collecting body, the method such as physical bonds, mechanical heat seal between separator and compound porous negative current collector, can be adopted to be combined into the sandwich composite construction layer fitted tightly mutually.
Technical advantage of the present invention is embodied in:
1) during battery assembling, compound porous positive/negative collector electric insulators side is adjacent with separator, prevent Li dendrite from separating out in the one side of the adjacent separator of compound porous negative current collector on the one hand, the electron conducting layer avoiding compound positive/negative porous current collector on the other hand directly contacts, and improves the fail safe of battery;
2) in compound porous collector, in porous electron conducting layer, the through-hole structure corresponding with electric insulators is conducive to lithium ion and moves and transmit, and reduces the internal resistance of cell;
3) in compound porous collector, pore structure and the homogeneous rough surface of porous electron conducting layer is conducive to fully contacting of electrode active material and collector, while evenly distributing electric current, improve catchment effect;
4) preparation method of air-flow punching is simple, clean energy-saving, has other numerous embodiments concurrently, is convenient to produce and application.
Accompanying drawing explanation
Fig. 1 is compound porous current collector structure schematic diagram, and Fig. 1 (a) is the stereogram of compound porous collector, and Fig. 1 (b) is the profile of compound porous collector, in figure: 1-through hole; 2-compound porous collector; 3-porous electron conducting layer; 4-electric insulators;
Fig. 2 is the structural representation of sandwich composite construction layer in existing lithium ion flow battery, the stereogram of sandwich composite construction in the existing lithium ion flow battery of Fig. 2 (a), Fig. 2 (b) is the profile of composite construction sandwich in existing lithium ion flow battery, in figure: 5-separator; 6-porous current collector layer; Sandwich composite construction in 7-existing lithium ion flow battery;
Fig. 3 is the stereogram of the structural representation of the Novel sandwich composite construction layer utilizing compound porous collector to form, Fig. 3 (a) Novel sandwich composite construction, and Fig. 3 (b) is the profile of Novel sandwich composite construction;
The transition graph of lithium ion in sandwich composite construction layer inside when Fig. 4 is charging, in figure: 8-positive active material.
Embodiment
Below in conjunction with the drawings and specific embodiments, that the present invention will be described is as follows:
As shown in Figure 1, compound porous collector 2 is composited by electric insulators 4 and porous electron conducting layer 3 one side, porous electron conducting layer 3 corresponds to electric insulators 4 lead to the hole site place one and is decided to be through hole, can be through hole corresponding to electric insulators 4 non through hole position, also can be blind hole or rough surface, the through hole porosity of porous electron conducting layer 3 be not less than the through hole porosity of electric insulators 4; The sandwich structure layer 7 that the compound porous collector of two panels 2 is composited new according to the electric insulators 4 of compound porous collector 2 with the mode of separator 5 close contact with a slice separator 5, as shown in Figure 3, what directly contact due to compound porous collector 2 and separator 5 is electric insulators 4, avoids the unexpected porous electron conducting layer 3 caused and directly contacts and short circuit; As Fig. 4, during battery charging, in the existence of negative pole due to electric insulators 4, the one side that lithium ion directly can not contact at compound porous collector 2 and separator 5 obtains electronics, thus prevent Li dendrite to separate out in the one side that compound porous collector 2 and separator 5 directly contact and puncture separator 5 to cause battery short circuit, improve the fail safe of battery.
Embodiment one:
In the present embodiment, compound porous collector comprises: electric insulators 4 is 30 μm of thick polyethylene films, and porous electron conducting layer 3 is 300 ~ 800 μm, aperture, porosity 80%, and the surface of thick 500 μm is coated with the porous PET conductive fabric of carbon.
The compound porous collector preparation method of the present embodiment is as follows:
1) preliminary treatment, specifically comprises:
A. cleaning and drying: under room temperature, porous PET conductive fabric surface being coated with carbon soaks and ultrasonic 10 minutes respectively in ethanol, acetone and dimethyl carbonate, with except degreasing, dust and soluble impurity, then clean with deionized water rinsing, drying 60 minutes under 90 DEG C of hot blasts.
Under room temperature, polyethylene film is soaked ultrasonic 10 minutes in acetone, to remove greasy dirt and the dust on surface, then clean with deionized water rinsing, drying 30 minutes under 60 DEG C of hot blasts.
B. surface treatment: for increasing the adhesion strength between porous PET conductive fabric and polyethylene film, improving interface performance, processing 20 minutes in the porous PET conductive fabric air plasma atmosphere after cleaning-drying; Polyethylene film was through gamma-ray irradiation 20 minutes.
2) compound: polyethylene film and porous PET conductive fabric one side are overlaped, after 140 DEG C of heating roll-ins, polyethylene film melting and porous PET conductive fabric fit tightly.
3) air-flow punching: by the porous PET conductive fabric of one side laminating polyethylene film traction to air-flow hole punched device upper and lower mould between, laminating polyethylene film one facing to cope match-plate pattern, while matched moulds, the high-pressure inert gas of heat is caused in patrix air inlet chamber, utilize hot high pressure air-flow to wash the film layer of porous PET conductive fabric through hole 1 position open; The temperature of thermal current controls at 120 DEG C; Described inert gas pressure is at 4MPa.
4) reprocessing: by the porous PET conductive fabric of the one side laminating polyethylene film of punching at room temperature cold wind purge 30 minutes, obtain the compound porous collector being applicable to being applied to lithium ion flow battery.
Embodiment two:
In the present embodiment, compound porous collector comprises: electric insulators 4 is the polyvinylidene fluoride film after solution evaporation, thickness 40 μm, and porous electron conducting layer 3 is 300 ~ 800 μm, aperture, porosity 80%, and the surface of thick 500 μm is coated with the porous PET conductive fabric of carbon.
The compound porous collector preparation method of the present embodiment is as follows:
1) preliminary treatment, specifically comprises:
A. cleaning and drying: under room temperature, porous PET conductive fabric surface being coated with carbon soaks and ultrasonic 10 minutes respectively in ethanol, acetone and dimethyl carbonate, with except degreasing, dust and soluble impurity, then clean with deionized water rinsing, drying 60 minutes under 90 DEG C of hot blasts.
B. surface treatment: for increasing the adhesion strength between porous PET conductive fabric and polyvinylidene difluoride film, improving interface performance, processing 20 minutes in the porous PET conductive fabric air plasma atmosphere after cleaning-drying.
2) compound: the Kynoar solution taking 1-METHYLPYRROLIDONE as solvent preparation 10wt%, be coated in above porous PET conductive fabric, the distance controlled between coater head and porous PET conductive fabric makes the thickness of polyvinylidene fluoride film at 40 μm, in cast coat process, the temperature of heating plate and warm-up mill controls at 80 DEG C, finally obtains the porous PET conductive fabric of one side coating Kynoar.
3) air-flow punching: Kynoar rete without obvious flowing but not yet dry before one side applied Kynoar porous PET conductive fabric draw between the upper and lower mould to air-flow hole punched device, apply one of Kynoar facing to cope match-plate pattern, while matched moulds, the high-pressure inert gas of heat is caused in patrix air inlet chamber, utilize hot high pressure air-flow to wash the Kynoar rete of porous PET conductive fabric through hole 1 position open; The temperature of thermal current controls at 120 DEG C; Described inert gas pressure is at 4MPa.
4) reprocessing: by the one side of punching coating polyvinylidene fluoride film porous PET conductive fabric at room temperature cold wind purge 30 minutes, obtain the compound porous collector being applicable to being applied to lithium ion flow battery.
Embodiment three:
In the present embodiment, compound porous collector comprises: electric insulators 4 is 50 μm of thick polyethylene films, and porous electron conducting layer 3 is 200 order stainless (steel) wires.
The compound porous collector preparation method of the present embodiment is as follows:
1) preliminary treatment, specifically comprises:
A. clean and drying: 40 DEG C, stainless (steel) wire is soaked ultrasonic 10 minutes in acetone, to remove greasy dirt and the dust on surface, then clean with deionized water rinsing, drying 30 minutes under 90 DEG C of hot blasts.
Under room temperature, polyethylene film is soaked ultrasonic 10 minutes in acetone, to remove greasy dirt and the dust on surface, then clean with deionized water rinsing, drying 30 minutes under 60 DEG C of hot blasts.
B. surface treatment: for increasing the adhesion strength between stainless (steel) wire and polyethylene film, improve interface performance, stainless (steel) wire after cleaning-drying soaks activation in acid solution, acid solution consists of (mass ratio) sodium metasilicate: washing powder: NaOH: water: sodium pyrophosphate=10:1:5:500:5, soaks 10 minutes at 80 DEG C; By polyethylene film through gamma-ray irradiation 20 minutes.
2) compound: polyethylene film and stainless (steel) wire one side are overlaped, after 140 DEG C of heating roll-ins, polyethylene film melting and stainless (steel) wire fit tightly.
3) air-flow punching: by the stainless (steel) wire of one side laminating polyethylene film traction to air-flow hole punched device upper and lower mould between, laminating polyethylene film one facing to cope match-plate pattern, while matched moulds, the high-pressure inert gas of heat is caused in patrix air inlet chamber, utilize hot high pressure air-flow to wash the film layer of stainless (steel) wire through hole 1 position open; The temperature of thermal current controls at 120 DEG C; Described inert gas pressure is at 3MPa.
4) reprocessing: by the stainless (steel) wire of the one side laminating polyethylene film of punching at room temperature cold wind purge 30 minutes, the one side of non-laminating polyethylene film is polished through coarse sandpaper, obtains the compound porous collector being applicable to being applied to lithium ion flow battery.
Embodiment four:
In the present embodiment, compound porous collector comprises: electric insulators 4 is 500 μm, aperture, percent opening 50%, and 50 μm of thick porous polyethylene films, porous electron conducting layer 3 is the conductive coating of conductive carbon black and Kynoar mixture.
The compound porous collector preparation method of the present embodiment is as follows:
1) preliminary treatment, specifically comprises:
A. clean and drying: under room temperature, porous polyethylene film is soaked ultrasonic 10 minutes in acetone, to remove greasy dirt and the dust on surface, then clean with deionized water rinsing, drying 30 minutes under 60 DEG C of hot blasts.
B. surface treatment: be increase the adhesion strength between conductive coating and porous polyethylene film, improve interface performance, the porous polyethylene film after cleaning-drying was through gamma-ray irradiation 20 minutes.
2) compound: by conductive black and Kynoar carbon black by weight percentage: Kynoar=9:1 is mixed in 1-METHYLPYRROLIDONE, make slurry, be coated in above porous polyethylene film, the distance controlled between coater head and porous polyethylene film makes conductive coating thickness between 800 ~ 1000 μm, in cast coat process, the temperature of heating plate and warm-up mill controls, at 80 DEG C, finally to obtain the porous polyethylene film of one side coated with conductive coating.
3) air-flow punching: before conductive coating without obvious flowing but not yet drying, by the porous polyethylene film of one side conductive composite coating traction to air-flow hole punched device upper and lower mould between, the porous polyethylene film one of uncoated conductive coating is facing to cope match-plate pattern, while matched moulds, the high-pressure inert gas of heat is caused in patrix air inlet chamber, utilize hot high pressure air-flow to wash the conductive coating of porous polyethylene film through hole 1 position open; The temperature of thermal current controls at 100 DEG C; Described inert gas pressure is at 5MPa.
4) reprocessing: by porous polyethylene film dry 12h at 100 DEG C of the one side coated with conductive coating of punching, by uncoated for a porous polyethylene film scrub, obtain the compound porous collector being applicable to being applied to lithium ion flow battery.
The specific embodiment of the invention is also not used to limit the present invention.Any those of ordinary skill in the art, do not departing under technical solution of the present invention ambit, the Method and Technology content of above-mentioned announcement all can be utilized to make many possible variations and modification to technical solution of the present invention, or be revised as the Equivalent embodiments of equivalent variations.Therefore, every content not departing from technical solution of the present invention, according to technical spirit of the present invention to any simple modification made for any of the above embodiments, equivalent variations and modification, all still belongs in the scope of technical solution of the present invention protection.
Claims (10)
1. for a compound porous collector for lithium ion flow battery, it is characterized in that: described compound porous collector is made up of porous electron conducting layer and electric insulators; Electric insulators has through hole and is closely compounded in the one side of porous electron conducting layer; Porous electron conducting layer has through hole, blind hole and rough surface; The through hole of porous electron conducting layer and electric insulators has following corresponding relation: porous electron conducting layer corresponds to electric insulators lead to the hole site place one and is decided to be through hole, is through hole, blind hole or rough surface corresponding to electric insulators non through hole position; The through hole porosity of porous electron conducting layer is not less than the through hole porosity of electric insulators.
2. compound porous collector as claimed in claim 1, is characterized in that: described compound porous collector is the coating of electric insulators substrate one side or is bonded with porous electron conducting layer.
3. compound porous collector as claimed in claim 2, is characterized in that: described electric insulators is that Eo+ window is wide, aligns negative active core-shell material and electrolyte is stablized, without the polymeric material that hole site maskable lithium ion passes; Described electric insulators is that in polyvinyl chloride, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, PETG, polyamide, polyimides, polyethers nitrile, polymethyl acrylate, Kynoar, polyurethane, polyacrylonitrile, butadiene-styrene rubber, improved polyalkene, one or more materials are blended; Described electric insulators has through-hole structure, and thickness is 5 ~ 300 μm, and through hole porosity is 30% ~ 90%, and pore diameter range is 0.1 ~ 2mm.
4. compound porous collector as claimed in claim 2, is characterized in that: described electron conducting layer is the porous mixture of conductive filler and binding agent, and wherein, the mass fraction of conductive filler is not less than 70%, described conductive filler is titanium valve, copper powder, aluminium powder, silver powder, rich lithium silica flour, rich lithium glass putty metalloid alloy conductive particle, or described conductive filler is one or more in carbon black, carbon nano-tube, carbon fiber, Graphene, described binding agent is polyvinyl chloride, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, PETG, polyamide, polyimides, polyethers nitrile, polymethyl acrylate, Kynoar, polyurethane, polyacrylonitrile, butadiene-styrene rubber, sodium carboxymethylcellulose, improved polyalkene, polyacetylene, polypyrrole and derivative thereof, polythiophene and derivative thereof, Polyaniline and its derivative, poly-phenylene vinylene (ppv) and derivative thereof, poly-to benzene and its derivative, one or more in polyfluorene and derivative thereof, the thickness of described porous electron conducting layer is between 10 ~ 1000 μm, and through hole porosity is not less than the through hole porosity of described electric insulators, and pore diameter range is 10nm ~ 2mm.
5. compound porous collector as claimed in claim 1, is characterized in that: described compound porous collector is the coating of porous electron conducting layer substrate one side or is bonded with electric insulators and forms.
6. compound porous collector as claimed in claim 5, it is characterized in that: described porous electron conducting layer is the metal conducting layer with through-hole structure: described metal conducting layer is that wire or surface form with the metal wire knitted of conductive carbon material coating, mesh is square, rhombus or rectangle; Or described metal conducting layer is the porous foam metal layer with through-hole structure; Or described metal conducting layer is that expanded metal or metal forming form through mechanical stamping or chemical corrosion, mesh is circular, oval, semicircle, square, hexagon, triangle, rhombus, trapezoidal or irregular polygon; Described expanded metal or metal forming, for being aluminium, alloy aluminum, stainless steel or titanium during anode collection layer, are preferably aluminium; Described expanded metal or metal forming, for being copper, stainless steel, nickel, titanium, tin, tin-coated copper, nickel-clad copper or silver-plated copper during negative pole currect collecting layer, are preferably nickel plating stainless steel; Further, the surface-coated of described metallic plate or metal forming has conductive carbon material coating;
Or described porous electron conducting layer is one or more in Polyester Porous silk conductive fabric, electric conduction of carbon fiber cloth, wire and organic fiber silk hybrid conductive cloth; Or, described porous electron conducting layer is porous organic conductive material, be that porous organic material surface-coated conductive carbon layer or plating or impregnated carbon slurry form, described porous organic material comprises the organic substance that natural linen-cotton, aramid fiber, nylon, polypropylene, polyethylene, polytetrafluoroethylene, PETG and other electrolyte resistance can be good;
Or described porous electron conducting layer is the above-mentioned composition of two or more compounds arbitrarily;
Described porous electron conducting layer has through-hole structure, and the region of non through hole arranges blind hole or rough surface; The thickness of described porous electron conducting layer is 10 ~ 1000 μm, and through hole porosity is 30% ~ 90%, and pore diameter range is between 10nm ~ 2mm.
7. compound porous collector as claimed in claim 5, it is characterized in that: described electric insulators is that Eo+ window is wide, align negative active core-shell material and electrolyte to stablize, the film that the organic or inorganic insulating material that maskable lithium ion passes is formed, described electric insulators is polyvinyl chloride, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, PETG, polyamide, polyimides, polyethers nitrile, polymethyl acrylate, Kynoar, polyurethane, polyacrylonitrile, butadiene-styrene rubber, improved polyalkene, pottery, metal oxide, one or more in metal hydroxides, described electric insulators has through-hole structure, the thickness of described electric insulators is at 0.01 ~ 300 μm, and through hole porosity is less than or equal to the through hole porosity of described electron conducting layer, and pore diameter range is not more than the effective aperture scope of described electron conducting layer.
8. compound porous collector as claimed in claim 1, is characterized in that: the shape of through holes of described compound porous collector comprises one or more in circle, square, rhombus, rectangle; Described structure by the method for vacuum evaporation, ion plating, sputtering, the CVD (Chemical Vapor Deposition) method of plasma CVD or melt impregnation cooling, solution impregnation solvent flashing at the coating of porous electron conducting layer substrate one side or bonding electric insulators, or obtain in the coating of electric insulators substrate one side or bonding porous electron conducting layer, or obtained by the method for machinery or air-flow punching after coating or bonding electric insulators and porous electron conducting layer.
9. a preparation method for compound porous collector, is characterized in that described preparation method comprises the steps:
1) preliminary treatment, specifically comprises:
A. cleaning and dry: within the scope of 20 ~ 60 DEG C, adopt spray, soak or the method organic solvent of wiping to porous electron conducting layer or/and electric insulators cleaning 3 ~ 10 minutes; Described organic solvent is one or more in the low boiling volatile liquids such as ethanol, acetone, gasoline; By drying under the hot blast of 60 ~ 90 DEG C 30 ~ 120 minutes after cleaning;
B. surface treatment: adopt alkali leaching, pickling, gamma-ray irradiation, ultra-violet radiation, plasma treatment surface treatment method to the porous electron conducting layer after cleaning-drying or/and electric insulators carries out surface treatment;
2) compound: compound porous collector is the coating of electric insulators substrate one side or bonding porous electron conducting layer, on electric insulators, cast coat forms the electrocondution slurry of porous electron conducting layer, the porous electron conduction layer thickness that distance between control coater head and electric insulators makes curtain coating obtain is 10 ~ 1000 μm, and in cast coat process, the temperature of heating plate and warm-up mill controls at 80 ~ 300 DEG C;
Or, compound porous collector is the coating of porous electron conducting layer substrate one side or bonding electric insulators, the melt of cast coat electric insulators or solution on porous electron conducting layer, the distance controlled between coater head and porous electron conducting layer makes the electronic isolation layer thickness of curtain coating be 0.01 ~ 300 μm, and in cast coat process, the temperature of heating plate and warm-up mill controls at 80 ~ 300 DEG C;
Or, compound porous collector is the coating of porous electron conducting layer substrate one side or bonding electric insulators and electric insulators is insulating organic polymer film, porous electron conducting layer and electric insulators one side are overlaped, through heating roll-in compound, the temperature of warm-up mill controls at 80 ~ 300 DEG C;
3) air-flow punching: the one side composite material of electric insulators and porous electron conducting layer is drawn between the upper and lower mould to air-flow hole punched device, composite electron insulating barrier one facing to cope match-plate pattern, the high-pressure inert gas of heat is caused in patrix air inlet chamber while matched moulds, utilize hot high pressure air-flow to wash the electron conducting layer at electric insulators lead to the hole site place open, electron conducting layer forms the through hole corresponding with electric insulators through hole; Or utilize hot high pressure air-flow to wash the electric insulators at porous electron conducting layer lead to the hole site place open, electric insulators forms the through hole corresponding with porous electron conducting layer through hole; The temperature of thermal current controls at 80 ~ 250 DEG C; Described inert gas pressure is at 0.5 ~ 5MPa;
4) reprocessing: drying, rear scouring or polishing are blown to the one side composite material of electric insulators after punching and porous electron conducting layer.
10. a sandwich composite construction layer, it is characterized in that: described sandwich composite construction layer is made up of compound porous plus plate current-collecting body, separator and compound porous negative current collector, separator is between compound porous plus plate current-collecting body and compound porous negative current collector, and the electric insulators side of compound porous plus plate current-collecting body and compound porous negative current collector contacts with separator; Described separator is polyethylene, polypropylene, Kynoar or the nonconducting porous polymer material of other electronics; Or described separator is the composite porous material of glass fibre non-woven, non-woven fabrics of synthetic fiber, ceramic fiber paper or the nonconducting Inorganic Non-metallic Materials of other electronics and organic polymer; Or the material of separator adopts the gel polymer electrolyte composite material of the nonconducting polymeric matrix of electronics, liquid organic plasticizers and lithium salts three part compound formation; Described compound porous plus plate current-collecting body and compound porous negative current collector are the compound porous collector in the present invention; Compound porous plus plate current-collecting body, the method such as physical bonds, mechanical heat seal between separator and compound porous negative current collector, is adopted to be combined into the sandwich composite construction layer fitted tightly mutually.
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