CN105186006B - A kind of compound porous collector and preparation method and application - Google Patents
A kind of compound porous collector and preparation method and application Download PDFInfo
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- CN105186006B CN105186006B CN201410270417.XA CN201410270417A CN105186006B CN 105186006 B CN105186006 B CN 105186006B CN 201410270417 A CN201410270417 A CN 201410270417A CN 105186006 B CN105186006 B CN 105186006B
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Abstract
The present invention provides a kind of compound porous collector and preparation method and application.The compound porous collector of the present invention includes porous electron conducting layer and electric insulators with through hole, the through hole porosity of wherein porous electron conducting layer is not less than the through hole porosity of electric insulators, it is set to through hole corresponding at electric insulators lead to the hole site one, can be through hole corresponding to the non-through hole location of electric insulators, or blind hole or rough surface.Electric insulators are adjacent with separation layer, can both prevent Li dendrite from separating out to puncture barrier film, turn avoid the direct contact of electron conducting layer, improve the security of battery；Corresponding through-hole structure is beneficial to lithium ion transport, reduces the internal resistance of cell；The pore structure and homogeneous rough surface of porous electron conducting layer are beneficial to fully contacting for electrode active material and collector, and evenly distributing electric current simultaneously can improve catchment effect；The preparation method of air-flow punching is simple and easy to apply, clean energy-saving, has other numerous embodiments concurrently, is easy to produce and applies.
Description
Technical field
The invention belongs to lithium ion flow battery technical field, relate generally to a kind of for the compound of lithium ion flow battery
Porous current collector and preparation method and application.
Background technology
Lithium ion flow battery is a kind of chemical cell technology that latest development is got up, and it combines lithium ion battery and liquid
The advantage of galvanic battery, is a kind of power output and stored energy capacitance is independent of one another, energy density big, lower-cost new chargeable
Pond.Cell reaction chamber is the important component of lithium ion flow battery reactor.Conventional lithium ion flow battery is by current collector layer
Gap between separation layer forms cell reaction chamber, because cell reaction chamber spacing is too big, can increase electric in electrode suspension
The conductive distance of son and ion so that battery polarization internal resistance increases, charge and discharge photoelectric transformation efficiency reduction, so needing to reduce as far as possible
Reaction chamber spacing, but the electrode suspension of lithium ion flow battery is relatively sticky, to make electrode suspension flowing smoothly then need
Increase cell reaction chamber spacing.Therefore, this is a contradiction.
Disclose a kind of new type lithium ion flow battery for this Chinese patent (CN201410027599.8), by it is porous just
Pole current collector layer and porous negative pole currect collecting layer are respectively placed in the both sides of separation layer and are in close contact with separation layer, pass through mechanical press
Or other methods constitute sandwich composite construction layer, then gap between adjacent sandwich composite construction layer forms cell reaction chamber.
Such structure design allows the size of cell reaction chamber electric without increasing according to the viscosity flexible modulation of electrode suspension
The polarization resistance in pond, solves above-mentioned contradiction.But, the problem of this design also brings new：Due to porous current collector layer with every
It is in close contact, when battery over multiple cycles or super-charge super-discharge, is closely connect with separation layer in the porous current collector layer of negative pole between absciss layer
Tactile side is possible to that Li dendrite can be formed, and pierces through separation layer and causes internal short-circuit of battery, influences the security performance of battery, especially
When separation layer is the low-intensity materials such as collosol and gel, this problem is more prominent.
The content of the invention
To solve the above problems, the present invention provides a kind of compound porous collector, the compound porous collector is above-mentioned
The side of conductive porous current collector layer is combined one or more layers electric insulators for containing through hole in sandwich composite construction layer, wherein
The side of composite electron insulating barrier is the side that porous current collector layer and separation layer are in close contact, and constitutes a face electronic conduction and another
The compound porous collector of face electronic isolation, compound porous collector is placed in both positive and negative polarity reaction chamber and is used as compound porous positive pole
Collector and compound porous negative current collector, and the electric insulators of the porous current collector are directly contacted with separation layer, from
And the porous current collector layer of conduction and directly contacting for separation layer are avoided, it can so prevent Li dendrite in porous negative pole currect collecting layer
The one side of adjacent separation layer persistently separate out and conductive porous both positive and negative polarity current collector layer between direct contact short circuit, improve sandwich
The security performance of composite construction layer.
It is an object of the present invention to provide a kind of compound porous collector for lithium ion flow battery, its feature exists
In：The compound porous collector is made up of porous electron conducting layer and electric insulators；Electric insulators have through hole and tight
The close one side for being compounded in porous electron conducting layer；Porous electron conducting layer has through hole, blind hole and rough surface；Porous electronics is led
The through hole of electric layer and electric insulators has following corresponding relation：Porous electron conducting layer corresponds to electric insulators through hole position
The place of putting one is set to through hole, can be through hole corresponding to the non-through hole location of electric insulators, or blind hole or coarse table
Face；The through hole porosity of porous electron conducting layer is not less than the through hole porosity of electric insulators.
Due to the face electronic isolation that compound porous negative current collector and separation layer are directly contacted, therefore repeatedly followed in battery
During ring and super-charge super-discharge, lithium ion with the one side that separation layer is directly contacted will not obtain electric in compound porous negative current collector
Son, is separated out so as to prevent Li dendrite directly to contact one side with separation layer in compound porous negative current collector；Simultaneously because with every
What absciss layer was directly contacted is the electric insulators of compound positive/negative porous current collector, it is to avoid the porous afflux of compound positive/negative
The electron conducting layer of body is directly contacted and short-circuit.
According to the present invention, the compound porous collector is that electric insulators substrate one side coats or be bonded with porous electronics
Conductive layer is formed.
The electric insulators are that oxidation-reduction potentials window is wide, align negative active core-shell material and electrolyte is stable, non-porous
Position can shield the polymeric material that lithium ion is passed through, such as polyvinyl chloride, polyethylene, polypropylene, polystyrene, polytetrafluoroethyl-ne
Alkene, polyethylene terephthalate, polyamide, polyimides, polyethers nitrile, PMA, Kynoar, poly- ammonia
One or more of material blendings in ester, polyacrylonitrile, butadiene-styrene rubber, improved polyalkene.
The electric insulators have through-hole structure, and thickness is 5~300 μm, and through hole porosity is 30%~90%, aperture
Scope is between 0.1~2mm.
The electron conducting layer is the porous mixture of conductive filler and binding agent, wherein, the mass fraction of conductive filler
Not less than 70%；The conductive filler is titanium valve, copper powder, aluminium powder, silver powder, rich lithium silica flour, rich lithium glass putty metalloid alloy conduction
Particle, or, the conductive filler is the one or more in carbon black, CNT, carbon fiber, graphene；The binding agent
For polyvinyl chloride, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene (PTFE), polyethylene terephthalate, polyamide, polyamides
Imines, polyethers nitrile, PMA, Kynoar, polyurethane, polyacrylonitrile, butadiene-styrene rubber, sodium carboxymethylcellulose,
Improved polyalkene, polyacetylene, polypyrrole and its derivative, polythiophene and its derivative, Polyaniline and its derivative, polyparaphenylene
It is ethene and its derivative, poly- to the one or more in benzene and its derivative, polyfluorene and its derivative.
The thickness of the porous electron conducting layer is at 10~1000 μm, and through hole porosity is equal to or more than the electronic isolation
The through hole porosity of layer, pore diameter range is in 10nm~2mm.
Or, according to the present invention, the compound porous collector is coated or is bonded by porous electron conducting layer substrate one side
There are electric insulators to form.
According to the present invention, the porous electron conducting layer is the metal conducting layer with through-hole structure.The metallic conduction
Metal wire knitted of the layer for wire or surface with conductive carbon material coating is formed, and mesh is square, rhombus or rectangle；Or
Person, the metal conducting layer is the porous foam metal layer with through-hole structure；Or, the metal conducting layer is porous metals
Plate or metal foil are formed through mechanical stamping or chemical attack, and mesh is circular, oval, semicircle, square, hexagon, triangle
Shape, rhombus, trapezoidal or not specification polygon.Be aluminium when the expanded metal or metal foil are used for anode collection layer, alloy aluminum,
Stainless steel or titanium, preferably aluminium；Be copper when the expanded metal or metal foil are used for negative pole currect collecting layer, stainless steel, nickel, titanium,
Tin, tin-coated copper, nickel-clad copper or silver-plated copper, preferably plate nickel and stainless steel；Further, the surface of the metallic plate or metal foil is applied
It is covered with conductive carbon material coating.
Or, the porous electron conducting layer is Polyester Porous silk conductive fabric, electric conduction of carbon fiber cloth, wire and organic fibre
Tie up the one or more in silk hybrid conductive cloth；Or, the porous electron conducting layer is porous organic conductive material, is porous
Organic material surface coats conductive carbon layer or plating metal or impregnated carbon slurry is formed, and the porous organic material includes natural cotton
Fiber crops, aramid fiber, nylon, polypropylene, polyethylene, polytetrafluoroethylene (PTFE), polyethylene terephthalate and other electrolyte resistance energy
Good organic matter.
Or, the porous electron conducting layer is two or more above-mentioned any compound compositions.
The porous electron conducting layer has through-hole structure；To increase contact of the porous electron conducting layer with electrode suspension
Area, preferably collects and conducts electric current, the non-through bore region of porous electron conducting layer sets blind hole or rough surface.
The thickness of the porous electron conducting layer is at 10~1000 μm, and through hole porosity is 30%~90%, pore diameter range
In 10nm~2mm.
According to the present invention, the electric insulators are that oxidation-reduction potentials window is wide, align negative active core-shell material and electrolysis
Liquid is stable, can shield the film for the organic or inorganic insulating material formation that lithium ion is passed through, can be polyvinyl chloride, poly- second
It is alkene, polypropylene, polystyrene, polytetrafluoroethylene (PTFE), polyethylene terephthalate, polyamide, polyimides, polyethers nitrile, poly-
Methyl acrylate, Kynoar, polyurethane, polyacrylonitrile, butadiene-styrene rubber, improved polyalkene, ceramics, metal oxide, gold
Belong to the one or more in hydroxide.
The electric insulators have through-hole structure；The thickness of the electric insulators is in 0.01~300 μm, through hole hole
Rate is less than or equal to the through hole porosity of the electron conducting layer, and pore diameter range is not more than the aperture model of the electron conducting layer
Enclose.
To prevent Li dendrite from being formed in the one side of the adjacent separation layer of porous electron conducting layer, it is to avoid porous electron conducting layer and
The direct contact of separation layer, increases the security of battery, while the electronics for retaining porous electron conducting layer to greatest extent again is led
Electrical property, it is ensured that catchment effect, reduces the influence that electric insulators covering is moved to lithium ion in electrode suspension, described compound
Porous current collector has following structure：Electric insulators have through hole and are fitted tightly over porous electron conducting layer one side, porous
Electron conducting layer is set to through hole corresponding at electric insulators lead to the hole site one, can corresponding to the non-through hole location of electric insulators
It can also be blind hole or rough surface to think through hole, and the through hole porosity of porous electron conducting layer is not less than electric insulators
Through hole porosity.
The shape of through holes can be the one or more in circular, square, rhombus, rectangle.The structure is by true
The CVD methods such as empty evaporation, ion plating, sputtering, plasma CVD or melt impregnation cooling, solution dipping solvent flashing
Method coated in porous electron conducting layer substrate one side or be bonded electric insulators, or in electric insulators substrate one side
Coat or be bonded porous electron conducting layer and obtain, or after coating or being bonded electric insulators and porous electron conducting layer
Obtained by the method for machinery or air-flow punching.Because mechanical hole fabrication is difficult to the preparation of micron order hole, and air-flow punching
With cost it is low, do not hinder matrix neatly without oil stain, otch, be easy to the advantage of micro molding, melt/molten is combined in the present invention
The method of liquid coating, prepares compound porous collector by the way of air-flow punching.
The preparation method for the compound porous collector that the present invention is provided is as follows：
1) pre-process, specifically include：
A. clean and dry：In the range of 20~60 DEG C, with organic solvent to porous electron conducting layer or/and electronic isolation
Layer cleaning 3~10 minutes, to remove the greasy dirt and dust on surface；Can be using spray, immersion or the method wiped；It is described to have
Machine solvent is the one or more in the low boiling volatile liquid such as ethanol, acetone, gasoline；By in 60~90 DEG C of heat after cleaning
Dried 30~120 minutes under wind.
B. it is surface-treated：To increase the bond strength between porous electron conducting layer and electric insulators, improve interface characteristics
Can, the porous electron conducting layer or/and electric insulators after cleaning-drying are surface-treated.Can using alkali leaching, pickling,
A variety of surface treatment methods chemically and physically such as gamma-ray irradiation, ultraviolet radioactive, corona treatment.
2) it is combined：As long as can make to form good interfacial adhesion between electric insulators and porous electron conducting layer, it is combined
Material and method can variation.If compound porous collector, which is electric insulators substrate one side, coats or is bonded porous electronics
Conductive layer, then cast coat can form the electrocondution slurry of porous electron conducting layer on electric insulators, control coater head
The porous electron conducting layer thickness for obtaining curtain coating with the distance between electric insulators is 10~1000 μm, cast coat process
Middle heating plate and the temperature control of heating roller are at 80~300 DEG C；If compound porous collector is porous electron conducting layer substrate list
Face coat or bonding electric insulators, can on porous electron conducting layer the melt of cast coat electric insulators or molten
Liquid, controls the distance between coater head and porous electron conducting layer to cause the electric insulators thickness of curtain coating to be 0.01~300 μ
Heating plate and the temperature control of heating roller are at 80~300 DEG C during m, cast coat；If compound porous collector is porous electricity
Conducting layer substrate one side coats or be bonded electric insulators and electric insulators are insulating organic polymer film, then by porous electricity
Conducting layer and electric insulators one side are overlaped, and heated roll-in is combined, according to different polymer melting temperatures not
Together, the temperature control of heating roller is at 80~300 DEG C.Which kind of method finally all obtains electric insulators and porous electronic conduction
The one side composite of layer.
3) air-flow punching：The one side composite of electric insulators and porous electron conducting layer is drawn to air-flow punching and filled
Between the upper and lower mould put, composite electron insulating barrier one facing to cope plate, the high-pressure inert gas of heat are drawn while matched moulds
In supreme mould inlet plenum, wash the electron conducting layer at electric insulators lead to the hole site open using hot high pressure air-flow, led in electronics
Through hole corresponding with electric insulators through hole is formed in electric layer；Or wash porous electron conducting layer through hole open using hot high pressure air-flow
Electric insulators at position, form through hole corresponding with porous electron conducting layer through hole on electric insulators；Thermal current
Temperature control is at 80~250 DEG C；The inert gas pressure is in 0.5~5MPa.
4) post-process：It is main to include carrying out the one side composite of electric insulators after punching and porous electron conducting layer
Blowing is dried, cleans or polish afterwards, finally gives the compound porous collector for being suitably applied lithium ion flow battery.
The present invention also provide it is a kind of using compound porous collector assemble be applied to lithium ion flow battery it is sandwich multiple
Close structure sheaf.
The sandwich composite construction layer is by compound porous plus plate current-collecting body, separation layer and compound porous negative current collector group
Into, it is characterised in that：Separation layer be located between compound porous plus plate current-collecting body and compound porous negative current collector, it is compound porous just
The electric insulators side of pole collector and compound porous negative current collector is in contact with separation layer.The separation layer is poly- second
Alkene, polypropylene, Kynoar or the nonconducting porous polymer material of other electronics；Or, described separation layer is glass
Fabric nonwoven cloth, non-woven fabrics of synthetic fiber, ceramic fiber paper or the nonconducting inorganic non-metallic material of other electronics gather with organic
The composite porous material of compound；Or, the material of separation layer uses the nonconducting polymeric matrix of electronics, liquid organic plasticizers
With the compound gel polymer electrolyte composite constituted in the part of lithium salts three.The compound porous plus plate current-collecting body and compound many
Hole negative current collector is the compound porous collector in the present invention.Compound porous plus plate current-collecting body, separation layer and compound porous
The sandwich composite construction being brought into close contact mutually can be combined into using methods such as physical bonds, mechanical heat seals between negative current collector
Layer.
The technical advantage of the present invention is embodied in：
1) compound porous positive/negative collector electric insulators side is adjacent with separation layer when battery is assembled, on the one hand anti-
Only Li dendrite is separated out in the one side of the adjacent separation layer of compound porous negative current collector, on the other hand avoids compound positive/negative many
The electron conducting layer of hole collector is directly contacted, and improves the security of battery；
2) through-hole structure corresponding with electric insulators is conducive to lithium in porous electron conducting layer in compound porous collector
Ion is moved and transmitted, and reduces the internal resistance of cell；
3) pore structure and homogeneous rough surface of porous electron conducting layer are conducive to electrode activity in compound porous collector
Material is fully contacted with collector, and catchment effect is improved while evenly distributing electric current；
4) preparation method of air-flow punching is simple and easy to apply, clean energy-saving, has other numerous embodiments concurrently, be easy to production and
Using.
Brief description of the drawings
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
In the profile of compound porous collector, figure：1-through hole；2-compound porous collector；3-porous electron conducting layer；4-electricity
Insulating sublayer layer；
Fig. 2 is the structural representation of sandwich composite construction layer in existing lithium ion flow battery, the existing lithium ions of Fig. 2 (a)
The stereogram of sandwich composite construction in flow battery, Fig. 2 (b) is the section of sandwich composite construction in existing lithium ion flow battery
In figure, figure：5-separation layer；6-porous current collector layer；Sandwich composite construction in 7-existing lithium ion flow battery；
Fig. 3 is the structural representation of the novel sandwich composite construction layer constituted using compound porous collector, and Fig. 3 (a) is new
The stereogram of the sandwich composite construction of type, Fig. 3 (b) is the profile of novel sandwich composite construction；
When Fig. 4 is charging in transition graph of the lithium ion inside sandwich composite construction layer, figure：8-positive active material.
Embodiment
That the present invention will be described is as follows with specific embodiment below in conjunction with the accompanying drawings：
As shown in figure 1, compound porous collector 2 is composited by electric insulators 4 with the porous one side of electron conducting layer 3,
Porous electron conducting layer 3 is set to through hole corresponding at the lead to the hole site of electric insulators 4 one, corresponding to the non through hole of electric insulators 4
Can be through hole at position, or blind hole or rough surface, the through hole porosity of porous electron conducting layer 3 is not less than electricity
The through hole porosity of insulating sublayer layer 4；The compound porous collector 2 of two panels and electricity of a piece of separation layer 5 according to compound porous collector 2
The interlayer structure layer 7 that the mode that insulating sublayer layer 4 is in close contact with separation layer 5 is composited new, as shown in figure 3, due to compound many
What hole collector 2 and separation layer 5 were directly contacted is electric insulators 4, it is to avoid porous electron conducting layer 3 is straight caused by unexpected
Contact and it is short-circuit；Such as Fig. 4, when battery charges, in presence of the negative pole due to electric insulators 4, lithium ion will not be compound more
The one side that hole collector 2 is directly contacted with separation layer 5 obtains electronics, thus prevent Li dendrite compound porous collector 2 with every
The one side that absciss layer 5 is directly contacted is separated out and puncturing separation layer 5 causes battery short circuit, improves the security of battery.
Embodiment one：
In the present embodiment, compound porous collector includes：Electric insulators 4 are the polyethylene film of 30 μ m-thicks, porous electricity
Conducting layer 3 is 300~800 μm of aperture, and porosity 80%, thick 500 μm surface applies the porous PET conductive fabrics of carbon.
The compound porous afflux preparation of the present embodiment is as follows：
1) pre-process, specifically include：
A. clean and dry：At room temperature, surface is applied into the porous PET conductive fabrics of carbon respectively in ethanol, acetone and carbonic acid two
Immersion is simultaneously ultrasonic 10 minutes in methyl esters, except degreasing, dust and soluble impurity, then to be rinsed well with deionized water,
Dried 60 minutes under 90 DEG C of hot blasts.
At room temperature, it is polyethylene film immersion is ultrasonic 10 minutes in acetone, to remove the greasy dirt and dust on surface, then
Rinsed well, dried 30 minutes under 60 DEG C of hot blasts with deionized water.
B. it is surface-treated：To increase the adhesion strength between porous PET conductive fabrics and polyethylene film, improve interface characteristics
Can, handled 20 minutes in the porous PET conductive fabrics air plasma atmosphere after cleaning-drying；Polyethylene film is through gamma-rays spoke
According to 20 minutes.
2) it is combined：Polyethylene film and porous PET conductive fabrics one side are overlaped, gathered after 140 DEG C of heating roll-ins
Vinyl film melting is brought into close contact with porous PET conductive fabrics.
3) air-flow punching：The porous PET conductive fabrics of one side laminating polyethylene film are drawn upper to air-flow hole punched device
Between lower mould, laminating polyethylene film one facing to cope plate, the high-pressure inert gas of heat are led into upper mould while matched moulds
In inlet plenum, the film layer at the porous position of PET conductive fabrics through hole 1 is washed open using hot high pressure air-flow；Thermal current
Temperature control is at 120 DEG C；The inert gas pressure is in 4MPa.
4) post-process：By the porous PET conductive fabrics of the one side laminating polyethylene film of punching, cold wind is purged at room temperature
30 minutes, obtain being suitably applied the compound porous collector of lithium ion flow battery.
Embodiment two：
In the present embodiment, compound porous collector includes：Electric insulators 4 are the polyvinylidene fluoride film after solution evaporation,
40 μm of thickness, porous electron conducting layer 3 is 300~800 μm of aperture, and porosity 80%, thick 500 μm surface applies the porous of carbon
PET conductive fabrics.
The compound porous afflux preparation of the present embodiment is as follows：
1) pre-process, specifically include：
A. clean and dry：At room temperature, surface is applied into the porous PET conductive fabrics of carbon respectively in ethanol, acetone and carbonic acid two
Immersion is simultaneously ultrasonic 10 minutes in methyl esters, except degreasing, dust and soluble impurity, then to be rinsed well with deionized water,
Dried 60 minutes under 90 DEG C of hot blasts.
B. it is surface-treated：To increase the adhesion strength between porous PET conductive fabrics and polyvinylidene difluoride film, improve interface
Handled 20 minutes in porous PET conductive fabrics air plasma atmosphere after performance, cleaning-drying.
2) it is combined：10wt% Kynoar solution is prepared by solvent of 1-METHYLPYRROLIDONE, porous PET is coated in
Above conductive fabric, the distance between control coater head and porous PET conductive fabrics cause the thickness of polyvinylidene fluoride film at 40 μm,
Heating plate and the temperature control of heating roller finally give the porous of one side coating Kynoar at 80 DEG C during cast coat
PET conductive fabrics.
3) air-flow punching：One side is coated into Kynoar without obvious flowing but before not yet drying in Kynoar film layer
Porous PET conductive fabrics draw between the upper and lower mould of air-flow hole punched device, coating Kynoar one facing to cope plate,
The high-pressure inert gas of heat are led in upper mould inlet plenum while matched moulds, it is conductive to wash porous PET open using hot high pressure air-flow
Kynoar film layer at the position of cloth through hole 1；The temperature control of thermal current is at 120 DEG C；The inert gas pressure is in 4MPa.
4) post-process：By the porous PET conductive fabrics of the one side coating polyvinylidene fluoride film of punching, cold wind blows at room temperature
Sweep 30 minutes, obtain being suitably applied the compound porous collector of lithium ion flow battery.
Embodiment three：
In the present embodiment, compound porous collector includes：Electric insulators 4 are the polyethylene film of 50 μ m-thicks, porous electricity
Conducting layer 3 is 200 mesh stainless (steel) wires.
The compound porous afflux preparation of the present embodiment is as follows：
1) pre-process, specifically include：
A. clean and dry：40 DEG C, by stainless (steel) wire immersion in acetone ultrasound 10 minutes, with remove surface greasy dirt and
Dust, is then rinsed well with deionized water, is dried 30 minutes under 90 DEG C of hot blasts.
At room temperature, it is polyethylene film immersion is ultrasonic 10 minutes in acetone, to remove the greasy dirt and dust on surface, then
Rinsed well, dried 30 minutes under 60 DEG C of hot blasts with deionized water.
B. it is surface-treated：For the adhesion strength between increase stainless (steel) wire and polyethylene film, improve interface performance, cleaning
Dried stainless (steel) wire soaks activation in acid solution, and acid solution composition is (mass ratio) sodium metasilicate：Washing powder：Sodium hydroxide：
Water：Sodium pyrophosphate=10:1:5:500:Soaked 10 minutes at 5,80 DEG C；By polyethylene film through gamma-ray irradiation 20 minutes.
2) it is combined：Polyethylene film and stainless (steel) wire one side are overlaped, polyethylene is thin after 140 DEG C of heating roll-ins
Film melting is brought into close contact with stainless (steel) wire.
3) air-flow punching：By the stainless (steel) wire of one side laminating polyethylene film draw to air-flow hole punched device upper and lower mould it
Between, laminating polyethylene film one facing to cope plate, the high-pressure inert gas of heat are led into upper mould inlet chamber while matched moulds
In room, the film layer at the position of stainless (steel) wire through hole 1 is washed open using hot high pressure air-flow；The temperature control of thermal current exists
120℃；The inert gas pressure is in 3MPa.
4) post-process：By the stainless (steel) wire of the one side laminating polyethylene film of punching, cold wind purges 30 points at room temperature
Clock, the one side of non-laminating polyethylene film is polished through coarse sandpaper, obtains being suitably applied the compound many of lithium ion flow battery
Hole collector.
Example IV：
In the present embodiment, compound porous collector includes：Electric insulators 4 are 500 μm of aperture, percent opening 50%, 50 μm
Thick porous polyethylene film, porous electron conducting layer 3 is the conductive coating of conductive carbon black and Kynoar mixture.
The compound porous afflux preparation of the present embodiment is as follows：
1) pre-process, specifically include：
A. clean and dry：At room temperature, it is porous polyethylene film immersion is ultrasonic 10 minutes in acetone, to remove surface
Greasy dirt and dust, then rinsed well with deionized water, under 60 DEG C of hot blasts dry 30 minutes.
B. it is surface-treated：For the adhesion strength between increase conductive coating and porous polyethylene film, improve interface performance,
Porous polyethylene film after cleaning-drying was through gamma-ray irradiation 20 minutes.
2) it is combined：By conductive black and Kynoar carbon black by weight percentage：Kynoar=9：1 is mixed in N-
In methyl pyrrolidone, slurry is made, is coated in above porous polyethylene film, control coater head and porous polyethylene film
The distance between cause conductive coating thickness between 800~1000 μm, heating plate and the temperature of heating roller during cast coat
Degree control finally gives the porous polyethylene film that one side coats conductive coating at 80 DEG C.
3) air-flow punching：Before conductive coating is without obvious flowing but not yet drying, by the porous of one side conductive composite coating
Polyethylene film is drawn between the upper and lower mould of air-flow hole punched device, and the porous polyethylene film one of uncoated conductive coating is faced
To cope plate, the high-pressure inert gas of heat are led in upper mould inlet plenum while matched moulds, washed open using hot high pressure air-flow many
Conductive coating at the position of hole polyethylene film through hole 1；The temperature control of thermal current is at 100 DEG C；The inert gas pressure exists
5MPa。
4) post-process：The porous polyethylene film that the one side of punching is coated into conductive coating dries 12h at 100 DEG C,
The uncoated one side of porous polyethylene film is scrubbed, obtains being suitably applied the compound porous afflux of lithium ion flow battery
Body.
The specific embodiment of the invention is not limited to the present invention.Any those skilled in the art, are not departing from
Under technical solution of the present invention ambit, all technical solution of the present invention is made using the methods and techniques content of the disclosure above
Many possible variations and modification, or it is revised as the equivalent embodiment of equivalent variations.Therefore, it is every without departing from the technology of the present invention side
The content of case, the technical spirit according to the present invention is to any simple modifications, equivalents, and modifications made for any of the above embodiments,
Still fall within technical solution of the present invention protection in the range of.
Claims (10)
1. a kind of compound porous collector for lithium ion flow battery, it is characterised in that：The compound porous collector by
Porous electron conducting layer and electric insulators composition；Electric insulators have through hole and are closely compounded in porous electron conducting layer
One side；Porous electron conducting layer has through hole, blind hole and rough surface；The through hole tool of porous electron conducting layer and electric insulators
There is following corresponding relation：Porous electron conducting layer is set to through hole corresponding at electric insulators lead to the hole site one, corresponding to electricity
The non-through hole location of insulating sublayer layer is through hole, blind hole or rough surface；The through hole porosity of porous electron conducting layer is not less than electricity
The through hole porosity of insulating sublayer layer.
2. compound porous collector as claimed in claim 1, it is characterised in that：The compound porous collector is electronic isolation
The coating of layer substrate one side is bonded with porous electron conducting layer.
3. compound porous collector as claimed in claim 2, it is characterised in that：The electric insulators are oxidationreduction electricity
Position window is wide, aligns negative active core-shell material and electrolyte is stable, the polymeric material that no maskable lithium ion in hole site is passed through；Institute
It is polyvinyl chloride, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene (PTFE), polyethylene terephthalate to state polymeric material
Ester, polyamide, polyimides, polyethers nitrile, PMA, Kynoar, polyurethane, polyacrylonitrile, butadiene-styrene rubber, change
Property polyolefin in one or more of materials blendings；The electric insulators have through-hole structure, and thickness is 5~300 μm, through hole hole
Gap rate is 30%~90%, and pore diameter range is 0.1~2mm.
4. compound porous collector as claimed in claim 2, it is characterised in that：The electron conducting layer is conductive filler with gluing
The porous mixture of agent is tied, wherein, the mass fraction of conductive filler is not less than 70%；The conductive filler is titanium valve, copper powder, aluminium
Powder, silver powder, rich lithium silica flour, rich lithium glass putty metalloid alloy conductive particle, or, the conductive filler be carbon black, CNT,
One or more in carbon fiber, graphene；The binding agent is polyvinyl chloride, polyethylene, polypropylene, polystyrene, poly- four
It is PVF, polyethylene terephthalate, polyamide, polyimides, polyethers nitrile, PMA, Kynoar, poly-
Urethane, polyacrylonitrile, butadiene-styrene rubber, sodium carboxymethylcellulose, improved polyalkene, polyacetylene, polypyrrole and its derivative, poly- thiophene
Fen and its derivative, Polyaniline and its derivative, poly-phenylene vinylene (ppv) and its derivative, it is poly- to benzene and its derivative, polyfluorene and
One or more in its derivative；The thickness of the porous electron conducting layer is between 10~1000 μm, and through hole porosity is not
Less than the through hole porosity of the electric insulators, pore diameter range is 10nm~2mm.
5. compound porous collector as claimed in claim 1, it is characterised in that：The compound porous collector is porous electronics
Conductive layer substrate one side coats or is bonded with electric insulators and forms.
6. compound porous collector as claimed in claim 5, it is characterised in that：The porous electron conducting layer is with through hole
The metal conducting layer of structure：The metal conducting layer be metal wire knitted with conductive carbon material coating of wire or surface and
Into mesh is square, rhombus or rectangle；Or, the metal conducting layer is the porous foam metal layer with through-hole structure；
Or, the metal conducting layer is that expanded metal or metal foil are formed through mechanical stamping or chemical attack, and mesh is circular, ellipse
Circular, semicircle, square, hexagon, triangle, rhombus, trapezoidal or irregular polygon；The expanded metal or metal foil
It is aluminium, alloy aluminum, stainless steel or titanium during for anode collection layer；When the expanded metal or metal foil are used for negative pole currect collecting layer
For copper, stainless steel, plating nickel and stainless steel, nickel, titanium, tin, tin-coated copper, nickel-clad copper or silver-plated copper；Further, the metallic plate or gold
The surface of category paper tinsel is coated with conductive carbon material coating；
Or, the porous electron conducting layer is Polyester Porous silk conductive fabric, electric conduction of carbon fiber cloth, wire and organic fiber silk
One or more in hybrid conductive cloth；Or, the porous electron conducting layer is porous organic conductive material, is porous organic
Material surface coat conductive carbon layer or plating metal or impregnated carbon slurry forms, the porous organic material include natural linen-cotton,
Aramid fiber, nylon, polypropylene, polyethylene, polytetrafluoroethylene (PTFE), polyethylene terephthalate and other electrolyte resistances can be good
Organic matter；
Or, the porous electron conducting layer is two or more above-mentioned any compound compositions；
The porous electron conducting layer has through-hole structure, and the region of non through hole sets blind hole or rough surface；The porous electricity
The thickness of 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 characterised in that：The electric insulators are oxidationreduction electricity
Position window is wide, aligns negative active core-shell material and electrolyte is stable, the organic or inorganic insulating material that maskable lithium ion is passed through
The film of formation, the material of the film includes polyvinyl chloride, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene (PTFE), poly- to benzene two
Formic acid glycol ester, polyamide, polyimides, polyethers nitrile, PMA, Kynoar, polyurethane, polyacrylonitrile,
One or more in butadiene-styrene rubber, improved polyalkene, ceramics, metal oxide, metal hydroxides；The electric insulators
With through-hole structure；The thickness of the electric insulators is at 0.01~300 μm, and through hole porosity is led less than or equal to the electronics
The through hole porosity of electric layer, aperture is not more than the effective aperture of the electron conducting layer.
8. compound porous collector as claimed in claim 1, it is characterised in that：The shape of through holes of the compound porous collector
It is to include the one or more in circular, square, rhombus, rectangle；The structure of the compound porous collector by be evaporated in vacuo,
The method that ion plating, sputtering, the CVD method of plasma CVD or melt impregnation cooling, solution impregnate solvent flashing
Porous electron conducting layer substrate one side coat or be bonded electric insulators, or electric insulators substrate one side coating or
It is bonded porous electron conducting layer and obtains, or is coating or be bonded electric insulators with passing through machine after porous electron conducting layer
Tool or the method for air-flow punching are obtained.
9. a kind of preparation method of compound porous collector, it is characterised in that the preparation method comprises the following steps：
1) pre-process, specifically include：
A. clean and dry：In the range of 20~60 DEG C, using spray, immersion or the method organic solvent wiped to porous
Electron conducting layer or/and electric insulators are cleaned 3~10 minutes；The organic solvent is one kind in low boiling volatile liquid
Or it is several, the low boiling volatile liquid includes ethanol, acetone and gasoline；It will be dried after cleaning under 60~90 DEG C of hot blast
30~120 minutes；
B. it is surface-treated：Soaked using alkali, pickling, gamma-ray irradiation, the surface treatment method of ultraviolet radioactive or corona treatment
Porous electron conducting layer or/and electric insulators after cleaning-drying is surface-treated；
2) it is combined：Compound porous collector is that electric insulators substrate one side coats porous electron conducting layer, in electric insulators
Cast coat forms the electrocondution slurry of porous electron conducting layer above, and the distance between control coater head and electric insulators make
It is 10~1000 μm, the temperature control of heating plate and heating roller during cast coat to be cast obtained porous electron conducting layer thickness
System is at 80~300 DEG C；
Or, compound porous collector is that porous electron conducting layer substrate one side coats electric insulators, in porous electronic conduction
The melt or solution of layer cast coat electric insulators above, the distance between control coater head and porous electron conducting layer make
The electric insulators thickness that must be cast is 0.01~300 μm, and heating plate and the temperature control of heating roller exist during cast coat
80~300 DEG C；
Or, compound porous collector is porous electron conducting layer substrate one side bonding electric insulators and electric insulators are exhausted
Edge organic polymer films, porous electron conducting layer and electric insulators one side are overlaped, and heated roll-in is combined, heating
The temperature control of roller is at 80~300 DEG C；
3) air-flow punching：The one side composite of electric insulators and porous electron conducting layer is drawn to air-flow hole punched device
Between upper and lower mould, composite electron insulating barrier one facing to cope plate, the high-pressure inert gas of heat are led to while matched moulds
In mould inlet plenum, the electron conducting layer at electric insulators lead to the hole site is washed open using hot high pressure air-flow, in electron conducting layer
It is upper to form through hole corresponding with electric insulators through hole；Or wash porous electron conducting layer lead to the hole site open using hot high pressure air-flow
The electric insulators at place, form through hole corresponding with porous electron conducting layer through hole on electric insulators；The temperature of thermal current
Control is at 80~250 DEG C；The inert gas pressure is in 0.5~5MPa；
4) post-process：The one side composite of electric insulators after punching and porous electron conducting layer is blowed dry, after
Clean or polish.
10. a kind of sandwich composite construction layer, it is characterised in that：The sandwich composite construction layer by compound porous plus plate current-collecting body,
Separation layer and compound porous negative current collector composition, compound porous plus plate current-collecting body and compound porous the negative current collector difference
For the compound porous collector according to any one of claim 1 to 8, separation layer be located at compound porous plus plate current-collecting body and
Between compound porous negative current collector, the electric insulators side of compound porous plus plate current-collecting body and compound porous negative current collector
It is in contact with separation layer；The separation layer is polyethylene, polypropylene, Kynoar or the nonconducting porous polymeric of other electronics
Thing material；Or, described separation layer is glass fibre non-woven, non-woven fabrics of synthetic fiber, ceramic fiber paper or other electronics
The composite porous material of nonconducting inorganic non-metallic material and organic polymer；Or, the material of separation layer uses electronics not
The compound gel polymer electrolyte composite wood constituted in conductive polymeric matrix, liquid organic plasticizers and the part of lithium salts three
Material；Using physical bonds or mechanical heat seal between compound porous plus plate current-collecting body, separation layer and compound porous negative current collector
Method is combined into the sandwich composite construction layer being brought into close contact mutually.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1379415A (en) * | 2001-04-06 | 2002-11-13 | 宝电通科技股份有限公司 | Composite structural material for thermosensitive resistor with positive temp coefficient and its preparing process |
| CN102610830A (en) * | 2012-03-26 | 2012-07-25 | 龙能科技（苏州）有限公司 | Lithium ion battery |
| CN103187551A (en) * | 2011-12-30 | 2013-07-03 | 北京好风光储能技术有限公司 | Lithium ion liquid flow battery |
| CN103219521A (en) * | 2012-01-20 | 2013-07-24 | 北京好风光储能技术有限公司 | Bipolarity current collector and preparation method |
| CN103427086A (en) * | 2012-05-17 | 2013-12-04 | 清华大学 | Current collector preparation method |
-
2014
- 2014-06-17 CN CN201410270417.XA patent/CN105186006B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1379415A (en) * | 2001-04-06 | 2002-11-13 | 宝电通科技股份有限公司 | Composite structural material for thermosensitive resistor with positive temp coefficient and its preparing process |
| CN103187551A (en) * | 2011-12-30 | 2013-07-03 | 北京好风光储能技术有限公司 | Lithium ion liquid flow battery |
| CN103219521A (en) * | 2012-01-20 | 2013-07-24 | 北京好风光储能技术有限公司 | Bipolarity current collector and preparation method |
| CN102610830A (en) * | 2012-03-26 | 2012-07-25 | 龙能科技（苏州）有限公司 | Lithium ion battery |
| CN103427086A (en) * | 2012-05-17 | 2013-12-04 | 清华大学 | Current collector preparation method |
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