CN106159277A - Porous current collector and preparation method thereof - Google Patents
Porous current collector and preparation method thereof Download PDFInfo
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- CN106159277A CN106159277A CN201510176130.5A CN201510176130A CN106159277A CN 106159277 A CN106159277 A CN 106159277A CN 201510176130 A CN201510176130 A CN 201510176130A CN 106159277 A CN106159277 A CN 106159277A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a kind of porous current collector for secondary cell, including current collector layers () and current collector layers (two), described current collector layers (one) is metal forming, described current collector layers (two) is the porous metallic layers with three-dimensional cavernous structure, and current collector layers () and current collector layers (two) are combined by metallic bond.Present invention also offers the preparation method of a kind of above-mentioned porous current collector.The porous current collector of the present invention is conducive to strengthening the electric conductivity of electrode, simultaneously works as fastening the effect of active electrode material, prevents electrode material from coming off, it is possible to significantly improve the performance of lithium ion battery.
Description
Technical field
The present invention relates to a kind of porous current collector and preparation method thereof, particularly relate to a kind of lithium ion battery porous
Collector and preparation method thereof.
Background technology
In recent years, lithium ion battery is at mobile electronic device, electric automobile, standby energy storage, intelligent grid etc.
Field is gradually applied.But, existing lithium ion battery is still difficult to meet electric tool, electric automobile (EVs),
The hybrid electric vehicle (PHEVs) power density to battery, the requirement of energy density.Conventional lithium ion battery electricity
The design of pole is anode and cathode active materials to be mixed in proportion with conductive agent (carbon), binding agent etc., is coated with respectively
Cloth is in aluminium foil, copper foil current collector.The result of this design is: active material is not easy with collector well
In conjunction with, need to use a certain amount of binding agent, cause electron transport ability poor, additionally use said method coating
Electrode material layer easily come off, and capacity play be affected.
The afflux physical ability efficient solution with three-dimensional porous structure is determined the technical problem of above-mentioned existence.Such as Chen Xin etc.
(Chinese patent application 201310488208.8) discloses a kind of three-dimensional Arrays of Copper Nanowires collector, and it is by directly
Connect the Arrays of Copper Nanowires composition being grown in copper surface.This three-dimensional Arrays of Copper Nanowires collector is by Copper Foil
Surface electrochemistry growth Copper hydrate nano wire, the most original preparation in hydrogen atmosphere the most again.First, electrification
During the long nano wire of student, the parameter such as thickness of three-dimensional manometer array layers to be controlled is relatively difficult, prepares in addition
Process needs substantial amounts of electrolyte, is unfavorable for industrialization.
Shi Chunsheng etc. (Chinese patent application 201210536209.0) disclose the preparation method of a kind of foam copper,
It is by the most compressing after sodium chloride particle and electrolytic copper powder mixing, sinters the most under an inert atmosphere,
After being placed in recirculated water removing sodium chloride, in hydrogen, reduction obtains foam copper again.The method preparation process is complicated,
And the mixing of sodium chloride particle and electrolytic copper powder is difficult to ensure that and mixs homogeneously, may the hole of serious impression foam copper
The performances such as gap rate.The foam copper prepared in this way is also difficult to meet the requirement of porous current collector.
Although said method can improve battery performance to a certain extent, but still there is a need to seek to improve lithium
Ion battery electrode performance takes into account that technique is simple simultaneously, low cost the technology that can produce in batches, supplying
Should the most extensive electric motor car and the demand of portable electric appts.
Summary of the invention
In order to solve the problems referred to above, the invention provides a kind of porous current collector for secondary cell and preparation thereof
Method.
The present invention is achieved through the following technical solutions:
A kind of porous current collector for secondary cell, including current collector layers () and current collector layers (two),
Described current collector layers (one) is metal forming, and described current collector layers (two) is the porous with three-dimensional cavernous structure
Metal level, current collector layers () and current collector layers (two) are combined by metallic bond.
According to the purpose of the present invention, the metal in described metal forming is selected from copper, aluminum, silver, gold, platinum, nickel, titanium
With at least one in palladium.
According to the purpose of the present invention, the thickness of described metal forming is 5～25 microns；Preferably, described metal forming
Thickness be 8～15 microns..
According to the purpose of the present invention, the metal in described porous metallic layers selected from copper, aluminum, silver, gold, platinum, nickel,
At least one in titanium and palladium.
According to the purpose of the present invention, the thickness of described porous metallic layers is 0.2～20 micron；Preferably, described
The thickness of porous metallic layers is 2～10 microns.According to the embodiment of the present invention, current collector layers (two) is permissible
It is positioned in the single side face of current collector layers (one), it is also possible to be positioned in the two sided of current collector layers (one).No matter
The one side of current collector layers () has current collector layers (two), or bilateral all has current collector layers (two),
The thickness of above-mentioned porous metallic layers (i.e. current collector layers (two)) refers both to the thickness of one side or monolayer.
According to the purpose of the present invention, the porosity of described porous metallic layers is between 20%～90%；Preferably,
The porosity of porous metallic layers is 40～90%；It is highly preferred that the porosity of porous metallic layers is 60～80%.
Present invention also offers the preparation method of a kind of above-mentioned porous current collector, comprise the steps:
(1) a kind of slurry being mixed into by slaine, organic complex and solvent is provided；
(2) provide a kind of metal forming as current collector layers (one), slurry described in step (1) is applied to gold
Belonging to paper tinsel surface, dry, rolling obtains the collector of coating；
(3) collector of step (2) described coating is calcined under reducing atmosphere obtain porous current collector, should
Porous current collector includes current collector layers () and current collector layers (two), and described current collector layers (two) is for having
The porous metallic layers of three-dimensional cavernous structure, current collector layers () and current collector layers (two) are combined by metallic bond.
According to the purpose of the present invention, in above-mentioned steps (1), slaine is selected from copper organic acid, curpic carbonate, nitric acid
At least one in copper, silver nitrate, nickel nitrate, nickel acetate and nickel oxalate.Wherein, described copper organic acid is selected from
At least one in Schweinfurt green and cupric oxalate；Preferably, described copper organic acid is Schweinfurt green.
According to the purpose of the present invention, in above-mentioned steps (1), organic complex is selected from polyacrylamide, acryloyl
At least one in amine, polyacrylic acid, polyacrylate, polyvinyl acetate and Polyurethane；Preferably, institute
Stating organic complex is acrylamide.
According to the purpose of the present invention, in above-mentioned steps (1), solvent is in dehydrated alcohol, methanol and ethylene glycol
At least one.
According to the purpose of the present invention, the slurry of above-mentioned steps (1) contains binding agent the most further, described viscous
Knot agent is selected from Polyethylene Glycol and polyvinyl alcohol at least one.
According to the purpose of the present invention, the metal in metal forming in above-mentioned steps (2) selected from copper, aluminum, silver,
At least one in gold, platinum, nickel, titanium and palladium.
According to the purpose of the present invention, above-mentioned metal foil thickness is 5～25 microns；Preferably, above-mentioned metal forming is thick
Degree is 8～15 microns.
According to the embodiment of the present invention, described slurry is applied to metal foil surface in (2) by above-mentioned steps, can
To be single spreading, it is also possible to be double spread.
According to the purpose of the present invention, in above-mentioned steps (3), reducing atmosphere is selected from hydrogen, methane, ethane and nothing
At least one in water-ethanol.
According to the purpose of the present invention, in above-mentioned steps (3), calcining heat is 500 DEG C～800 DEG C；Preferably,
In above-mentioned steps (3), calcining heat is 600 DEG C～700 DEG C.
According to the purpose of the present invention, above-mentioned current collector layers (two) thickness is 0.2～20 micron, preferably 2～
10 microns.
According to the purpose of the present invention, the porosity of above-mentioned current collector layers (two) is between 20%～90%；Preferably
Ground, the porosity of current collector layers (two) is 40～90%；It is highly preferred that the porosity of current collector layers (two)
It is 60～80%.
According to the purpose of the present invention, above-mentioned porous current collector gross thickness is 5～45 microns.
In the present invention, porous current collector be modified by metal foil surface and obtain have 3 D stereo porous knot
The metal forming of structure.Collection liquid surface is modified and can be formed co-ordination complex by slaine and Organic substance, then adds viscous
The method of mixture, is made into slurry with solvent, after being applied to metal foil surface process drying rolling with coating machine,
Under reducing atmosphere, calcining forms three-dimensional poroid metal collector.This three dimensional structure can make active material with embedding
Enter mode and enter collector, greatly reduce or eliminate the use of binding agent and conductive agent, and provide than tradition
The use more preferable electric conductivity of adhesive coated method.The density specific activity material of conductive agent and binding agent is low, subtracts
The use of few additive, can be effectively increased volume capacity.
The three dimensional structure of collection liquid surface is micron order or nano level solid apertured structure, and this three dimensional structure makes
Active material can contact with collector in the way of a kind of specific surface is bigger, strengthens the electric conductivity of electrode, simultaneously
Play the effect of fastening active electrode material, prevent electrode material from coming off.
Accompanying drawing explanation
Fig. 1 is embodiment 1 gained positive pole porous current collector figure；
Fig. 2 is embodiment 2 gained negative pole porous current collector figure.
Detailed description of the invention
Metal in current collector layers () and current collector layers (two) selected from copper, aluminum, silver, gold, platinum, nickel,
At least one in titanium and palladium.Current collector layers (one) and current collector layers (two) can with identical metal material,
Can also need according to specific embodiment optimized choice with different metal materials.
Current collector layers (two) be current collector layers (one) surface modify after formed there is 3 D stereo loose structure
Collector.The porosity of current collector layers (two) is between 20～90%.The porosity of current collector layers (two)
Too low, the coating rate of active material can be reduced, cause the conduction of 3 D stereo porous current collector decorative layer and torr solid
Effect can not make full use of.The porosity of current collector layers (two) is too high, can cause the auxiliaring effect of electronic conduction
Insufficient, thus need to add conductive agent and binding agent in active material, reduce the effective weight of active material.
The thickness in monolayer of current collector layers (two) should be with the thickness matching of active material layer, typically 0.2 to 20
Between Wei meter.The gross thickness of current collector layers () and current collector layers (two) is typically between 5 to 45 microns.
The thinnest meeting causes mechanical performance to reduce, and the defects such as fracture occurs in the course of processing；The thickest can increase the nonactive material of battery
The proportion of material.
The present invention is described in detail by following specific embodiment, but the present invention is not restricted to following
Embodiment.
Embodiment 1:
Plus plate current-collecting body layer (one) selects Copper Foil, and thickness is 10 microns.On plus plate current-collecting body layer ()
With coating machine double spread by Schweinfurt green, polyacrylamide, Polyethylene Glycol, polyvinyl alcohol and dehydrated alcohol mixing
Slurry.Plate coating thickness is 40 microns, 100 DEG C of drying afterwards, rolling, and after rolling, unilateral thickness is 20 micro-
Rice.Pole piece calcines pore-creating under 650 DEG C of hydrogen environments.Gained positive pole porous current collector, as shown in Figure 1.
Embodiment 2:
Negative current collector layer (one) selects Copper Foil, and thickness is 10 microns.On plus plate current-collecting body layer ()
Mixed by Schweinfurt green, polyacrylamide, Polyethylene Glycol, polyvinyl alcohol, and dehydrated alcohol with coating machine double spread
The slurry closed.Plate coating thickness is 20 microns, afterwards 100 DEG C of drying, rolling, and after rolling, unilateral thickness is 10
Micron.Pole piece calcines pore-creating under 750 DEG C of hydrogen environments.Gained negative pole porous current collector, as shown in Figure 2.
Claims (22)
1. for a porous current collector for secondary cell, including current collector layers () and current collector layers (two),
Described current collector layers (one) is metal forming, and described current collector layers (two) is for have three-dimensional cavernous structure
Porous metallic layers, current collector layers () and current collector layers (two) are combined by metallic bond.
Porous current collector the most according to claim 1, it is characterised in that the metal in described metal forming is selected from
At least one in copper, aluminum, silver, gold, platinum, nickel, titanium and palladium.
Porous current collector the most according to claim 2, it is characterised in that the thickness of described metal forming be 5～
25 microns.
Porous current collector the most according to claim 1, it is characterised in that the metal in described porous metallic layers
At least one in copper, aluminum, silver, gold, platinum, nickel, titanium and palladium.
Porous current collector the most according to claim 4, it is characterised in that the thickness of described porous metallic layers is
0.2～20 micron.
Porous current collector the most according to claim 5, it is characterised in that the thickness of described porous metallic layers is
2～10 microns.
Porous current collector the most according to claim 1, it is characterised in that the porosity of described porous metallic layers
It is between 20%～90%.
8. a preparation method for the porous current collector as described in claim 1-7 is arbitrary, comprises the steps:
(1) a kind of slurry being mixed into by slaine, organic complex and solvent is provided；
(2) provide a kind of metal forming as current collector layers (one), slurry described in step (1) is applied to gold
Belonging to paper tinsel surface, dry, rolling obtains the collector of coating；
(3) collector of step (2) described coating is calcined under reducing atmosphere obtain porous current collector, should
Porous current collector includes current collector layers () and current collector layers (two), and described current collector layers (two) is
There is the porous metallic layers of three-dimensional cavernous structure, current collector layers () and current collector layers (two) by gold
Belong to bond to close.
Preparation method the most according to claim 8, it is characterised in that slaine choosing in described step (1)
In copper organic acid, curpic carbonate, copper nitrate, silver nitrate, nickel nitrate, nickel acetate and nickel oxalate at least
A kind of.
Preparation method the most according to claim 9, it is characterised in that described copper organic acid selected from Schweinfurt green and
At least one in cupric oxalate.
11. preparation methoies according to claim 8, it is characterised in that organic complex in described step (1)
Thing is selected from polyacrylamide, acrylamide, polyacrylic acid, polyacrylate, polyvinyl acetate and gathers
At least one in amine ester.
12. preparation methoies according to claim 11, it is characterised in that described organic complex is acryloyl
Amine.
13. preparation methoies according to claim 8, it is characterised in that in described step (1), solvent is selected from
At least one in dehydrated alcohol, methanol and ethylene glycol.
14. preparation methoies according to claim 8, it is characterised in that in the slurry of described step (1) also
Containing binding agent further, described binding agent is selected from Polyethylene Glycol and polyvinyl alcohol at least one.
15. preparation methoies according to claim 8, it is characterised in that the metal forming in described step (2)
In at least one in copper, aluminum, silver, gold, platinum, nickel, titanium and palladium of metal.
16. preparation methoies according to claim 15, it is characterised in that described metal foil thickness is 5～25
Micron.
17. preparation methoies according to claim 16, it is characterised in that described metal foil thickness is 8～15
Micron.
18. preparation methoies according to claim 8, it is characterised in that reducing atmosphere in described step (3)
At least one in hydrogen, methane, ethane and dehydrated alcohol.
19. preparation methoies according to claim 8, it is characterised in that calcining heat in described step (3)
It it is 500 DEG C～800 DEG C.
20. preparation methoies according to claim 19, it is characterised in that calcining heat in described step (3)
It it is 600 DEG C～700 DEG C.
21. preparation methoies according to claim 8, it is characterised in that described current collector layers (two) thickness is
0.2～20 micron.
22. preparation methoies according to claim 8, it is characterised in that the hole of described current collector layers (two)
Rate is between 20%～90%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510176130.5A CN106159277A (en) | 2015-04-15 | 2015-04-15 | Porous current collector and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510176130.5A CN106159277A (en) | 2015-04-15 | 2015-04-15 | Porous current collector and preparation method thereof |
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| CN106159277A true CN106159277A (en) | 2016-11-23 |
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| CN201510176130.5A Pending CN106159277A (en) | 2015-04-15 | 2015-04-15 | Porous current collector and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108511681A (en) * | 2017-12-11 | 2018-09-07 | 吉安市优特利科技有限公司 | Electrode slice and preparation method thereof and battery |
| CN108598490A (en) * | 2018-04-20 | 2018-09-28 | 南京邮电大学 | A kind of three-dimensional porous metal negative electrode collector and its preparation method and application |
| CN109509877A (en) * | 2018-11-30 | 2019-03-22 | 清华大学深圳研究生院 | Carbon coating porous metal coating collector, preparation method and lithium battery |
| CN109698319A (en) * | 2018-12-28 | 2019-04-30 | 蜂巢能源科技有限公司 | Cathode of solid state battery and preparation method thereof and solid state electrode |
| CN111193005A (en) * | 2020-01-07 | 2020-05-22 | 北京航空航天大学 | Copper foil current collector and preparation method and application thereof |
| WO2023070548A1 (en) * | 2021-10-29 | 2023-05-04 | 宁德时代新能源科技股份有限公司 | Battery current collector and preparation method therefor, secondary battery, battery module, battery packet, and electric device |
| WO2023097457A1 (en) * | 2021-11-30 | 2023-06-08 | 宁德时代新能源科技股份有限公司 | Current collector and preparation method therefor, secondary battery, battery module, battery pack, and electric device |
| WO2024026970A1 (en) * | 2022-08-01 | 2024-02-08 | 宁德时代新能源科技股份有限公司 | Conductive film, preparation method therefor, electrode, current collector, secondary battery and apparatus |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108511681A (en) * | 2017-12-11 | 2018-09-07 | 吉安市优特利科技有限公司 | Electrode slice and preparation method thereof and battery |
| CN108511681B (en) * | 2017-12-11 | 2024-04-09 | 吉安市优特利科技有限公司 | Electrode plate, preparation method thereof and battery |
| CN108598490A (en) * | 2018-04-20 | 2018-09-28 | 南京邮电大学 | A kind of three-dimensional porous metal negative electrode collector and its preparation method and application |
| CN109509877A (en) * | 2018-11-30 | 2019-03-22 | 清华大学深圳研究生院 | Carbon coating porous metal coating collector, preparation method and lithium battery |
| CN109698319A (en) * | 2018-12-28 | 2019-04-30 | 蜂巢能源科技有限公司 | Cathode of solid state battery and preparation method thereof and solid state electrode |
| CN111193005A (en) * | 2020-01-07 | 2020-05-22 | 北京航空航天大学 | Copper foil current collector and preparation method and application thereof |
| WO2023070548A1 (en) * | 2021-10-29 | 2023-05-04 | 宁德时代新能源科技股份有限公司 | Battery current collector and preparation method therefor, secondary battery, battery module, battery packet, and electric device |
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| WO2023097457A1 (en) * | 2021-11-30 | 2023-06-08 | 宁德时代新能源科技股份有限公司 | Current collector and preparation method therefor, secondary battery, battery module, battery pack, and electric device |
| WO2024026970A1 (en) * | 2022-08-01 | 2024-02-08 | 宁德时代新能源科技股份有限公司 | Conductive film, preparation method therefor, electrode, current collector, secondary battery and apparatus |
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