CN103489649A - Composite current collector and method for manufacturing same - Google Patents
Composite current collector and method for manufacturing same Download PDFInfo
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- CN103489649A CN103489649A CN201210192682.1A CN201210192682A CN103489649A CN 103489649 A CN103489649 A CN 103489649A CN 201210192682 A CN201210192682 A CN 201210192682A CN 103489649 A CN103489649 A CN 103489649A
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Abstract
The invention discloses a composite current collector and a method for manufacturing the composite current collector. The method includes the following steps that S1, graphene oxide suspension liquid with the concentration of 0.25-1mg/ml is filtered and dried, so that a graphene oxide film is obtained; S2, the graphene oxide film is soaked into a metal precursor solution and then filtered, the filtered graphene oxide film is taken out and cleaned, so that a graphene oxide/metal precursor film is obtained, the concentration of the metal precursor solution is 0.01-0.05mol/L, and PH is from one to four; S3, the graphene oxide/metal precursor film is placed into a reactor and firstly heated in the vacuum state at the temperature of 150-200 DEG C, reduction reaction is performed for 1-2 hours, then reducibility gas is injected into the reactor, the temperature is raised to 500-1000 DEG C, and the reduction reaction is continuously performed for 0.5-2 hours, so that the composite current collector with the graphene/metal film as a substrate is obtained. The manufactured current collector improves the energy density of a super capacitor.
Description
Technical field
The present invention relates to the battery technology field, more particularly, relate to a kind of composite current collector and preparation method thereof.
Background technology
Ultracapacitor is a kind of novel energy storage device, there is the advantages such as high power density (for more than 10 times of common batteries), high cycle life (cycle-index can reach more than 100,000 times), fast charging and discharging performance are good, be widely used in the AC-battery power source of military field, device for mobile communication, computer and electric automobile etc.Usually ultracapacitor mainly by electrode active material layer, electrolyte, assemble every film, collector, shell etc.The energy density of existing ultracapacitor is generally lower, the influencing factor of the energy density of ultracapacitor mainly contains: the electric capacity of electrode material, the voltage of system, electrode material accounts for the proportion of the total weight of electrode active material layer, collector, sheathing material composition.Therefore, the weight of the energy-storage property of increase electrode material and each composition material of reduction device can effectively improve the performance of device.Wherein, the quality of reduction collector is a method that effectively improves energy density.
Collector is a kind of structure or part that collects electric current, and major function is that the electric current that cell active materials is produced collects, and electron channel is provided, and accelerates electric charge and shifts, and improves and discharges and recharges a coulomb efficiency.Need to meet the characteristics such as conductivity is high, good mechanical property, quality is light, internal resistance is little as collector.
At present, in most document or in industry, anodal aluminium foil, the negative pole of adopting of general collector adopts Copper Foil, because the density of metal collector is larger, quality is heavier, and the weight of general collector accounts for 20 ~ 25% of whole battery, in the case, the proportion that electrode material accounts for whole battery greatly reduces, and finally causes the energy density of ultracapacitor lower.
Given this, be necessary the collector that provides a kind of quality less.
Graphene has good character, the lighter weight of the graphene film prepared by Graphene, its high mechanical performance and high conductivity also can meet the key property index of collector application simultaneously, therefore based on Graphene, prepared graphene film can serve as the collector use, and can reduce the quality of collector.
Preparing the graphene film great majority is to be prepared into graphene oxide film by graphene oxide suspension, then thermal reduction prepares graphene film through high temperature.Prepare graphene oxide film by graphene oxide comparatively easy, and the film of preparing is comparatively regular, but is easier at high temperature fragmentation when being reduced to graphene film, affect the performance of collector.
Therefore, in prior art, have following technical problem: the quality of metal collector energy density heavier, that cause ultracapacitor is lower, Graphene use as collector the quality can reduce collector but in manufacturing process graphene film easily broken.
Summary of the invention
The technical problem to be solved in the present invention is, above-mentioned defect for prior art: the quality of metal collector energy density heavier, that cause ultracapacitor is lower, Graphene use as collector the quality can reduce collector but in manufacturing process graphene film easily broken, a kind of preparation method of composite current collector is provided.
The technical problem that the present invention further will solve is, a kind of composite current collector is provided.
The present invention is in graphene oxide film surface deposition metal precursor, method by thermal reduction prepares Graphene/metallic film again, in the process of reduction, avoided Graphene fragmentation, protected the integrality of Graphene, and the existence of metal has improved the conductivity of collector; Prepare Graphene/metallic film and can be used as collector, compare with traditional Copper Foil, aluminium foil with the collector of this film preparation, collector weight greatly alleviates, and then has improved the energy density of ultracapacitor.
The technical solution adopted for the present invention to solve the technical problems is: construct a kind of preparation method of composite current collector, comprise the following steps:
S1: the graphene oxide suspension filtered, the drying that by concentration, are 0.25 ~ 1mg/ml obtain graphene oxide film;
S2: described graphene oxide film is immersed in metal precursor solution, and subsequent filtration, take out screening and clean, and obtains graphene oxide/metal precursor film, and the concentration of described metal precursor solution is 0.01 ~ 0.05mol/L, and pH value is 1 ~ 4;
S3: described graphene oxide/metal precursor film is put into to reactor, at first in 150 ~ 200 ℃ of vacuum state heat reduction reactions 1 ~ 2 hour; Then, in reactor, pass into reducibility gas, and be warming up to 500 ~ 1000 ℃, continue reduction reaction 0.5 ~ 2 hour, obtaining Graphene/metallic film is the described composite current collector of base material.
In the preparation method of composite current collector of the present invention, in described step S1: the solvent of described graphene oxide suspension comprises at least one in deionized water, ethanol, methyl alcohol and isopropyl alcohol.
In the preparation method of composite current collector of the present invention, in described step S1, the filtration of described graphene oxide suspension comprises: described graphene oxide suspension is obtained to the described graphene oxide film that thickness is 3 ~ 10 μ m by the miillpore filter vacuum filtration.
In the preparation method of composite current collector of the present invention, in described step S2: described metal precursor solution comprises AgNO
3solution, PdCl
2solution or Mg(NO
3)
2solution.
In the preparation method of composite current collector of the present invention, in described step S2: the time that described graphene oxide film is immersed in described metal precursor solution is 10 ~ 30 minutes.
In the preparation method of composite current collector of the present invention, in described step S3: described reactor is tube furnace.
In the preparation method of composite current collector of the present invention, in described step S3: after passing into reducibility gas, according to the heating rates of 5 ~ 10 ℃/minute, be warming up to 500 ~ 1000 ℃.
In the preparation method of composite current collector of the present invention, in described step S3: the flow that passes into of reducibility gas is 50 ~ 70ml/ minute.
In the preparation method of composite current collector of the present invention, the mist that described reducibility gas is hydrogen or hydrogen and nitrogen; Wherein, in the mist of hydrogen and nitrogen, the volume fraction of nitrogen is 90 ~ 95%, and the volume fraction of hydrogen is 5 ~ 10%.
A kind of composite current collector, adopt above-mentioned preparation method to prepare.
At first the present invention filters graphene oxide suspension, obtains filter cake, takes off the film on filter membrane after drying, obtain graphene oxide film, adopt and filter the method that graphene oxide suspension makes graphene oxide film, simple to operate, be easier to make graphene oxide film.
Graphene oxide film is immersed in metal precursor solution again, in graphene oxide film surface deposition metal precursor, forms graphene oxide/metal precursor film, the existence of metal can improve the conductivity of collector.
Reduced, graphene oxide/metal precursor film is at first 150 ~ 200 ℃ of vacuum state heat reductions 1 ~ 2 hour again; Pass into again reducibility gas, be warming up to 500 ~ 1000 ℃, reduce 0.5 ~ 2 hour, obtain Graphene/metallic film; Reducibility gas is selected hydrogen; because hydrogen can be repaired the defect of graphene film in reduction process; can protect the integrality of graphene film by the reduction of step S2 heating; in passing into the process that reducibility gas reduced; can also pass into protective gas so that protection to be provided; by graphene oxide/metal precursor film and air insulated, avoid the Graphene oxidation again made.Protective gas can be nitrogen, certainly, can be also inert gas well known in the art.
Method of reducing of the present invention has effectively avoided graphene oxide problem in being reduced into the process of Graphene, the problem includes: Graphene breakable problem, to protect the integrality of Graphene, prepares more complete Graphene/metallic film.
Simultaneously, the graphene oxide film that the present invention makes has the complete and uniform advantage of film of film, therefore, after being immersed in metal precursor solution by graphene oxide film, metal precursor at the graphene oxide film surface deposition also has coherent, uniform advantage, has improved the performance of the collector made with this Graphene/metallic film.
And, this graphene oxide film can provide stronger mechanical performance, and can strengthen the electric conductivity of graphene film at the metal of graphene oxide film surface deposition, therefore Graphene/metallic film of preparing has the advantage of high-mechanical property and high conductivity concurrently, has guaranteed when it uses as collector to have the higher life-span.
The present invention prepares Graphene/metallic film and can be used as collector, with the collector of this film preparation, with traditional Copper Foil, aluminium foil, compares, and collector weight greatly alleviates, and then has improved the energy density of ultracapacitor.
The accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
Fig. 1 is the preparation method's of composite current collector of the present invention flow chart.
Embodiment
Understand for technical characterictic of the present invention, purpose and effect being had more clearly, now contrast accompanying drawing and describe the specific embodiment of the present invention in detail.
Below in conjunction with Fig. 1, the preparation method of composite current collector of the present invention is described.As shown in Figure 1, the preparation method's that Fig. 1 is composite current collector of the present invention flow chart.The preparation method of composite current collector of the present invention comprises the following steps:
S1: the graphene oxide suspension filtered, the drying that by concentration, are 0.25 ~ 1mg/ml obtain graphene oxide film.
Wherein, the solvent of graphene oxide suspension comprises at least one in deionized water, ethanol, methyl alcohol and isopropyl alcohol, for graphene oxide is uniformly dispersed in solvent, all right ultrasonic processing graphene oxide suspension, obtain finely dispersed graphene oxide suspension; During filtration, adopt the miillpore filter vacuum filtration process to filter stable, finely dispersed graphene oxide suspension, obtain filter cake, after dry (preferably 40 ℃ of baking temperatures), take off the film on filter membrane, obtain graphene oxide film; The THICKNESS CONTROL of graphene oxide film is at 3 ~ 10 μ m, and the volume of pouring graphene oxide suspension during by filtration into is controlled the thickness of graphene oxide film.Drying means can adopt natural air drying or vacuum drying chamber drying.
S2: graphene oxide film is immersed in metal precursor solution, and subsequent filtration, take out screening and clean, and obtains graphene oxide/metal precursor film, and the concentration of metal precursor solution is 0.01 ~ 0.05mol/L, and pH value is 1 ~ 4.
Wherein, metal precursor solution comprises AgNO
3solution, PdCl
2solution or Mg(NO
3)
2solution; The time that graphene oxide film is immersed in metal precursor solution is 10 ~ 30 minutes.Graphene oxide film can also stir metal precursor solution after being immersed in metal precursor solution, makes the abundant plated metal presoma of positive and negative of graphene oxide film, and it is ultrasonic agitation that stirring means can be, but not limited to.
S3: described graphene oxide/metal precursor film is put into to reactor, and at first, in 150 ~ 200 ℃ of vacuum state heat reduction reactions 1 ~ 2 hour, this step can be carried out in vacuum drying chamber; Then, toward reactor, be preferably in tube furnace, pass into reducibility gas, and be warming up to 500 ~ 1000 ℃ according to the heating rate of 5 ~ 10 ℃/minute, continue reduction reaction 0.5 ~ 2 hour, obtaining Graphene/metallic film is the described composite current collector of base material, and this step can be carried out in tube furnace.
The mist that reducibility gas is hydrogen or hydrogen and protective gas, as the mist of hydrogen and nitrogen; Wherein, in the mist of hydrogen and protective gas, the volume fraction of protective gas is 90 ~ 95%, and the volume fraction of hydrogen is 5 ~ 10%.The flow that passes into of reducibility gas is 50 ~ 70ml/ minute.
Embodiment 1
1. prepare graphene oxide film
With the deionization water as solvent, the graphene oxide suspension that configuration concentration is 0.25mg/ml: the graphene oxide of 25mg is joined in the deionized water of 100ml, stir 20 minutes, obtain the graphene oxide aaerosol solution.
Adopt the miillpore filter vacuum filtration process to filter graphene oxide suspension, obtain filter cake, filter cake is placed in to baking oven in 40 ℃ of oven dry, from filter membrane, take off film, obtain graphene oxide film.The volume of pouring graphene oxide suspension during by filtration into is controlled the thickness of graphene oxide film, and THICKNESS CONTROL is at 3 μ m.
2. prepare graphene oxide/silver nitrate film
1. the graphene oxide film tow sides in are immersed in respectively to the AgNO of PH=1
3in solution, its concentration is 0.01mol/L, soaks 10 minutes, takes out, and with deionized water, repeatedly cleans the graphene oxide film that skin is metal ion, obtains graphene oxide/silver nitrate laminated film.
3. prepare Graphene/metallic film
By the graphene oxide in 2./silver nitrate film, put into vacuum drying chamber, 150 ℃ of vacuum reductions 1 hour; Put it in tube furnace again, pass into hydrogen, the flow of controlling hydrogen is 50ml/ minute; Be warming up to 500 ℃ with the heating rates of 5 ℃/minute, this temperature reduction 0.5 hour, obtain Graphene/Ag laminated film, this Graphene/Ag laminated film of usining makes composite current collector as base material.
Embodiment 2
1. prepare graphene oxide film
Make solvent with ethanol, the graphene oxide suspension that configuration concentration is 1mg/ml: the graphene oxide of 100mg is joined in the ethanol of 100ml, stir 50 minutes, obtain the graphene oxide aaerosol solution.
Adopt the miillpore filter vacuum filtration process to filter graphene oxide suspension, obtain filter cake, filter cake is placed in to baking oven in 40 ℃ of oven dry, from filter membrane, take off film, obtain graphene oxide film.The volume of pouring graphene oxide suspension during by filtration into is controlled the thickness of graphene oxide film, and THICKNESS CONTROL is at 10 μ m.
2. prepare graphene oxide/palladium bichloride film
1. the graphene oxide film tow sides in are immersed in respectively to the PdCl of PH=4
2in solution, its concentration is 0.05mol/L, soaks 30 minutes, takes out, and with deionized water, repeatedly cleans the graphene oxide film that skin is metal ion, obtains graphene oxide/palladium bichloride laminated film.
3. prepare Graphene/palladium film
By the graphene oxide in 2./palladium bichloride film, put into vacuum drying chamber, 150 ℃ of vacuum reductions 2 hours; Put it in tube furnace again, pass into hydrogen, the flow of hydrogen is 50ml/ minute; Be warming up to 1000 ℃ with the heating rates of 10 ℃/minute, at this temperature reductase 12 hour, obtain Graphene/Pd laminated film, this Graphene/Pd laminated film of usining makes composite current collector as base material.
Embodiment 3
1. prepare graphene oxide film
Make solvent with methyl alcohol, the graphene oxide suspension that configuration concentration is 0.25mg/ml: the graphene oxide of 25mg is joined in the methyl alcohol of 100ml, stir 20 minutes, obtain the graphene oxide aaerosol solution.
Adopt the miillpore filter vacuum filtration process to filter graphene oxide suspension, obtain filter cake, filter cake is placed in to baking oven in 40 ℃ of oven dry, from filter membrane, take off film, obtain graphene oxide film.The volume of pouring graphene oxide suspension during by filtration into is controlled the thickness of graphene oxide film, and THICKNESS CONTROL is at 3 μ m.
2. prepare graphene oxide/Mg(NO
3)
2film
1. the graphene oxide film tow sides in are immersed in respectively to the Mg(NO of PH=1
3)
2in solution, its concentration is 0.01mol/L, soaks 10 minutes, takes out, and with deionized water, repeatedly cleans the graphene oxide film that skin is metal ion, obtains graphene oxide/Mg(NO
3)
2laminated film.
3. prepare Graphene/Mg film
By the graphene oxide/Mg(NO in 2.
3)
2laminated film, put into vacuum drying chamber, 200 ℃ of vacuum reductions 1 hour; Put it into again in tube furnace, pass into nitrogen and drive the air in stove away; Then pass into mist in stove, mist is that volume fraction is the hydrogen that 90% nitrogen and volume fraction are 10%, the flow of mist is 50ml/ minute, be warming up to 1000 ℃ with the heating rates of 10 ℃/minute, at this temperature reductase 12 hour, obtain Graphene/Mg laminated film, with this Graphene/Mg laminated film, make composite current collector.
Embodiment 4
1. prepare graphene oxide film
Make solvent with isopropyl alcohol, the graphene oxide suspension that configuration concentration is 0.5mg/ml: the graphene oxide of 50mg is joined in the isopropyl alcohol of 100ml, stir 30 minutes, obtain the graphene oxide aaerosol solution.
Adopt the miillpore filter vacuum filtration process to filter graphene oxide suspension, obtain filter cake, filter cake is placed in to baking oven in 40 ℃ of oven dry, from filter membrane, take off film, obtain graphene oxide film.The volume of pouring graphene oxide suspension during by filtration into is controlled the thickness of graphene oxide film, and THICKNESS CONTROL is at 6 μ m.
2. prepare graphene oxide/silver nitrate film
1. the graphene oxide film tow sides in are immersed in respectively to the AgNO of PH=2
3in solution, its concentration is 0.03mol/L, soaks 20 minutes, takes out, and with deionized water, repeatedly cleans the graphene oxide film that skin is metal ion, obtains graphene oxide/silver nitrate laminated film.
3. prepare Graphene/silver-colored film
By the graphene oxide in 2./silver nitrate film, put into vacuum drying chamber, 180 ℃ of vacuum reductions 1.5 hours; Put it into again in tube furnace, pass into nitrogen and drive the air in stove away; Then pass into mist in stove, mist is that volume fraction is the hydrogen that 92% nitrogen and volume fraction are 8%, the flow of mist is 60ml/ minute, be warming up to 900 ℃ with the heating rates of 7 ℃/minute, this temperature reduction 1.5 hours, obtain Graphene/Ag laminated film, this Graphene/Ag laminated film of usining makes composite current collector as base material.
Embodiment 5
1. prepare graphene oxide film
Make solvent with deionized water and ethanol, the graphene oxide suspension that configuration concentration is 0.7mg/ml: the graphene oxide of 70mg is joined in the deionized water and ethanol (volume ratio is 1:1) of 100ml, stir 35 minutes, obtain the graphene oxide aaerosol solution.
Adopt the miillpore filter vacuum filtration process to filter graphene oxide suspension, obtain filter cake, filter cake is placed in to baking oven in 40 ℃ of oven dry, from filter membrane, take off film, obtain graphene oxide film.The volume of pouring graphene oxide suspension during by filtration into is controlled the thickness of graphene oxide film, and THICKNESS CONTROL is at 8 μ m.
2. prepare graphene oxide/palladium bichloride film
1. the graphene oxide film tow sides in are immersed in respectively to the PdCl of PH=3
2in solution, its concentration is 0.04mol/L, soaks 15 minutes, takes out, and with deionized water, repeatedly cleans the graphene oxide film that skin is metal ion, obtains graphene oxide/palladium bichloride laminated film.
3. prepare Graphene/palladium film
By the graphene oxide in 2./palladium bichloride film, put into vacuum drying chamber, 170 ℃ of vacuum reductions 1.6 hours; Put it into again in tube furnace, pass into argon gas and drive the air in stove away; Then pass into mist in stove, mist is that volume fraction is the hydrogen that 91% argon gas and volume fraction are 9%, the flow of mist is 65ml/ minute, be warming up to 900 ℃ with the heating rates of 8 ℃/minute, this temperature reduction 1 hour, obtain Graphene/Pd laminated film, with this Graphene/Pd laminated film, make composite current collector.
Embodiment 6
1. prepare graphene oxide film
With the deionization water as solvent, the graphene oxide suspension that configuration concentration is 0.8mg/ml: the graphene oxide of 80mg is joined in the deionized water of 100ml, stir 40 minutes, obtain the graphene oxide aaerosol solution.
Adopt the miillpore filter vacuum filtration process to filter graphene oxide suspension, obtain filter cake, filter cake is placed in to baking oven in 40 ℃ of oven dry, from filter membrane, take off film, obtain graphene oxide film.The volume of pouring graphene oxide suspension during by filtration into is controlled the thickness of graphene oxide film, and THICKNESS CONTROL is at 7 μ m.
2. prepare graphene oxide/Mg(NO
3)
2film
1. the graphene oxide film tow sides in are immersed in respectively to the Mg(NO of PH=3
3)
2in solution, its concentration is 0.02mol/L, soaks 18 minutes, takes out, and with deionized water, repeatedly cleans the graphene oxide film that skin is metal ion, obtains graphene oxide/Mg(NO
3)
2laminated film.
3. prepare Graphene/Mg film
By the graphene oxide/Mg(NO in 2.
3)
2laminated film, put into vacuum drying chamber, 200 ℃ of vacuum reductions 1.3 hours; Put it into again in tube furnace, pass into argon gas and drive the air in stove away; Then pass into mist in stove, mist is that volume fraction is the hydrogen that 92% argon gas and volume fraction are 8%, the flow of mist is 60ml/ minute, be warming up to 600 ℃ with the heating rates of 6 ℃/minute, this temperature reduction 1 hour, obtain Graphene/Mg laminated film, this Graphene/Mg laminated film of usining makes composite current collector as base material.
Conductivity and hot strength test
1, conductivity
Measure the conductivity of Graphene/metallic film by four probe method.Instrument: the two electrical measurement four point probe tester of D41-11D/ZM type (manufacturer: Beijing Co., Ltd of Sevenstar Huachuang Electronic); Temperature: room temperature (as 28 ℃).
When measuring current is shown as the probe coefficient, press electricalresistivityρ's button, screen directly shows that the electricalresistivityρ is worth, and according to conductivity gamma=l/ ρ, directly calculates conductivity.
2, hot strength
Extension test is that (U.S. TA instrument, model: DMA Q800/TA), carry out, Graphene/metallic film is cut into 3 * 15mm at dynamic mechanical analyzer
2rectangular sheet carry out the tension test test.Draw speed: 0.01-0.05%min
-1.
Test result is as follows:
Table 1: the conductivity of Graphene/metallic film and hot strength
The above is described embodiments of the invention by reference to the accompanying drawings; but the present invention is not limited to above-mentioned embodiment; above-mentioned embodiment is only schematic; rather than restrictive; those of ordinary skill in the art is under enlightenment of the present invention; not breaking away from the scope situation that aim of the present invention and claim protect, also can make a lot of forms, within these all belong to protection of the present invention.
Claims (10)
1. the preparation method of a composite current collector, is characterized in that, comprises the following steps:
S1: the graphene oxide suspension filtered, the drying that by concentration, are 0.25 ~ 1mg/ml obtain graphene oxide film;
S2: described graphene oxide film is immersed in metal precursor solution, and subsequent filtration, take out screening and clean, and obtains graphene oxide/metal precursor film, and the concentration of described metal precursor solution is 0.01 ~ 0.05mol/L, and pH value is 1 ~ 4;
S3: described graphene oxide/metal precursor film is put into to reactor, at first in 150 ~ 200 ℃ of vacuum state heat reduction reactions 1 ~ 2 hour; Then, in reactor, pass into reducibility gas, and be warming up to 500 ~ 1000 ℃, continue reduction reaction 0.5 ~ 2 hour, obtaining Graphene/metallic film is the described composite current collector of base material.
2. the preparation method of composite current collector according to claim 1, is characterized in that, in described step S1: the solvent of described graphene oxide suspension comprises at least one in deionized water, ethanol, methyl alcohol and isopropyl alcohol.
3. the preparation method of composite current collector according to claim 1, it is characterized in that, in described step S1, the filtration of described graphene oxide suspension comprises: described graphene oxide suspension is obtained to the described graphene oxide film that thickness is 3 ~ 10 μ m by the miillpore filter vacuum filtration.
4. the preparation method of composite current collector according to claim 1, is characterized in that, in described step S2: described metal precursor solution comprises AgNO
3solution, PdCl
2solution or Mg(NO
3)
2solution.
5. the preparation method of composite current collector according to claim 1, is characterized in that, in described step S2: the time that described graphene oxide film is immersed in described metal precursor solution is 10 ~ 30 minutes.
6. the preparation method of composite current collector according to claim 1, is characterized in that, in described step S3: described reactor is tube furnace.
7. the preparation method of composite current collector according to claim 1, is characterized in that, in described step S3: after passing into reducibility gas, according to the heating rates of 5 ~ 10 ℃/minute, be warming up to 500 ~ 1000 ℃.
8. the preparation method of composite current collector according to claim 1, is characterized in that, in described step S3: the flow that passes into of reducibility gas is 50 ~ 70ml/ minute.
9. the preparation method of composite current collector according to claim 8, is characterized in that, the mist that described reducibility gas is hydrogen or hydrogen and nitrogen; Wherein, in the mist of hydrogen and nitrogen, the volume fraction of nitrogen is 90 ~ 95%, and the volume fraction of hydrogen is 5 ~ 10%.
10. a composite current collector, is characterized in that, adopts the described preparation method of the claims 1 ~ 9 any one to prepare.
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| CN201210192682.1A CN103489649A (en) | 2012-06-12 | 2012-06-12 | Composite current collector and method for manufacturing same |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105110794A (en) * | 2015-08-07 | 2015-12-02 | 常州富烯科技股份有限公司 | Graphene film and preparation method therefor |
| CN105938907A (en) * | 2016-05-26 | 2016-09-14 | 江苏深苏电子科技有限公司 | Preparation method of high-conductivity graphene current collector |
-
2012
- 2012-06-12 CN CN201210192682.1A patent/CN103489649A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105110794A (en) * | 2015-08-07 | 2015-12-02 | 常州富烯科技股份有限公司 | Graphene film and preparation method therefor |
| CN108178148A (en) * | 2015-08-07 | 2018-06-19 | 常州富烯科技股份有限公司 | The preparation method and graphene film of a kind of graphene film |
| CN108178148B (en) * | 2015-08-07 | 2020-04-28 | 常州富烯科技股份有限公司 | Preparation method of graphene film and graphene film |
| CN105938907A (en) * | 2016-05-26 | 2016-09-14 | 江苏深苏电子科技有限公司 | Preparation method of high-conductivity graphene current collector |
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Application publication date: 20140101 |