CN103811766A - Preparation method of current collector - Google Patents
Preparation method of current collector Download PDFInfo
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- CN103811766A CN103811766A CN201210460719.4A CN201210460719A CN103811766A CN 103811766 A CN103811766 A CN 103811766A CN 201210460719 A CN201210460719 A CN 201210460719A CN 103811766 A CN103811766 A CN 103811766A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
- C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
- C25F3/04—Etching of light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Cell Electrode Carriers And Collectors (AREA)
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Abstract
The invention discloses a preparation method of a current collector. The preparation method comprises the following steps of taking an aluminum foil as a work electrode, and etching the aluminum foil for 0.5-30 minutes under the current density at 50mA/cm<2>-900mA/cm<2>; adding an oxygenation graphite into a solvent, carrying out ultrasonic dispersion on an oxygenation graphite suspending liquid so as to obtain a graphene oxide suspending liquid, and regulating the PH value of the graphene oxide suspending liquid to be 10-11; mixing the graphene oxide suspending liquid and hydrazine hydrate to react for 12 hours to 24 hours, and adding a metal salt solution in the graphene oxide suspending liquid to obtain an electrolytic solution; placing the two etched aluminum foils which are utilized as the electrodes in the electrolytic solution, and carrying out electrophoresis on the electrolytic solution for 5 min-20 min under the voltage at 40V-80V; and heating the aluminum foils which are utilized as cathodes at 500 DEG C-1000 DEG C, and carrying out reducing treatment on the aluminum foils for 0.5h-2h to obtain the current collector. The current collector prepared by the preparation method of the current collector can reduce the internal resistance of a lithium ion battery.
Description
Technical field
The present invention relates to a kind of preparation method of collector.
Background technology
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 features such as conductivity is high, good mechanical property, quality is light, internal resistance is little as collector.
The anodal aluminium foil that adopts of general collector.But while use as collector with aluminium foil, can there is embedding lithium with Li and react in Al, generate LiAl alloy or Li under electronegative potential
3al
2, cause Al lattice dilatation, break, meanwhile, metal material is easily corroded, and can cause the contact resistance between it and electrode active material to enlarge markedly, thereby has improved the internal resistance that uses the battery of collector.
Summary of the invention
Based on this, be necessary to provide a kind of preparation method of the collector that can reduce the internal resistance of cell.
A preparation method for collector, comprises the steps:
Using aluminium foil as work electrode, and electrode and reference electrode composition three-electrode system is placed in to etching liquid, at 50mA/cm
2~ 900mA/cm
2current density under to described aluminium foil etching 0.5 minute ~ 30 minutes, described etching liquid contains hydrochloric acid and sulfuric acid, the concentration of described hydrochloric acid is 1mol/L ~ 2mol/L, the concentration of described sulfuric acid is 0.5mol/L ~ 1mol/L;
Graphite oxide is added in solvent, be mixed with graphite oxide suspension, by the ultrasonic dispersion of described graphite oxide suspension, obtain homodisperse graphene oxide suspension;
The pH value that regulates described graphene oxide suspension is 10 ~ 11;
After described graphene oxide suspension is mixed with hydrazine hydrate, at 80 ℃ ~ 120 ℃, react 12 hours ~ 24 hours, obtain graphene suspension;
In described graphene suspension, add metal salt solution, and ultrasonic dispersion obtains electrolyte;
Be placed in described electrolyte two aluminium foils through over etching as electrode, under the voltage of 40V ~ 80V, electrophoresis 5min ~ 20min; And
Under the atmosphere of reducibility gas, will be warming up to 500 ℃ ~ 1000 ℃ as the aluminium foil of negative electrode, reduction is processed 0.5h ~ 2h and is obtained collector.
In an embodiment, described aluminium foil was first put into aluminium foil in the sodium hydroxide solution that concentration is 1mol/L ~ 2mol/L and is soaked 0.5 minute ~ 3 minutes before carrying out etching therein, then cleaned, dry.
In an embodiment, when preparation graphite oxide suspension, described solvent is at least one in deionized water, ethanol, isopropyl alcohol and n-butanol therein, and the concentration of described graphite oxide is 0.25mg/ml ~ 1mg/ml.
In an embodiment, the alkaline solution that working concentration is 0.05mol/L ~ 1.5mol/L regulates the pH value of described graphene oxide suspension therein, and described alkaline solution is sodium hydroxide solution, potassium hydroxide solution or ammoniacal liquor.
In an embodiment, while preparing graphene suspension, the mass ratio of described hydrazine hydrate and described graphene oxide is 1:10 ~ 7:10 therein.
In an embodiment, the slaine in described metal salt solution is selected from Mg (NO therein
3)
26H
2o, Mg (SO
4)
27H
2o, Fe (NO
3)
39H
2o and Zn (NO
3)
26H
2at least one in O.
In an embodiment, the concentration of described metal salt solution is 0.25mg/ml ~ 2mg/ml therein.
In an embodiment, the Graphene in described electrolyte and the mass ratio of slaine are 1:1 ~ 1:2 therein.
In an embodiment, described reducibility gas is the mist of hydrogen and argon gas therein, and the volumn concentration of wherein said hydrogen is 5% ~ 10%.
In an embodiment, the aluminium foil as negative electrode is warming up to 500 ℃ ~ 1000 ℃ with the heating rate of 5 ℃/min ~ 10 ℃/min therein.
The preparation method of above-mentioned collector, by carrying out electrochemical etching at aluminium foil surface, form comparatively coarse surface, method by electro-deposition is at the surface deposition Graphene of aluminium foil, Graphene chemical stability is high, is difficult for being corroded, and protection collector is not corroded, can reduce the internal resistance that contacts between active material and collector, the life-span that can improve collector simultaneously; The graphene film of preparing by the method for electro-deposition is comparatively even, and film forming speed is fast, and productive rate is high.
Accompanying drawing explanation
Fig. 1 is the preparation method's of the collector of an execution mode flow chart.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details are set forth in the following description so that fully understand the present invention.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can do similar improvement without prejudice to intension of the present invention in the situation that, and therefore the present invention is not subject to the restriction of following public concrete enforcement.
Refer to Fig. 1, the preparation method of the collector of an execution mode, comprises the steps:
Step S110, using aluminium foil as work electrode, and electrode is placed in to etching liquid, at 50mA/cm
2~ 900mA/cm
2current density under etching 0.5 minute ~ 30 minutes.
In present embodiment, etching liquid contains hydrochloric acid and sulfuric acid, and the concentration of hydrochloric acid is 1mol/L ~ 2mol/L, and the concentration of sulfuric acid is 0.5mol/L ~ 1mol/L.
Preferably, the temperature of etching is 20 ℃ ~ 30 ℃.
Preferably, be stainless steel to the material of electrode.
Preferably, the thickness of aluminium foil is 10 μ m ~ 18 μ m.
Preferably, it is that the sodium hydroxide solution of 1mol/L ~ 2mol/L soaks 0.5 minute ~ 3 minutes that aluminium foil was first put into concentration before carrying out etching, dry after cleaning.It should be noted that, if aluminium foil surface has dirt, just aluminium foil is used to acetone, ethanol, the ultrasonic processing of deionized water 20 minutes ~ 30 minutes successively, rinse well with deionized water more afterwards, dry at 55 ℃.
Step S120, graphite oxide is added in solvent, be mixed with graphite oxide suspension, by ultrasonic graphite oxide suspension dispersion, obtain homodisperse graphene oxide suspension.
Preferably, solvent is at least one in deionized water, ethanol, isopropyl alcohol and n-butanol, and the concentration of described graphite oxide is 0.25mg/ml ~ 1mg/ml.
Preferably, the time of ultrasonic dispersion is 0.5 hour ~ 1 hour.
The pH value of step S130, adjusting graphene oxide suspension is 10 ~ 11.
Preferably, the alkaline solution that working concentration is 0.05mol/L ~ 1.5mol/L regulates the pH value of graphene oxide suspension, and alkaline solution is sodium hydroxide solution, potassium hydroxide solution or ammoniacal liquor.
Step S140, at 80 ℃ ~ 120 ℃, react 12 hours ~ 24 hours after graphene oxide suspension is mixed with hydrazine hydrate, obtain graphene suspension.
Preferably, the hydrazine hydrate solution that is 80% ~ 90% by graphene oxide suspension with mass concentration mixes.
Preferably, the mass ratio of hydrazine hydrate and graphene oxide is 1:10 ~ 7:10.
Step S150, in graphene suspension, add metal salt solution, and ultrasonic agitation obtains electrolyte.
Preferably, the slaine in metal salt solution is Mg (NO
3)
26H
2o, Mg (SO
4)
27H
2o, Fe (NO
3)
39H
2o or Zn (NO
3)
26H
2o.
Preferably, the concentration of the middle slaine (hydrated salt) of metal salt solution is 0.25mg/ml ~ 2mg/ml.
Preferably, the mass ratio of the slaine (hydrated salt) in Graphene and the metal salt solution in graphene suspension is 1:1 ~ 1:2.
Preferably, the time of ultrasonic dispersion is 15min ~ 30min.
Step S160, two aluminium foils through over etching are placed in electrolyte as electrode, under the voltage of 40V ~ 80V, electrophoresis 5min ~ 20min.
Preferably, two parallel being placed in electrolyte of aluminium foil, and spacing between two aluminium foils is 0.5cm ~ 1cm.
Preferably, the aluminium foil as negative electrode is taken off, dry in the vacuum drying chamber of 100 ℃.
In this step, the reaction of negative electrode is initially cell reaction, produces hydrogen and hydroxyl (OH
-), thereby make cathode surface form an electronegative high alkalinity boundary face.Prepare in Graphene process in reduction, on Graphene, remain hydroxyl and carboxyl, hydroxyl and carboxyl are combined with metal cation and are formed ionic bond, under the effect of extra electric field, with the Graphene of metal cation, to movable cathode, the anion anode in solution moves.Cathode surface is electronegative, with the Graphene surface band positive electricity of metal cation, on Graphene, residual carboxyl and the hydrogen ion of hydroxyl and the anion of cathode surface react, thereby Graphene is deposited on to cathode surface, thereby at the aluminium foil surface deposition one deck graphene layer as negative electrode.
Step S170, under the atmosphere of reducibility gas, will be warming up to 500 ℃ ~ 1000 ℃ as the aluminium foil of negative electrode, reduction is processed and within 0.5 hour ~ 2 hours, is obtained collector.
Preferably, reducibility gas is the mist of hydrogen and argon gas, and wherein the molar content of hydrogen is 5% ~ 10%.
Preferably, the flow of reducibility gas is 50ml/min ~ 70ml/min.
Preferably, the aluminium foil as negative electrode is warming up to 500 ℃ ~ 1000 ℃ with the heating rate of 5 ℃/min ~ 10 ℃/min.
Preferably, first the aluminium foil as negative electrode is put into tube furnace, pass into argon gas and drive the air in stove away, then be warming up to 500 ℃ under reducibility gas atmosphere ~ 1000 ℃.
The preparation method of above-mentioned collector, by carrying out electrochemical etching at aluminium foil surface, form comparatively coarse surface, method by electro-deposition is at the surface deposition Graphene of aluminium foil, Graphene chemical stability is high, is difficult for being corroded, and protection collector is not corroded, can reduce the internal resistance that contacts between active material and collector, the life-span that can improve collector simultaneously; The graphene film of preparing by the method for electro-deposition is comparatively even, and film forming speed is fast, and productive rate is high.
It should be noted that, the preparation method of above-mentioned collector does not need necessarily to carry out according to above-mentioned steps, such as step S110 can carry out after step S150, or between step S120 ~ step S150 or with step S120 ~ step S150, synchronize and carry out, as long as can carry out before step S160.
Further illustrate below in conjunction with specific embodiment.
Embodiment 1
Preparation technology's flow process of collector prepared by the present invention is as follows:
(1) preliminary treatment of aluminium foil: aluminium foil thick 10 μ m is placed in to acetone, ethanol, deionized water for ultrasonic processing 20min successively.After processing totally, use a large amount of deionized water rinsings, dry at 55 ℃, then the NaOH solution of the aluminium foil after cleaning being put into 1mol/L soaks, time is 0.5min, distilled water clean and and dry up with rubber pipette bulb after, under normal temperature with its surface of electrochemical process etching.
Etching condition: constant current (50mA/cm
2), temperature: 25 ℃, etch period: 3min, etching liquid: 1mol/LHCl+0.5mol/LH
2sO
4mixed solution, basis material: the aluminium foil of processing, to electrode adopt stainless steel.
(2) graphene oxide suspension: graphite oxide is added to deionized water, and being configured to concentration is the ultrasonic 0.5h of graphite oxide solution of 0.25mg/ml, obtains homodisperse graphene oxide suspension.Then slowly add the NaOH solution of 0.1mol/L to regulate pH to 10.
(3) graphene suspension: in graphene oxide suspension, add hydrazine hydrate (mass concentration of hydrazine hydrate is 85%) (wherein mass ratio RN
2h
4/ GO=1:10) solution, at the temperature of 100 ℃, react 12h, obtain graphene suspension.
(4) preparation of collector: in the graphene suspension in (3), adding concentration is the Mg (NO of 0.25mg/ml
3)
26H
2o solution, wherein the mass ratio of Graphene and slaine is (1:1) ultrasonic 15min, obtain uniform electrolyte, using the aluminium foil in above-mentioned 1 as electrode, its Parallel Symmetric is placed in electrolyte, add the direct current of 40V at the two ends of electrode, two die openings are 0.5cm, electrophoresis 5min, taken off, dry in the vacuum drying chamber of 100 ℃, then it is put into tube furnace again, pass into argon gas and drive the air in stove away, then pass into the mist of argon gas and hydrogen (5%), control the flow of gas at 50ml/min, with the heating rate of 5 ℃/min, slowly be warming up to 500 ℃, at this temperature, reduce 0.5h, just can obtain required collector.
Collector prepared by embodiment 1 is applied to lithium ion battery and carries out electro-chemical test.
Wherein, lithium ion battery is prepared by following steps: the ratio that is 92:3:5 according to mass ratio, LiFePO4, Kynoar binding agent and conductive black Super P are mixed, add suitable solvent to obtain slurry, then slurry is coated on collector prepared by embodiment 1, drying, roll film, trimming processing, make anode electrode sheet; The ratio that is 92:3:5 according to mass ratio, graphite, Kynoar binding agent and conductive black Super P are mixed, add suitable solvent to obtain slurry, then slurry is coated on collector prepared by embodiment 1, drying, roll film, trimming processing, make negative electricity pole piece.In glove box by both positive and negative polarity electrode slice, barrier film and electrolyte are assembled into button cell according to cell making process, its septation is celgard2000, electrolyte is the 1-ethyl-3-methylimidazole tetrafluoroborate of 0.5mol/L, assemble latter standing one day, utilized CHI660A electrochemical workstation to carry out constant current charge-discharge test to it.
In comparative example, the anodal aluminium foil that adopts of collector, negative pole adopts Copper Foil, and other are identical with the lithium ion battery of collector prepared by above-mentioned use embodiment 1.
Test result is as follows:
| Test event | Embodiment 1 | Comparative example |
| Internal resistance (m Ω) | 11 | 18 |
| Power density (kw/kg) | 2.2 | 2.0 |
| Capability retention (after 1200 circulations) | 95% | 90% |
| Pole piece peel strength (180 °) (N) | 2.7 | 1.5 |
As can be seen from the above table, the collector lithium ion battery that uses embodiment 1 to prepare is lower than using the ion battery internal resistance of aluminium foil and Copper Foil, and the peel strength of power density and cycle performance and pole piece all increases.
Embodiment 2
Preparation technology's flow process of collector prepared by the present invention is as follows:
(1) preliminary treatment of aluminium foil: aluminium foil thick 10 μ m is placed in to acetone, ethanol, deionized water for ultrasonic processing 20min successively.After processing totally, use a large amount of deionized water rinsings, dry at 55 ℃, then the NaOH solution of the aluminium foil after cleaning being put into 1mol/L soaks, time is 0.5min, distilled water clean and and dry up with rubber pipette bulb after, under normal temperature with its surface of electrochemical process etching.
Etching condition: constant current (50mA/cm
2), temperature: 25 ℃, etch period: 0.5-3min, etching liquid: 1mol/LHCl+0.5mol/LH
2sO
4mixed solution, basis material: the aluminium foil of processing, to electrode adopt stainless steel.
(2) graphene oxide suspension: graphite oxide is added to deionized water, and being configured to concentration is the ultrasonic 0.5h of graphite oxide solution of 0.25mg/ml, obtains homodisperse graphene oxide suspension.Then slowly add the NaOH solution of 0.1mol/L to regulate pH to 10.
(3) graphene suspension: in graphene oxide suspension, add hydrazine hydrate (mass concentration of hydrazine hydrate is 85%) (wherein mass ratio RN
2h
4/ GO=1:10) solution, at the temperature of 100 ℃, react 12h, obtain graphene suspension.
(4) preparation of collector: in the graphene suspension in (3), adding concentration is the Mg (NO of 0.25mg/ml
3)
26H
2o solution, wherein the mass ratio of Graphene and slaine is (1:1) ultrasonic 15min, obtain uniform electrolyte, using the aluminium foil in above-mentioned 1 as electrode, its Parallel Symmetric is placed in electrolyte, add the direct current of 40V at the two ends of electrode, two die openings are 0.5cm, electrophoresis 5min, taken off, dry in the vacuum drying chamber of 100 ℃, then it is put into tube furnace again, pass into argon gas and drive the air in stove away, then pass into the mist of argon gas and hydrogen (5%), control the flow of gas at 50ml/min, with the heating rate of 5 ℃/min, slowly be warming up to 500 ℃, at this temperature, reduce 0.5h, just can obtain required collector.
Embodiment 3
Preparation technology's flow process of collector prepared by the present invention is as follows:
(1) preliminary treatment of aluminium foil: aluminium foil thick 18 μ m is placed in to acetone, ethanol, deionized water for ultrasonic processing 30min successively.After processing totally, use a large amount of deionized water rinsings, dry at 55 ℃, then the NaOH solution of the aluminium foil after cleaning being put into 2mol/L soaks, time is 3min, distilled water clean and and dry up with rubber pipette bulb after, under normal temperature with its surface of electrochemical process etching.
Etching condition: constant current (900mA/cm
2), temperature: 25 ℃, etch period: 3min, etching liquid: 2mol/LHCl+1mol/LH
2sO
4mixed solution, basis material: the aluminium foil of processing, to electrode adopt stainless steel.
(2) graphene oxide suspension: graphite oxide is added to deionized water (ethanol, isopropyl alcohol, n-butanol), and being configured to concentration is the ultrasonic 1h of graphite oxide solution of 1mg/ml, obtains homodisperse graphene oxide suspension.Then slowly add the alkaline solution such as NaOH solution or ammonia spirit or potassium hydroxide of 0.1mol/L to regulate pH to 11.
(3) graphene suspension: in graphene oxide suspension, add hydrazine hydrate (mass concentration of hydrazine hydrate is 85%) (wherein mass ratio RN
2h
4/ GO=1:10) solution, at the temperature of 100 ℃, react 24h, obtain graphene suspension.
(4) preparation of collector: in the graphene suspension in (3), adding concentration is the Fe (NO of 2mg/ml
3)
39H
2o solution, wherein the mass ratio of Graphene and slaine is (1:2), ultrasonic 15min, obtain uniform electrolyte, using the aluminium foil in above-mentioned 1 as electrode, its Parallel Symmetric is placed in electrolyte, add the direct current of 40V at the two ends of electrode, two die openings are 1cm, electrophoresis 20min, taken off, dry in the vacuum drying chamber of 100 ℃, then it is put into tube furnace again, pass into argon gas and drive the air in stove away, then pass into the mist of argon gas and hydrogen (5%), control the flow of gas at 70ml/min, with the heating rate of 10 ℃/min, slowly be warming up to 500 ℃, at this temperature, reduce 0.5h, obtain required collector.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a preparation method for collector, is characterized in that, comprises the steps:
Using aluminium foil as work electrode, and electrode and reference electrode composition three-electrode system is placed in to etching liquid, at 50mA/cm
2~ 900mA/cm
2current density under to described aluminium foil etching 0.5 minute ~ 30 minutes, described etching liquid contains hydrochloric acid and sulfuric acid, the concentration of described hydrochloric acid is 1mol/L ~ 2mol/L, the concentration of described sulfuric acid is 0.5mol/L ~ 1mol/L;
Graphite oxide is added in solvent, be mixed with graphite oxide suspension, by the ultrasonic dispersion of described graphite oxide suspension, obtain homodisperse graphene oxide suspension;
The pH value that regulates described graphene oxide suspension is 10 ~ 11;
After described graphene oxide suspension is mixed with hydrazine hydrate, at 80 ℃ ~ 120 ℃, react 12 hours ~ 24 hours, obtain graphene suspension;
In described graphene suspension, add metal salt solution, and ultrasonic dispersion obtains electrolyte;
Be placed in described electrolyte two aluminium foils through over etching as electrode, under the voltage of 40V ~ 80V, electrophoresis 5min ~ 20min; And
Under the atmosphere of reducibility gas, will be warming up to 500 ℃ ~ 1000 ℃ as the aluminium foil of negative electrode, reduction is processed and within 0.5 hour ~ 2 hours, is obtained collector.
2. the preparation method of collector according to claim 1, is characterized in that, described aluminium foil was first put into aluminium foil in the sodium hydroxide solution that concentration is 1mol/L ~ 2mol/L and soaked 0.5 minute ~ 3 minutes before carrying out etching, then cleans, dry.
3. the preparation method of collector according to claim 1, it is characterized in that, when preparation graphite oxide suspension, described solvent is at least one in deionized water, ethanol, isopropyl alcohol and n-butanol, and the concentration of described graphite oxide is 0.25mg/ml ~ 1mg/ml.
4. the preparation method of collector according to claim 1, it is characterized in that, working concentration is the pH value that the alkaline solution of 0.05mol/L ~ 1.5mol/L regulates described graphene oxide suspension, and described alkaline solution is sodium hydroxide solution, potassium hydroxide solution or ammoniacal liquor.
5. the preparation method of collector according to claim 1, is characterized in that, while preparing graphene suspension, the mass ratio of described hydrazine hydrate and described graphene oxide is 1:10 ~ 7:10.
6. the preparation method of collector according to claim 1, is characterized in that, the slaine in described metal salt solution is selected from Mg (NO
3)
26H
2o, Mg (SO
4)
27H
2o, Fe (NO
3)
39H
2o and Zn (NO
3)
26H
2at least one in O.
7. the preparation method of collector according to claim 1, is characterized in that, the concentration of described metal salt solution is 0.25mg/ml ~ 2mg/ml.
8. the preparation method of collector according to claim 1, is characterized in that, the Graphene in described electrolyte and the mass ratio of slaine are 1:1 ~ 1:2.
9. the preparation method of collector according to claim 1, is characterized in that, described reducibility gas is the mist of hydrogen and argon gas, and the volumn concentration of wherein said hydrogen is 5% ~ 10%.
10. the preparation method of collector according to claim 1, is characterized in that, the aluminium foil as negative electrode is warming up to 500 ℃ ~ 1000 ℃ with the heating rate of 5 ℃/min ~ 10 ℃/min.
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| CN113097493A (en) * | 2021-03-31 | 2021-07-09 | 珠海冠宇电池股份有限公司 | Preparation method of composite current collector and lithium ion battery |
| CN114464815A (en) * | 2022-03-11 | 2022-05-10 | 广汽埃安新能源汽车有限公司 | Metal foil, preparation method thereof and metal current collector |
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| CN105714360A (en) * | 2014-12-04 | 2016-06-29 | 中国科学院宁波材料技术与工程研究所 | Alkaline graphene-nickel electroplating liquid, and preparation method and application thereof |
| CN105714360B (en) * | 2014-12-04 | 2017-12-29 | 中国科学院宁波材料技术与工程研究所 | Alkaline graphene nickel plating solution, its preparation method and application |
| CN105931861A (en) * | 2016-06-14 | 2016-09-07 | 南京工程学院 | Preparation method for supercapacitor electrode coated with active electrode membrane |
| CN105931861B (en) * | 2016-06-14 | 2018-04-03 | 南京工程学院 | A kind of preparation method for the electrode of super capacitor for being covered with active electrode film |
| CN108172838A (en) * | 2018-01-03 | 2018-06-15 | 河南工学院 | A kind of preparation method and application of graphene coating copper foil current collector |
| CN108550787A (en) * | 2018-04-26 | 2018-09-18 | 北京石墨烯研究院 | Lithium ion cell positive and lithium ion battery comprising it |
| CN110117810A (en) * | 2019-06-10 | 2019-08-13 | 广西师范大学 | A kind of method that electrophoresis prepares modified graphene oxide aluminium composite heat conducting material |
| CN110117810B (en) * | 2019-06-10 | 2021-03-30 | 广西师范大学 | Method for preparing modified graphene oxide aluminum composite heat conduction material through electrophoresis |
| CN111155161A (en) * | 2019-12-31 | 2020-05-15 | 新疆烯金石墨烯科技有限公司 | Graphene-aluminum composite material and preparation method thereof |
| CN113097493A (en) * | 2021-03-31 | 2021-07-09 | 珠海冠宇电池股份有限公司 | Preparation method of composite current collector and lithium ion battery |
| CN113097493B (en) * | 2021-03-31 | 2023-03-14 | 珠海冠宇电池股份有限公司 | Preparation method of composite current collector and lithium ion battery |
| CN114464815A (en) * | 2022-03-11 | 2022-05-10 | 广汽埃安新能源汽车有限公司 | Metal foil, preparation method thereof and metal current collector |
| CN114464815B (en) * | 2022-03-11 | 2024-03-26 | 广汽埃安新能源汽车有限公司 | Metal foil, preparation method thereof and metal current collector |
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