CN103633334A - Graphene/aluminum foil composite current collector, preparation method thereof, electrochemical electrode and electrochemical cell or capacitor - Google Patents

Graphene/aluminum foil composite current collector, preparation method thereof, electrochemical electrode and electrochemical cell or capacitor Download PDF

Info

Publication number
CN103633334A
CN103633334A CN201210305300.1A CN201210305300A CN103633334A CN 103633334 A CN103633334 A CN 103633334A CN 201210305300 A CN201210305300 A CN 201210305300A CN 103633334 A CN103633334 A CN 103633334A
Authority
CN
China
Prior art keywords
graphene
current collector
composite current
preparation
paper tinsel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201210305300.1A
Other languages
Chinese (zh)
Inventor
周明杰
王要兵
吴凤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
Original Assignee
Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Oceans King Lighting Science and Technology Co Ltd, Shenzhen Oceans King Lighting Engineering Co Ltd filed Critical Oceans King Lighting Science and Technology Co Ltd
Priority to CN201210305300.1A priority Critical patent/CN103633334A/en
Publication of CN103633334A publication Critical patent/CN103633334A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • 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
    • 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 graphene/aluminum foil composite current collector and a preparation method thereof. The preparation method comprises steps of: adding graphite oxide into a solvent and performing ultrasonic dispersion to obtain a graphene oxide suspension; adjusting the pH value to 10-11, adding a hydrazine hydrate solution, reacting at 80-120 DEG C for 12-24 h, and performing suction filtration to obtain graphene; adding the graphene into an organic solvent to obtain a graphene suspension; coating an aluminum foil with the graphene suspension, rolling with a double-roller for a plurality of times after the aluminum foil is dried, dipping in the organic solvent for 10-60 min, and then continuously rolling with the double-roller for a plurality of times to obtain the graphene/aluminum foil composite current collector. The technology of the preparation method is simple. The graphene/aluminum foil composite current collector has little contact internal resistance with a cell active material, and the graphene can protect the aluminum foil from being corroded by an electrolyte, thus prolonging the cycle lifetime of an energy storage device. The invention also provides an electrochemical electrode, and an electrochemical cell or a capacitor which adopts the electrode.

Description

Graphene/aluminum paper tinsel composite current collector, its preparation method, electrochemical electrode and electrochemical cell or capacitor
Technical field
The present invention relates to the synthetic preparation field of new material, particularly relate to a kind of graphene/aluminum paper tinsel composite current collector and preparation method thereof and electrochemical electrode.The invention still further relates to a kind of electrochemical cell or capacitor.
Background technology
Collector is a kind of structure or part that collects electric current, major function is that the electric current that cell active materials is produced collects, electron channel is provided, accelerating electric charge shifts, improve and discharge and recharge a coulomb efficiency, as collector, need to meet the features such as conductivity is high, good mechanical property, quality is light, internal resistance is little.
Graphene is a kind of Two-dimensional Carbon atomic crystal of the discoveries such as the strong K sea nurse of the peace moral of Univ Manchester UK in 2004 (Andre K.Geim), because its unique structure and photoelectric property become the study hotspot in the fields such as material with carbon element, nanometer technology, Condensed Matter Physics and functional material, many scientific workers have been attracted.Graphene has good conduction, heat conductivility and low thermal coefficient of expansion, can be used for electrode material, composite material etc.
At present, lithium ion cell positive collector generally adopts aluminium foil, and negative current collector adopts the metal collector such as Copper Foil, and in charging process, metal collector directly contacts electrolyte, and therefore, corrosion phenomenon more easily occurs both positive and negative polarity collector; In addition, metal collector and active material adhere to not firm, and interface is difficult to combine closely, and has affected the utilance of electrode material and has increased contact resistance; In addition, can there is embedding lithium with aluminium foil and react in lithium ion, destroys aluminium foil, thereby cause collector stability and life-span to be reduced.The method of at present more conventional this phenomenon of solution is to reduce contact resistance in metal collector surface-coated conductive carbon layer, but still the generation that can not stop embedding lithium to react, and coated with conductive carbon-coating technical sophistication, cost is high, therefore, urgent need is sought a kind of being difficult for and is corroded, and has the collector of excellent compatibility with electrode active material.
Summary of the invention
For addressing the above problem, the present invention aims to provide a kind of graphene/aluminum paper tinsel composite current collector and preparation method thereof, the graphene/aluminum paper tinsel composite current collector that the method makes, with between battery active material to contact internal resistance little, thereby can reduce the internal resistance of electrochemical cell or capacitor, improve its power density, and Graphene can avoid aluminium foil directly to contact with electrolyte, thereby improve cyclical stability and the life-span of electrochemical cell or capacitor.The present invention is also corresponding provides a kind of electrochemical electrode, and a kind of electrochemical cell or capacitor that uses this electrode.
First aspect, the invention provides a kind of preparation method of graphene/aluminum paper tinsel composite current collector, comprises the following steps:
Get graphite oxide, join in solvent, after ultrasonic dispersion 0.5 ~ 1h, obtain graphene oxide suspension, the pH value of described graphene oxide suspension is adjusted to 10 ~ 11, add hydrazine hydrate solution, at 80 ~ 120 ℃ of temperature, react 12 ~ 24 hours, suction filtration, obtains Graphene, described Graphene is joined in organic solvent, obtain graphene suspension;
Described graphene suspension is coated on the aluminium foil of processing through cleaning-drying, dry after 1 ~ 12 hour at 60 ~ 100 ℃, repeatedly pair roller compacting, soaks after 10 ~ 60min with described organic solvent, continue again repeatedly pair roller compacting, obtain graphene/aluminum paper tinsel composite current collector.
Preferably, the thickness of aluminium foil is 5 ~ 50 μ m; More preferably, the thickness of aluminium foil is 10 ~ 20 μ m.
Preferably, the cleaning-drying of aluminium foil is processed and is operating as: aluminium foil is placed in after acetone, ethanol, deionized water for ultrasonic processing 20 ~ 30min successively, and dry at 55 ℃, then soak 0.5 ~ 3min, vacuumize, starvation with the acetum of 0.1mol/L.
Aluminium foil is carried out to acid and clean, remove after oxide layer, aluminium foil, by forming more coarse surface, is conducive to the compacting of follow-up Graphene like this.
Preferably, solvent is deionized water, ethanol, isopropyl alcohol or n-butanol.
Preferably, the concentration of graphene oxide suspension is 0.25 ~ 1mg/mL.
Preferably, organic solvent is dimethyl sulfoxide (DMSO) (DMSO), DMF (DMF), DMA (DMAc), 1-METHYLPYRROLIDONE (NMP).
Preferably, organic solvent accounts for 10 ~ 30% of described graphene suspension gross mass.
Wherein, the pH value of graphene oxide suspension is adjusted to 10 ~ 11, can adopts the sodium hydroxide solution, ammonia spirit or the potassium hydroxide solution that slowly add 0.1mol/L to realize.
Adding of hydrazine hydrate solution, graphene oxide can be reduced into Graphene.
Preferably, with N 2h 4quality meter, the mass concentration of described hydrazine hydrate solution is 85%, described hydrazine hydrate solution is pressed N 2h 4with the mass ratio of described graphite oxide be that 1 ~ 7:10 adds.
After reduction reaction, in the reactant liquor obtaining, contain the complete hydrazine hydrate of unreacted, suction filtration operation can be removed, and obtains Graphene.The Graphene of gained after suction filtration is joined in organic solvent, just obtain graphene suspension.
Graphene suspension is coated on aluminium foil, at 60 ~ 100 ℃, is dried 1 ~ 12 hour, it is dry that graphene suspension obtains part, repeatedly pair roller compacting, then soak after 10 ~ 60min with organic solvent, then continue repeatedly pair roller and suppress.Wherein, after pair roller compacting repeatedly, then soak 10 ~ 60min with organic solvent, pair roller compacting repeatedly again, organic solvent soaks Main Function and has been into and turns use into, and the molecular structure in solvation relief graphene layer is further adjusted, to obtain the more graphene layer of rock-steady structure.Repeatedly pair roller pressing operation, can make Graphene and aluminium foil have better combination, thereby effectively prevents the generation of dry linting phenomenon.The number of times of described pair roller compacting is not limit, and can be applicable to as required the compacting of number of times, preferably, suppresses 2 ~ 3 times.
At roll squeezer, carry out in the operating process of pair roller compacting, the surface that part Graphene particle is pressed into aluminium foil by mechanical pressure by force finally forms graphene layer, and another part is pressed in the internal structure of aluminium foil, is uniformly distributed in aluminium foil inside.So just, obtain having the graphene/aluminum paper tinsel composite current collector of composite construction, in this graphene/aluminum paper tinsel composite current collector, the combination between Graphene and aluminium foil is tight, has larger peel strength, is difficult for producing dry linting phenomenon.Conventionally binding agent add the reduction that membership causes collector conductivity, in the present invention, between Graphene and aluminium foil, do not use binding agent, and Graphene has high conductivity, so this graphene/aluminum paper tinsel composite current collector has stronger electric conductivity.Like this, Graphene can strengthen the compatibility of collector and electrode active material as conductive layer, reduces the interface contact resistance of collector and electrode active material, thereby reduces the internal resistance of electrochemical cell or capacitor, effectively improves its power density.Simultaneously, graphene layer also can stop the corrosion of electrolyte to aluminium foil, thereby extends the useful life of electrochemical cell or capacitor, for lithium ion battery, can effectively stop lithium ion to embed aluminium foil from active material layer, thereby improve cyclical stability and the life-span of lithium ion battery.
Second aspect, the invention provides a kind of graphene/aluminum paper tinsel composite current collector being prepared by above-mentioned preparation method.
The third aspect, the invention provides a kind of electrochemical electrode, this electrochemical electrode comprises the described graphene/aluminum paper tinsel composite current collector that second aspect present invention provides, and the electrode material of preparation on this graphene/aluminum paper tinsel composite current collector, this electrode material comprises that mass ratio is LiFePO4, Kynoar binding agent and the conductive black Super P of 92:3:5.
Fourth aspect, the invention provides a kind of electrochemical cell or capacitor, the described electrochemical electrode that the electrode of this electrochemical cell or capacitor adopts third aspect present invention to provide.
The present invention also provides the application in the negative or positive electrode collector of lithium ion battery and ultracapacitor of graphene/aluminum paper tinsel composite current collector that said method makes.
Graphene/aluminum paper tinsel composite current collector provided by the invention and preparation method thereof, has following beneficial effect:
(1) the present invention is suppressed and is used the method for mechanical pressure to make graphene/aluminum paper tinsel composite current collector by pair roller, and preparation technology is simple, and cost is low, is easy to realize large-scale industrial and produces;
(2) the graphene/aluminum paper tinsel composite current collector making by preparation method of the present invention, Graphene is combined with aluminium foil closely, and between Graphene and aluminium foil, do not use binding agent, dry linting not, Graphene has strengthened the compatibility of collector and battery active material as conductive layer, reduce the interface contact resistance of collector and active material, thereby reduced the internal resistance of electrochemical cell or capacitor, effectively improved its power density;
(3) Graphene can stop the corrosion of electrolyte to aluminium foil, thereby extends the useful life of electrochemical cell or capacitor.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the prepared graphene/aluminum paper tinsel of the embodiment of the present invention one composite current collector.
Embodiment
The following stated is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Embodiment mono-
A preparation method for graphene/aluminum paper tinsel composite current collector, comprises the following steps:
(1) providing thickness is the aluminium foil of 10 μ m, aluminium foil is removed to surface and oil contaminant for 20 minutes through acetone, ethanol, deionized water ultrasonic cleaning respectively, and then the acetum that is 0.1mol/L by concentration soaks 3 minutes removal oxide on surface, vacuumize, starvation;
(2) get graphite oxide, join in deionized water, ultrasonic dispersion 0.5h, obtaining concentration is the graphene oxide suspension of 0.25mg/mL, then slowly adds the sodium hydroxide solution of 0.1mol/L to regulate PH to 10, subsequently, adds hydrazine hydrate solution (with N 2h 4quality meter, mass concentration is 85%), at 100 ℃ of temperature, reacting 12 hours, suction filtration, obtains Graphene, and described Graphene is joined in DMSO, obtains graphene suspension;
Wherein, hydrazine hydrate solution is pressed N 2h 4with the mass ratio of graphite oxide be that 1:10 adds; DMSO solvent accounts for 10% of described graphene suspension gross mass;
(3) graphene suspension is coated on aluminium foil, dry after 12 hours at 60 ℃, pair roller compacting 3 times, soaks after 10min with DMSO, then pair roller compacting 3 times, obtains graphene/aluminum paper tinsel composite current collector.
Fig. 1 is the SEM figure of the prepared graphene/aluminum paper tinsel of the embodiment of the present invention one composite current collector.As can be seen from Figure 1, Graphene is successfully prepared at aluminium foil surface.
The preparation of electrochemical electrode
Take 9.2g LiFePO4,0.5g conductive black Super P and 0.3g PVDF, and add 20g NMP, fully stir and make it to become the slurry mixing.Then, on the doped with boron graphene/aluminum paper tinsel composite current collector its blade coating being made in the present embodiment cleaning through ethanol, under the vacuum of 0.01MPa, 80 ℃ are dried to constant weight, and are pressed into iron phosphate lithium electrode in 10 ~ 15MPa pressure lower roll, and are cut into positive plate.Equally, take 4.6g graphite, 0.25g conductive black Super P and 0.15g PVDF, and add 10g NMP, fully stir and make it to become the slurry mixing, then, on the doped with boron graphene/aluminum paper tinsel composite current collector its blade coating being made in the present embodiment cleaning through ethanol, be pressed into negative plate.
The preparation of electrochemical cell
By above-mentioned positive plate, celgard2000 barrier film, above-mentioned negative plate in order stack of laminations dress up battery core, use again battery housing seal battery core, toward the 1-ethyl-3-methylimidazole tetrafluoro boric acid electrolyzed saline solution liquid that injects 0.5mol/L in battery container, sealing liquid injection port, obtains lithium ion battery.
With CHI660A electrochemical workstation, the lithium ion battery assembling in the present embodiment is carried out to constant current charge-discharge test, the internal resistance that records this lithium ion battery is 10m Ω, power density is 3.2kw/kg, carry out after 1200 charge and discharge cycles, capability retention is 96%, and 180 ° of peel strengths that record electrode slice with peel strength tester are 2.8N.
Embodiment bis-
A preparation method for graphene/aluminum paper tinsel composite current collector, comprises the following steps:
(1) providing thickness is the aluminium foil of 15 μ m, aluminium foil is removed to surface and oil contaminant for 30 minutes through acetone, ethanol, deionized water ultrasonic cleaning respectively, and then the acetum that is 0.1mol/L by concentration soaks 0.5 minute removal oxide on surface, vacuumize, starvation;
(2) get graphite oxide, join in ethanol, ultrasonic dispersion 0.5h, obtaining concentration is the graphene oxide suspension of 1mg/mL, then slowly adds the ammonia spirit of 0.1mol/L to regulate PH to 11, subsequently, adds hydrazine hydrate solution (with N 2h 4quality meter, mass concentration is 85%), at 90 ℃ of temperature, reacting 18 hours, suction filtration, obtains Graphene, and described Graphene is joined in 1-METHYLPYRROLIDONE (NMP), obtains graphene suspension;
Wherein, hydrazine hydrate solution is pressed N 2h 4with the mass ratio of graphite oxide be that 5:10 adds; Nmp solvent accounts for 20% of described graphene suspension gross mass;
(3) graphene suspension is coated on aluminium foil, dry after 6 hours at 80 ℃, pair roller compacting 2 times, soaks after 10min with NMP, then pair roller compacting 2 times, obtains graphene/aluminum paper tinsel composite current collector.
The present embodiment gained graphene/aluminum paper tinsel composite current collector is prepared into electrochemical electrode according to the method for embodiment mono-, and be assembled into lithium ion battery, with CHI660A electrochemical workstation, the lithium ion battery assembling in the present embodiment is carried out to constant current charge-discharge test, the internal resistance that records this lithium ion battery is 2m Ω, power density is 11kw/kg, carry out after 1200 charge and discharge cycles, capability retention is 90%.180 ° of peel strengths that record electrode slice with peel strength tester are 6N.
Embodiment tri-
A preparation method for graphene/aluminum paper tinsel composite current collector, comprises the following steps:
(1) providing thickness is the aluminium foil of 20 μ m, aluminium foil is removed to surface and oil contaminant for 20 minutes through acetone, ethanol, deionized water ultrasonic cleaning respectively, and then the acetum that is 0.1mol/L by concentration soaks 2 minutes removal oxide on surface, vacuumize, starvation;
(2) get graphite oxide, join in n-butanol, ultrasonic dispersion 1h, obtaining concentration is the graphene oxide suspension of 0.5mg/mL, then slowly adds the potassium hydroxide solution of 0.1mol/L to regulate PH to 11, subsequently, adds hydrazine hydrate solution (with N 2h 4quality meter, mass concentration is 85%), at 80 ℃ of temperature, reacting 24 hours, suction filtration, obtains Graphene, and described Graphene is joined in DMF (DMF), obtains graphene suspension;
Wherein, hydrazine hydrate solution is pressed N 2h 4with the mass ratio of graphite oxide be that 7:10 adds; DMF solvent accounts for 30% of described graphene suspension gross mass;
(3) graphene suspension is coated on aluminium foil, dry after 1 hour at 100 ℃, pair roller compacting 2 times, soaks after 60min with DMF, then pair roller compacting 2 times, obtains graphene/aluminum paper tinsel composite current collector.
The present embodiment gained graphene/aluminum paper tinsel composite current collector is prepared into electrochemical electrode according to the method for embodiment mono-, and be assembled into lithium ion battery, with CHI660A electrochemical workstation, the lithium ion battery assembling in the present embodiment is carried out to constant current charge-discharge test, the internal resistance that records this lithium ion battery is 2.8m Ω, power density is 8kw/kg, carry out after 1200 charge and discharge cycles, capability retention is 93%.180 ° of peel strengths that record electrode slice with peel strength tester are 8N.
Embodiment tetra-
A preparation method for graphene/aluminum paper tinsel composite current collector, comprises the following steps:
(1) providing thickness is the aluminium foil of 50 μ m, aluminium foil is removed to surface and oil contaminant for 30 minutes through acetone, ethanol, deionized water ultrasonic cleaning respectively, and then the acetum that is 0.1mol/L by concentration soaks 2 minutes removal oxide on surface, vacuumize, starvation;
(2) get graphite oxide, join in isopropyl alcohol, ultrasonic dispersion 1h, obtaining concentration is the graphene oxide suspension of 0.8mg/mL, then slowly adds the sodium hydroxide solution of 0.1mol/L to regulate PH to 10, subsequently, adds hydrazine hydrate solution (with N 2h 4quality meter, mass concentration is 85%), at 100 ℃ of temperature, reacting 12 hours, suction filtration, obtains Graphene, and described Graphene is joined in DMF (DMF), obtains graphene suspension;
Wherein, hydrazine hydrate solution is pressed N 2h 4with the mass ratio of graphite oxide be that 5:10 adds; DMF solvent accounts for 25% of described graphene suspension gross mass;
(3) graphene suspension is coated on aluminium foil, dry after 1 hour at 90 ℃, pair roller compacting 3 times, soaks after 40min with DMF, then pair roller compacting 3 times, obtains graphene/aluminum paper tinsel composite current collector.
The present embodiment gained graphene/aluminum paper tinsel composite current collector is prepared into electrochemical electrode according to the method for embodiment mono-, and be assembled into lithium ion battery, with CHI660A electrochemical workstation, the lithium ion battery assembling in the present embodiment is carried out to constant current charge-discharge test, the internal resistance that records this lithium ion battery is 4m Ω, power density is 5kw/kg, carry out after 1200 charge and discharge cycles, capability retention is 91%.180 ° of peel strengths that record electrode slice with peel strength tester are 4N.
The graphene/aluminum paper tinsel composite current collector making by preparation method of the present invention, the associativity of aluminium foil and Graphene is good, there is larger peel strength, be difficult for producing dry linting phenomenon, and between Graphene and aluminium foil, do not use binding agent, Graphene has strengthened the compatibility of collector and battery active material as conductive layer, has reduced the interface contact resistance of collector and active material, thereby reduced the internal resistance of electrochemical cell or capacitor, effectively improved its power density; Meanwhile, graphene layer can stop the corrosion of electrolyte to aluminium foil, thereby extends the useful life of electrochemical cell or capacitor.The lithium ion battery that uses this graphene/aluminum paper tinsel composite current collector simultaneously to make as anodal and negative current collector, the capability retention after 1200 times that circulates reaches more than 90%.
Comparative example:
Take 9.2g LiFePO4,0.5g conductive black Super P and 0.3g PVDF, and add 20g NMP, fully stir and make it to become the slurry mixing.Then by its blade coating in the normal aluminium foil of cleaning through ethanol, under the vacuum of 0.01MPa, 80 ℃ are dried to constant weight, and are pressed into iron phosphate lithium electrode in 10 ~ 15MPa pressure lower roll, and are cut into anodal disk.Equally, take 4.6g graphite, 0.25g conductive black Super P and 0.15g PVDF, and add 10g NMP, fully stir and make it to become the slurry mixing, then by its blade coating on the common Copper Foil cleaning through ethanol, be pressed into negative plate.By positive plate, celgard2000 barrier film, negative plate in order stack of laminations dress up battery core, use again battery housing seal battery core, toward the 1-ethyl-3-methylimidazole tetrafluoro boric acid electrolyzed saline solution liquid that injects 0.5mol/L in battery container, sealing liquid injection port, obtains lithium ion battery.
After testing, this comparative example's gained lithium ion battery internal resistance is 18m Ω, and power density is 2.0kw/kg, carries out after 1200 charge and discharge cycles, and capability retention is 90%, and 180 ° of peel strengths of electrode slice are 1.5N.
As can be seen here, compare with comparative example, the graphene/aluminum paper tinsel composite current collector that the embodiment of the present invention one makes, because surface has Graphene, positive pole using it as lithium ion battery and negative current collector, Graphene has strengthened the compatibility of collector and battery active material as conductive layer, reduced the interface contact resistance of collector and active material, thereby reduced the internal resistance of lithium ion battery, improved its power density, graphene layer can also stop that aluminium foil contacts with electrolyte, thereby improves cyclical stability and the life-span of lithium ion battery.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.

Claims (10)

1. a preparation method for graphene/aluminum paper tinsel composite current collector, is characterized in that, comprises the following steps:
Get graphite oxide, join in solvent, after ultrasonic dispersion 0.5 ~ 1h, obtain graphene oxide suspension, the pH value of described graphene oxide suspension is adjusted to 10 ~ 11, add hydrazine hydrate solution, at 80 ~ 120 ℃ of temperature, react 12 ~ 24 hours, suction filtration, obtains Graphene, described Graphene is joined in organic solvent, obtain graphene suspension;
Described graphene suspension is coated on the aluminium foil of processing through cleaning-drying, dry after 1 ~ 12 hour at 60 ~ 100 ℃, repeatedly pair roller compacting, soaks after 10 ~ 60min with described organic solvent, continue again repeatedly pair roller compacting, obtain graphene/aluminum paper tinsel composite current collector.
2. the preparation method of graphene/aluminum paper tinsel composite current collector as claimed in claim 1, is characterized in that, the thickness of described aluminium foil is 5 ~ 50 μ m.
3. the preparation method of graphene/aluminum paper tinsel composite current collector as claimed in claim 1, it is characterized in that, the cleaning-drying of described aluminium foil is processed and is operating as: aluminium foil is placed in after acetone, ethanol, deionized water for ultrasonic processing 20 ~ 30min successively, dry at 55 ℃, with the acetum of 0.1mol/L, soak 0.5 ~ 3min again, vacuumize, starvation.
4. the preparation method of graphene/aluminum paper tinsel composite current collector as claimed in claim 1, is characterized in that, described solvent is deionized water, ethanol, isopropyl alcohol or n-butanol, and the concentration of described graphene oxide suspension is 0.25 ~ 1mg/mL.
5. the preparation method of graphene/aluminum paper tinsel composite current collector as claimed in claim 1, is characterized in that, described organic solvent is dimethyl sulfoxide (DMSO), DMF, DMA or 1-METHYLPYRROLIDONE.
6. the preparation method of graphene/aluminum paper tinsel composite current collector as claimed in claim 1, is characterized in that, described organic solvent accounts for 10 ~ 30% of described graphene suspension gross mass.
7. the preparation method of graphene/aluminum paper tinsel composite current collector as claimed in claim 1, is characterized in that, with N 2h 4quality meter, the mass concentration of described hydrazine hydrate solution is 85%, described hydrazine hydrate solution is pressed N 2h 4with the mass ratio of described graphite oxide be that 1 ~ 7:10 adds.
8. a graphene/aluminum paper tinsel composite current collector, is characterized in that, this collector is made by the arbitrary described preparation method of claim 1 to 7.
9. an electrochemical electrode, it is characterized in that, this electrochemical electrode comprises graphene/aluminum paper tinsel composite current collector claimed in claim 8, and the electrode material of preparation on this graphene/aluminum paper tinsel composite current collector, this electrode material comprises that mass ratio is LiFePO4, Kynoar binding agent and the conductive black Super P of 92:3:5.
10. electrochemical cell or a capacitor, is characterized in that, the electrode of this electrochemical cell or capacitor adopts electrochemical electrode claimed in claim 9.
CN201210305300.1A 2012-08-24 2012-08-24 Graphene/aluminum foil composite current collector, preparation method thereof, electrochemical electrode and electrochemical cell or capacitor Pending CN103633334A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210305300.1A CN103633334A (en) 2012-08-24 2012-08-24 Graphene/aluminum foil composite current collector, preparation method thereof, electrochemical electrode and electrochemical cell or capacitor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210305300.1A CN103633334A (en) 2012-08-24 2012-08-24 Graphene/aluminum foil composite current collector, preparation method thereof, electrochemical electrode and electrochemical cell or capacitor

Publications (1)

Publication Number Publication Date
CN103633334A true CN103633334A (en) 2014-03-12

Family

ID=50214123

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210305300.1A Pending CN103633334A (en) 2012-08-24 2012-08-24 Graphene/aluminum foil composite current collector, preparation method thereof, electrochemical electrode and electrochemical cell or capacitor

Country Status (1)

Country Link
CN (1) CN103633334A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106876716A (en) * 2017-03-14 2017-06-20 中国人民解放军63971部队 A kind of metal/carbon composite current collector material and preparation method thereof
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
CN108808001A (en) * 2018-06-11 2018-11-13 四会市恒星智能科技有限公司 A kind of multiple elements design conductive layer and preparation method thereof
CN112599780A (en) * 2020-12-14 2021-04-02 中国科学院过程工程研究所 Method for modifying surface of current collector of lithium slurry battery

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090325071A1 (en) * 2008-05-20 2009-12-31 Gm Global Technology Operations, Inc. Intercalation Electrode Based on Ordered Graphene Planes
CN102024941A (en) * 2010-11-06 2011-04-20 合肥国轩高科动力能源有限公司 Surface treatment method of negative current collector copper foil of lithium ion battery
CN102208598A (en) * 2011-05-12 2011-10-05 中国科学院宁波材料技术与工程研究所 Electrode plate of graphene coating modified lithium secondary battery and manufacturing method thereof
CN102610793A (en) * 2011-01-25 2012-07-25 海洋王照明科技股份有限公司 Nitride substituted graphene oxide electrode and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090325071A1 (en) * 2008-05-20 2009-12-31 Gm Global Technology Operations, Inc. Intercalation Electrode Based on Ordered Graphene Planes
CN102024941A (en) * 2010-11-06 2011-04-20 合肥国轩高科动力能源有限公司 Surface treatment method of negative current collector copper foil of lithium ion battery
CN102610793A (en) * 2011-01-25 2012-07-25 海洋王照明科技股份有限公司 Nitride substituted graphene oxide electrode and preparation method thereof
CN102208598A (en) * 2011-05-12 2011-10-05 中国科学院宁波材料技术与工程研究所 Electrode plate of graphene coating modified lithium secondary battery and manufacturing method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106876716A (en) * 2017-03-14 2017-06-20 中国人民解放军63971部队 A kind of metal/carbon composite current collector material and preparation method thereof
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
CN108808001A (en) * 2018-06-11 2018-11-13 四会市恒星智能科技有限公司 A kind of multiple elements design conductive layer and preparation method thereof
CN112599780A (en) * 2020-12-14 2021-04-02 中国科学院过程工程研究所 Method for modifying surface of current collector of lithium slurry battery

Similar Documents

Publication Publication Date Title
CN103633333A (en) Nitrogen-doped or boron-doped graphene/aluminum foil composite current collector, preparation method thereof, electrochemical electrode and electrochemical cell or capacitor
CN108258323B (en) A kind of production method of high specific energy solid lithium battery
CN103632845A (en) Graphene/organic thin film composite current collector, preparation method thereof, electrochemical electrode and electrochemical battery or capacitor
CN103839694B (en) A kind of preparation method of Graphene/metal collector
CN105655592A (en) Silicon-based negative electrode of lithium ion battery and method for preparing silicon-based negative electrode of lithium ion battery
CN102544502A (en) Anode and cathode conductive additive for secondary lithium battery, method for preparing conductive additive, and method for preparing secondary lithium battery
CN109713269B (en) Preparation method of polyene/S composite positive electrode material for lithium-sulfur battery
CN104795559A (en) High-energy-density lithium-ion battery
CN103000390B (en) A kind of negative pole currect collecting preparation and use the ultracapacitor of this collector
CN103515119A (en) Positive electrode current collector and preparation method and application of positive electrode current collector
CN108400292B (en) Preparation method and application of bismuth elementary substance nanosheet composite electrode
CN103579630A (en) Preparation method for aluminum foil current collector and application
CN109273694A (en) A kind of graphene/stannous oxide two-dimensional hetero-junction composite material and preparation method
CN103779569A (en) Lithium ion battery anode sheet and preparation method thereof
CN105226274A (en) A kind of preparation method of LiFePO4/graphene composite material of graphene uniform dispersion
CN112652757B (en) Modified silicon-carbon negative electrode material and preparation method and application thereof
CN103779084A (en) Anode current collector and preparation method and application thereof
CN105293467A (en) Phenolic resin/coal tar pitch composite-base modified hard carbon negative electrode material and preparation method and application thereof
CN103545491A (en) Preparation method of graphene/titanium dioxide composite material for lithium ion battery cathode material
CN103633334A (en) Graphene/aluminum foil composite current collector, preparation method thereof, electrochemical electrode and electrochemical cell or capacitor
CN109802107B (en) Preparation method of polyalkenyl composite negative electrode material for sodium ion battery
CN104882631A (en) Method for improving uniform heat dispersion performance of lithium ion battery electrode piece
CN114256560A (en) Cellulose inorganic composite membrane, high-temperature-resistant battery diaphragm, and preparation method and application thereof
CN110391415A (en) A kind of positive electrode active materials and the Zinc ion battery including the positive electrode active materials
CN102299375B (en) Lithium ion power battery and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
EXSB Decision made by sipo to initiate substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20140312

WD01 Invention patent application deemed withdrawn after publication