CN105938907A - Preparation method of high-conductivity graphene current collector - Google Patents
Preparation method of high-conductivity graphene current collector Download PDFInfo
- Publication number
- CN105938907A CN105938907A CN201610365128.7A CN201610365128A CN105938907A CN 105938907 A CN105938907 A CN 105938907A CN 201610365128 A CN201610365128 A CN 201610365128A CN 105938907 A CN105938907 A CN 105938907A
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- Prior art keywords
- graphene
- current collector
- preparation
- collector
- vacuum
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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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- 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
-
- 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 discloses a preparation method of a high-conductivity graphene current collector. The method comprises the steps of directly taking graphene as the current collector, and ultrasonically dispersing graphene oxide firstly; carrying out suction filtration on ultrasonically dispersed graphene oxide dispersion liquid, controlling the thickness of a film in the suction filtration process, and then carrying out high-vacuum and high-temperature treatment to form a graphene film; and cutting the graphene film into slices along the direction vertical to the direction in which the graphene slices are stacked. The surface appearance of the obtained current collector is a fluctuating gully which is formed by staking the graphene slices. The specific surface area of the current collector is greatly improved; the adhesive force of the current collector and an active electrode material is improved; the resistance of a device is reduced; and the active electrode material is effectively prevented from falling off from the current collector.
Description
Technical field
The present invention relates to a kind of collector, particularly relate to the preparation method of a kind of high conductivity Graphene collector.
Background technology
Along with the progress of technology, the application of lithium ion battery is no longer limited to the numbers such as mobile phone, MP3, camera
Code product and small-sized electric tool, have spread over electric automobile and large-scale stored energy application.Power used for electric vehicle
The life requirements of battery is 3 years 100000 kilometers of distance travelleds, and energy-storage battery required especially up to more than 10 years
Service life.The factor affecting the lithium ion battery life-span is a lot, the conductive capability between positive and negative pole material and collector
It is exactly one of them with peel strength.Now, positive and negative pole material is to be applied directly onto ganoid afflux mostly
On body, the pole piece that this coating method makes, contacting not fully closely between material with collector, cause material
Peel strength between material and collector is relatively low, poorly conductive.The position that contact difference electric conductivity is bad, discharge and recharge
Journey overpotential is big, reduces energy output, adds battery-heating, and affects the service life of battery.
Currently in order to the contact resistance between raising components and parts, take to use the mode of machinery at aluminium foil at aluminium foil surface
Holes punched on surface, but still there is charge and discharge process and be susceptible to the serious phenomenon that active substance comes off.Another kind side
Method is to be re-used as collector at one layer of activated carbon of surface-coated of aluminium foil to use, but the method too increases technique stream
Journey and processing cost.Such as Chinese patent application CN105406083A, disclose a kind of anode composite collector,
Described anode composite collector is made up of plus plate current-collecting body matrix and the composite coating being coated in matrix surface, compound
Coating includes binding agent, conductive agent and additive, wherein conductive agent selected from white carbon black, CNT, carbon fiber,
At least one in Graphene.The method remains a need for coating one layer of material with carbon element on aluminium foil, Copper Foil, increases technique.
Summary of the invention
The invention aims to overcome deficiency of the prior art to provide a kind of high conductivity Graphene collection
The preparation method of fluid, graphene oxide directly using graphene film as collector, is first passed through ultrasonic by the present invention
Dispersion, carries out sucking filtration by the graphene oxide dispersion after ultrasonic, controls the thickness of film during sucking filtration, it
After again after condition of high vacuum degree, high-temperature process formed graphene film；And along being perpendicular to the side of graphene sheet layer stacking
Cutting into slices to graphene film, the surface topography of the collector obtained is that graphene sheet layer stacking forms height
The gully of volt；Substantially increase the specific surface area of collector, and improve the viscous of collector and active electrode material
Attached power, reduces the resistance of device, and is prevented effectively from electrode active material and comes off from collector.
The present invention is that the technical scheme realizing the employing of above-mentioned technology mesh is:
The preparation method of a kind of high conductivity Graphene collector, comprises the following steps:
Step (1): by graphene oxide ultrasonic disperse 4-7h, sucking filtration to thickness reaches more than 1cm, forms oxygen
Functionalized graphene film；
Step (2): the graphene oxide membrane described in step (1) is entered in the mixed atmosphere of hydrogen and argon
Row fine vacuum, high annealing reduce, and obtain graphene film；The volume ratio of described hydrogen and argon is 1:3-7；
The total flow of the mixed atmosphere of described hydrogen and argon is 10-30sccm；The vacuum of described fine vacuum is
50-80mTorr；Temperature 2500-3000 DEG C of described high annealing reduction；The time of described high annealing reduction
For 40-60min；Described heating rate is 1 DEG C/min-3 DEG C/min；
Step (3): carry out being naturally cooling to room temperature by the graphene film described in step (2), takes out；And edge
Graphene film is cut into slices by the direction being perpendicular to graphene sheet layer stacking, and slice thickness is 10-20 micron,
To Graphene collector；The surface topography of described Graphene collector is that graphene sheet layer stacking forms height fluctuating
Gully.
Entering of the preparation method of a kind of flexible High conductivity graphene CNT composite current collector that the present invention provides
The preferred version of one step is:
Wherein, the temperature of the high annealing reduction described in step (2) is preferably 2800-3000 DEG C, described intensification
Speed is preferably 1 DEG C/min-2 DEG C/min.The vacuum of step (2) described fine vacuum is preferably 50-60mTorr,
More preferably 50mTorr.The time of step (2) described high annealing reduction is preferably 50-60min.
Hydrogen and the volume ratio of argon described in step (2) are preferably 1:4-6；Described hydrogen and the gaseous mixture of argon
The total flow of atmosphere is preferably 20-30sccm.
Wherein, the time of the graphene oxide ultrasonic disperse described in step (1) is preferably 5-6h.Step (1)
Described graphene oxide uses hummers method to prepare.
The preparation method of a kind of Flexible graphene CNT composite current collector that the present invention provides, with prior art
That compares has the beneficial effect that:
(1) present invention by graphene film directly as collector, the present invention by the temperature of regulation and control high annealing,
The vacuum of high annealing and heating rate prepare the film of high conductivity；The present invention is by the temperature of high annealing
Regulation and control are to 2500-3000 DEG C, and vacuum regulates and controls to 50-80mTorr, and heating rate regulates and controls to 1-3 DEG C/min,
Especially being 2800-3000 DEG C when temperature, vacuum is 50mTorr, and heating rate is 1-2 DEG C/min, obtains
Graphene film in graphene sheet layer closely stack, electric conductivity significantly promotes.
(2) present invention take the direction along being perpendicular to graphene sheet layer stacking graphene film is cut into slices,
The surface topography of the Graphene collector obtained is that graphene film interlayer stacking forms the gully that height rises and falls；Significantly
Improve the specific surface area of collector.
(3) electric conductivity of the Graphene collector that the present invention prepares is up to 300000-500000S/m.Thin
The gully shape pattern on film surface is conducive to active substance and collector contact area are substantially improved, and increases adherence,
Reduce the resistance of device, and be prevented effectively from active substance and come off from collector.
Detailed description of the invention
Embodiment 1:
The preparation of graphene oxide: weigh 2g graphite powder and 1gNaNO3In round-bottomed flask, add 50mL
Concentrated sulphuric acid, ice bath stirring 5-8min；It is slowly added to 6gKMnO afterwards4；Remove ice bath, flask is placed in 35
0.5-1.5h is reacted at ± 5 DEG C；Adding 92mL deionized water afterwards, temperature is increased to 90 ± 5 DEG C, keeps 15min
Add 280mL warm water afterwards, after stirring 5min, add 30mLH2O2；It is centrifuged washing after stirring 12h
Wash, use deionized water and ethanol centrifuge washing three times respectively, carry out being vacuum dried 24h, i.e. obtain graphite oxide
Alkene.
The preparation method of Graphene collector:
Step (1): by graphene oxide ultrasonic disperse 4h, sucking filtration to thickness reaches more than 1cm, forms oxidation
Graphene film；
Step (2): the graphene oxide membrane described in step (1) is entered in the mixed atmosphere of hydrogen and argon
Row fine vacuum, high annealing reduce, and obtain graphene film；Wherein, the volume ratio of hydrogen and argon is 1:3；
The total flow of the mixed atmosphere of described hydrogen and argon is 10sccm；The vacuum of described fine vacuum is 80
mTorr；The temperature 2500 DEG C of described high annealing reduction；The time of described high annealing reduction is 40min；
Described heating rate is 3 DEG C/min；
Step (3): carry out being naturally cooling to room temperature by the graphene film described in step (2), takes out；And edge
Graphene film is cut into slices by the direction being perpendicular to graphene sheet layer stacking, and slice thickness is 20 microns, obtains
Graphene collector；The surface topography of described Graphene collector is that graphene sheet layer stacking forms height fluctuating
Gully.
Embodiment 2:
The preparation side of the graphene oxide in the preparation method of the graphene oxide in the present embodiment and embodiment 1
Method is identical；
The preparation method of Graphene collector:
Step (1): by graphene oxide ultrasonic disperse 6h, sucking filtration to thickness reaches more than 1cm, forms oxidation
Graphene film；
Step (2): the graphene oxide membrane described in step (1) is entered in the mixed atmosphere of hydrogen and argon
Row fine vacuum, high annealing reduce, and obtain graphene film；Wherein, the volume ratio of hydrogen and argon is 1:5；
The total flow of the mixed atmosphere of described hydrogen and argon is 20sccm；The vacuum of described fine vacuum is 50mTorr；
The temperature 2800 DEG C of described high annealing reduction；The time of described high annealing reduction is 50min；Described intensification
Speed is 1 DEG C/min；
Step (3): carry out being naturally cooling to room temperature by the graphene film described in step (2), takes out；And edge
Graphene film is cut into slices by the direction being perpendicular to graphene sheet layer stacking, and slice thickness is 10 microns, obtains
Graphene collector；The surface topography of described Graphene collector is that graphene sheet layer stacking forms height fluctuating
Gully.
Embodiment 3:
The preparation side of the graphene oxide in the preparation method of the graphene oxide in the present embodiment and embodiment 1
Method is identical；
The preparation method of Graphene collector:
Step (1): by graphene oxide ultrasonic disperse 7h, sucking filtration to thickness reaches more than 1cm, forms oxidation
Graphene film；
Step (2): the graphene oxide membrane described in step (1) is entered in the mixed atmosphere of hydrogen and argon
Row fine vacuum, high annealing reduce, and obtain graphene film；Wherein, the volume ratio of hydrogen and argon is 1:7；
The total flow of the mixed atmosphere of described hydrogen and argon is 30sccm；The vacuum of described fine vacuum is 70mTorr；
The temperature 3000 DEG C of described high annealing reduction；The time of described high annealing reduction is 60min；Described intensification
Speed is 2 DEG C/min；
Step (3): carry out being naturally cooling to room temperature by the graphene film described in step (2), takes out；And edge
Graphene film is cut into slices by the direction being perpendicular to graphene sheet layer stacking, and slice thickness is 15 microns, obtains
Graphene collector；The surface topography of described Graphene collector is that graphene sheet layer stacking forms height fluctuating
Gully.
The explanation being not directed in the detailed description of the invention of the present invention belongs to techniques well known, refers to known skill
Art is carried out.
The present invention, through validation trial, achieves satisfied trial effect.
Embodiments of the present invention are not limited to above-described embodiment, make on the premise of without departing from present inventive concept
Within various changes belong to protection scope of the present invention.
Claims (8)
1. the preparation method of a high conductivity Graphene collector, it is characterised in that comprise the following steps:
Step (1): by graphene oxide ultrasonic disperse 4-7h, sucking filtration to thickness reaches more than 1cm, forms oxidation stone
Ink alkene film；
Step (2): the graphene oxide membrane described in step (1) is carried out height in the mixed atmosphere of hydrogen and argon
Vacuum, high annealing reduce, and obtain graphene film；The volume ratio of described hydrogen and argon is 1:3-7；Described
The total flow of the mixed atmosphere of hydrogen and argon is 10-30sccm；The vacuum of described fine vacuum is 50-80
mTorr；Temperature 2500-3000 DEG C of described high annealing reduction；Described high annealing reduction time be
40-60min；Described heating rate is 1 DEG C/min-3 DEG C/min；
Step (3): carry out being naturally cooling to room temperature by the graphene film described in step (2), takes out；And along vertical
Cutting into slices graphene film in the direction of graphene sheet layer stacking, slice thickness is 10-20 micron, obtains stone
Ink alkene collector；The surface topography of described Graphene collector is that graphene sheet layer stacking forms the ditch that height rises and falls
Gully.
The preparation of a kind of flexible High conductivity graphene CNT composite current collector the most according to claim 1
Method, it is characterised in that temperature 2800-3000 DEG C of the high annealing reduction described in step (2), described liter
Temperature speed is 1 DEG C/min-2 DEG C/min.
The preparation of a kind of flexible High conductivity graphene CNT composite current collector the most according to claim 1
Method, it is characterised in that the vacuum of step (2) described fine vacuum is 50-60mTorr.
The preparation of a kind of flexible High conductivity graphene CNT composite current collector the most according to claim 1
Method, it is characterised in that the vacuum of step (2) described fine vacuum is 50mTorr.
The preparation of a kind of flexible High conductivity graphene CNT composite current collector the most according to claim 1
Method, it is characterised in that the time of step (2) described high annealing reduction is 50-60min.
The preparation of a kind of flexible High conductivity graphene CNT composite current collector the most according to claim 1
Method, it is characterised in that hydrogen and the volume ratio of argon described in step (2) are 1:4-6；Described hydrogen
It is 20-30sccm with the total flow of the mixed atmosphere of argon.
The preparation of a kind of flexible High conductivity graphene CNT composite current collector the most according to claim 1
Method, it is characterised in that the time of the graphene oxide ultrasonic disperse described in step (1) is 5-6h.
The preparation of a kind of flexible High conductivity graphene CNT composite current collector the most according to claim 1
Method, it is characterised in that the graphene oxide described in step (1) uses hummers method to prepare.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610365128.7A CN105938907A (en) | 2016-05-26 | 2016-05-26 | Preparation method of high-conductivity graphene current collector |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107706354A (en) * | 2017-10-16 | 2018-02-16 | 中国科学院宁波材料技术与工程研究所 | A kind of depositing base and preparation method thereof |
| CN109301157A (en) * | 2018-09-30 | 2019-02-01 | 东莞市三臻科技发展有限公司 | A kind of lithium ion battery based on graphene film |
| CN110718676A (en) * | 2018-07-12 | 2020-01-21 | 中国科学技术大学 | Lithium ion battery positive pole piece, preparation method thereof and lithium ion battery |
| CN111661838A (en) * | 2020-04-03 | 2020-09-15 | 武汉汉烯科技有限公司 | Light high-conductivity flexible lithium battery current collector material and preparation method and application thereof |
| CN112582105A (en) * | 2020-11-24 | 2021-03-30 | 西安交通大学 | Preparation method of high-conductivity and internally continuous graphene hybrid film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107706354A (en) * | 2017-10-16 | 2018-02-16 | 中国科学院宁波材料技术与工程研究所 | A kind of depositing base and preparation method thereof |
| CN110718676A (en) * | 2018-07-12 | 2020-01-21 | 中国科学技术大学 | Lithium ion battery positive pole piece, preparation method thereof and lithium ion battery |
| CN109301157A (en) * | 2018-09-30 | 2019-02-01 | 东莞市三臻科技发展有限公司 | A kind of lithium ion battery based on graphene film |
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| CN111661838A (en) * | 2020-04-03 | 2020-09-15 | 武汉汉烯科技有限公司 | Light high-conductivity flexible lithium battery current collector material and preparation method and application thereof |
| CN112582105A (en) * | 2020-11-24 | 2021-03-30 | 西安交通大学 | Preparation method of high-conductivity and internally continuous graphene hybrid film |
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Application publication date: 20160914 |