CN109887768A - A kind of roll-to-roll manufacturing method of upright graphene - Google Patents
A kind of roll-to-roll manufacturing method of upright graphene Download PDFInfo
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- CN109887768A CN109887768A CN201910270471.7A CN201910270471A CN109887768A CN 109887768 A CN109887768 A CN 109887768A CN 201910270471 A CN201910270471 A CN 201910270471A CN 109887768 A CN109887768 A CN 109887768A
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- 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
- Y02E60/13—Energy storage using capacitors
Abstract
A kind of roll-to-roll manufacturing method of upright graphene, big depth-to-width ratio micro-structure is continuously prepared using roll-in print technology, utilize microstructure Modulation graphene flowing positioning assembly behavior, it realizes that graphene sheet layer becomes upright orientation assembling from horizontal layer stacking, realizes the roll-to-roll large scale preparation of upright graphene；The present invention can be used for sandwich structure supercapacitor, keep direction of an electric field parallel with lamellar orientation, form fast ionic channel, it solves the restricting relation between the big film thickness high load of graphene supercapacitor and ion transmission range, while breaking through limitation of the interdigital structure micro super capacitor to load capacity；It suitable for chip radiator, guides heat to orient conduction along the high direction of thermal conductivity, realizes high efficiency and heat radiation in the confined space, important in inhibiting is manufactured for integrated chips such as CPU.
Description
Technical field
The invention belongs to oriented graphite alkene membrane preparation technology fields, and in particular to a kind of roll-to-roll manufacture of upright graphene
Method.
Background technique
Graphene possesses the theoretical specific surface area of super large due to its unique monoatomic thickness two-dimension plane structure
(2630m2/ g), it is good that conductive (resistivity is down to 10-6Ω cm), the capacity of heat transmission and excellent mechanical property be considered super
The ideal electrode material of capacitor.Although graphene is ideal electrode material for super capacitor, not any production
Graphene electrodes can express outstanding charge storage, and existing research shows that Graphene electrodes must satisfy specific item
The physical property advantage of part competence exertion graphene.(1) when the two-dimensional graphene synusia in Graphene electrodes is vertical with charge/discharge electric field
When, electrolyte ion will receive " obstructing layer by layer " of two-dimensional graphene along the diffusion motion of direction of an electric field, and diffusion length is much big
In the overall thickness of Graphene electrodes, such as when the lamella that the average synusia spacing (d-spacing) of graphene is 1nm, graphene
Average diameter when being 10 μm, the average diffusion distance of ion is about 2500 times of graphene film thickness, directly result in the filling of device/
The velocity of discharge is slow, the surface area utilization rate of graphene is low, power/energy density is small；(2) when the two-dimentional graphite in Graphene electrodes
When alkene synusia and the field parallel of charge/discharge, diffusion process " unblocked " (i.e. diffusion fortune of the electrolyte ion along direction of an electric field
The dynamic blocking no longer by two-dimensional graphene lamella), ion diffusion length is suitable with the thickness of Graphene electrodes film, thus discharge/charge
Electric speed is fast, graphene surface area utilization rate is high, power/energy density is big.Under the same conditions, Graphene electrodes synusia side
To compared with charge and discharge electric field is vertical and parallel, the capacitor storage capacity of the latter is higher by 1 to 2 orders of magnitude than the former is usual, because
When this is using grapheme material production electrode, graphene two-dimensional slice must go out graphite with charge/discharge field parallel competence exertion
The physical property advantage of alkene.
The capacity of heat transmission of graphene is also closely related with its lamellar orientation, can be by perpendicular to the hot-fluid in graphene planes direction
To the strong limitation of interlayer Van der Waals force, thermal conductivity is very low, and is being parallel to lamella direction, and thermal conductivity is up to 5300WmK-1.Therefore, realize graphene orientation to the graphene-based radiator heat-dissipation efficiency important in inhibiting of promotion.
Oriented graphite alkene membrane preparation method mainly has directly growth deposition and two kinds of liquid phase self assembly at present.Although the former can
With the vertical-growth Graphene electrodes film on various metals substrate, the supercapacitor of preparation is with the power density of superelevation and surely
Qualitative, but reaction process is complicated, power consumption is big, low efficiency, load capacity are small, it is difficult to high-energy density super capacitor is prepared, and
Be not suitable for the preparation of scale magnanimity.In contrast, liquid phase self-assembly method has extensive raw material sources, low cost, high efficiency, is suitble to
The advantage of large-scale production has the potentiality of industrialized development.
In liquid phase self assembling process, microcosmic two-dimensional graphene lamella, will be excellent under the action of flow field and capillary liquid bridge power
Stacked in layers first is formed on being parallel to filter membrane or gas-liquid interface direction, to reach stable stress.Therefore, pass through liquid phase
The obtained Graphene electrodes film of self-assembly method has the characteristic of stacked in layers, can not in the supercapacitor of sandwich structure
Play its physical property advantage (graphene sheet layer is vertical with charge and discharge electric field), and sandwich structure be easiest to realize it is roll-to-roll continuous
The supercapacitor structures form of preparation.Therefore, upright graphene directional assembly, especially roll-to-roll scale system how to be realized
It is standby, it is the prerequisite and technological difficulties for realizing High-performance graphene supercapacitor scale manufacture.
Summary of the invention
In order to overcome the disadvantages of the above prior art, the object of the present invention is to provide a kind of volumes pair of upright graphene
Manufacturing method is rolled up, the upright Graphene electrodes structure with good mechanical properties and fast ionic channel is capable of forming, is suitable for
The supercapacitor of sandwich structure and efficient radiator.
In order to achieve the above object, the technical scheme adopted by the invention is as follows:
A kind of roll-to-roll manufacturing method of upright graphene, comprising the following steps:
1) continuous rolling of big depth-to-width ratio micro-structure is printed as shape: by the tensioning of fexible film 1 of package spread over compression roller 4,
Flexible substrate between mold roller 5, demoulding roller 6 and idler roller 12 as micro-structure uniformly applies ultraviolet cured adhesive UV glue 3
It overlays on fexible film 1, UV glue 3 imprints excipient through mold roller 5, solidifies after the exposure of ultraviolet lamp 14, demoulds through demoulding roller 6, shape
At the flexible micro structure array 7 with big depth-to-width ratio；
2) filling and self assembly of graphene dispersing solution: graphene dispersing solution 9 is uniformly coated and is substantially filled in flexibility
Inside micro structure array 7, the flexible microstructure film 10 of graphene dispersing solution 9 is filled up under the heating of infrared heat source 13, graphene point
The evaporation of 9 internal solvent of dispersion liquid, induction graphene sheet layer form the straight of flexible microstructure Modulation along flexible micro-structure surface directional assembly
Vertical Graphene electrodes film 11.
The UV glue 3 with a thickness of 0.01mm-1mm.
A kind of roll-to-roll manufacturing method realization of upright graphene is prepared into greatly from big depth-to-width ratio flexibility micro-structure
It is prepared by the serialization of the upright graphene self assembly of thickness, using rolling process preparation flexible microstructure features size as low as
500nm, maximum depth-to-width ratio reach 15:1.
The graphene dispersing solution 9 includes graphene aqueous liquid dispersion, graphene aqueous slurry, graphene organic solvent
Dispersion liquid.
The solvent of the graphene dispersing solution 9 is water, methanol, ethyl alcohol, isopropanol, DMF or NMP.
A kind of roll-to-roll manufacturing method of the upright graphene be equally applicable to there is class graphene-structured other
Two-dimensional material dispersion.
The invention has the benefit that
The present invention is suitable for the roll-to-roll extensive manufacture of upright graphene film, utilizes upright microstructure Modulation graphene
Flowing positioning assembly behavior, make graphene from horizontal layer stack assembly become upright orientation assembling, to produce big thickness
The upright Graphene electrodes of degree high load make graphene sheet layer direction and electric field suitable for the supercapacitor of sandwich structure
Direction is parallel, forms fast ionic channel, solves the big film thickness high load of graphene supercapacitor and ion transmission range
Between restricting relation, while breaking through limitation of the interdigital structure micro super capacitor to load capacity；Suitable for chip cooling
Device, guidance heat orient conduction along the high direction of thermal conductivity, realize confined space interior orientation, high efficiency and heat radiation, CPU etc. is collected
Important in inhibiting is manufactured at circuit chip.
Detailed description of the invention
Fig. 1 is the flow chart of the method for the present invention.
Fig. 2 is the horizontal alignment of the upright oxidation graphene film of the embodiment of the present invention and same unit area load capacity
The cyclic voltammetry curve comparison diagram of redox graphene film preparation sandwich structure supercapacitor.
Specific embodiment
The present invention is described in further details with reference to the accompanying drawings and examples.
As shown in Figure 1, a kind of roll-to-roll manufacturing method of upright graphene, comprising the following steps:
1) continuous rolling of big depth-to-width ratio micro-structure is printed as shape: the tensioning of PI fexible film 1 of package is spread over compression roller
4, flexible substrate as micro-structure between mold roller 5, demoulding roller 6 and idler roller 12, with being fed scraper 2 for the purple of 0.1mm thickness
Outer optic-solidified adhesive UV glue 3 is coated uniformly on fexible film 1, and 3 thickness of UV glue is by between the first feed scraper 2 and fexible film 1
Distance determine, UV glue 3 through mold roller 5 imprint excipient, through ultraviolet lamp 14 expose 300s after solidify, through demoulding roller 6 demould, formed
The flexible micro structure array 7 of 15:1 is reached with depth-to-width ratio；
2) filling and self assembly of graphene dispersing solution: graphene dispersing solution 9 is uniformly coated and is filled through the second feed scraper 8
Divide and be filled into inside flexible micro structure array 7, the flexible microstructure film 10 for filling up graphene dispersing solution 9 adds in infrared heat source 13
Under heat, 9 internal solvent of graphene dispersing solution evaporation, induction graphene sheet layer is formed flexible along flexible micro-structure surface directional assembly
The upright Graphene electrodes film 11 of microstructure Modulation.
A kind of roll-to-roll manufacturing method realization of upright graphene is prepared into greatly from big depth-to-width ratio flexibility micro-structure
It is prepared by the serialization of the upright graphene self assembly of thickness, using rolling process preparation flexible microstructure features size as low as
500nm, maximum depth-to-width ratio reach 15:1.
The graphene dispersing solution 9 is graphene oxide aqueous liquid dispersion, and the solvent of graphene dispersing solution 9 is water.
Having the beneficial effect that for the present embodiment loads 0.5mg/cm using unit area manufactured in the present embodiment2Upright stone
The super electricity of horizontal alignment redox graphene film preparation sandwich structure of black alkene electrode film and same unit area load capacity
Container, under the same test conditions specific capacitance the former than the latter be higher by 8.8 times, reach 2.45mF/cm2, as shown in Fig. 2, straight simultaneously
Vertical redox graphene supercapacitor has lesser equivalent internal resistance, shows the redox graphene structure of upright orientation
Redox graphene structure relative to horizontal alignment be more advantageous to ion quickly through.
Utilize the oxygen reduction fossil of upright Graphene electrodes film manufactured in the present embodiment and the horizontal alignment of same load capacity
Black alkene film carries out hydrone permeability test, to simulate the diffusion motion process of sandwich structure supercapacitor intermediate ion, together
Deng under the conditions of upright orientation redox graphene can allow in 10h 100mL pure water quickly through, and be horizontally oriented reduction
Graphene oxide needs 120h by communicating the pure water of volume, show upright orientation redox graphene be conducive to hydrone,
Ion for preparing sandwich structure high-performance super capacitor quickly through being of great significance.
The above method realizes the roll-to-roll extensive continuous preparation of upright graphene film, utilizes upright microstructure Modulation
The flowing positioning assembly behavior of graphene makes graphene become upright orientation assembling from horizontal layer stack assembly, to manufacture
The upright Graphene electrodes of big thickness high load out make graphene sheet layer direction suitable for the supercapacitor of sandwich structure
It is parallel with direction of an electric field, fast ionic channel is formd, the big film thickness high load of graphene supercapacitor is solved and ion passes
Restricting relation between defeated distance, while breaking through limitation of the interdigital structure micro super capacitor to load capacity；Suitable for core
Sheet heat radiator, guidance heat orient conduction along the high direction of thermal conductivity, high efficiency and heat radiation in the confined space are realized, for CPU etc.
Integrated chip manufactures important in inhibiting.
Claims (6)
1. a kind of roll-to-roll manufacturing method of upright graphene, it is characterised in that: the following steps are included:
1) continuous rolling of big depth-to-width ratio micro-structure is printed as shape: by fexible film (1) tensioning of package spread over compression roller (4),
Flexible substrate between mold roller (5), demoulding roller (6) and idler roller (12) as micro-structure, by ultraviolet cured adhesive UV glue (3)
It is coated uniformly on fexible film (1), UV glue (3) imprints excipient through mold roller (5), solidifies after ultraviolet lamp (14) exposure, passes through
Roller (6) demoulding is demoulded, the flexible micro structure array (7) with big depth-to-width ratio is formed；
2) filling and self assembly of graphene dispersing solution: graphene dispersing solution (9) is uniformly coated and is substantially filled to flexible micro-
Array of structures (7) is internal, fills up the flexible microstructure film (10) of graphene dispersing solution (9) under infrared heat source (13) heating, stone
Black alkene dispersion liquid (9) internal solvent evaporation, induction graphene sheet layer form flexible micro-structure along flexible micro-structure surface directional assembly
The upright Graphene electrodes film (11) of modulation.
2. a kind of roll-to-roll manufacturing method of upright graphene according to claim 1, it is characterised in that: the UV glue
(3) with a thickness of 0.01mm-1mm.
3. a kind of roll-to-roll manufacturing method of upright graphene according to claim 1, it is characterised in that: described one kind
The roll-to-roll manufacturing method of upright graphene, which is realized from big depth-to-width ratio flexibility micro-structure, is prepared into the upright graphene of big thickness from group
Prepared by the serialization of dress, the flexible microstructure features size as low as 500nm prepared using rolling process, and maximum depth-to-width ratio is up to 15:
1。
4. a kind of roll-to-roll manufacturing method of upright graphene according to claim 1, it is characterised in that: the graphite
Alkene dispersion liquid (9) includes graphene aqueous liquid dispersion, graphene aqueous slurry, graphene dispersion in organic solvent.
5. a kind of roll-to-roll manufacturing method of upright graphene according to claim 1, it is characterised in that: the graphite
The solvent of alkene dispersion liquid (9) is water, methanol, ethyl alcohol, isopropanol, DMF or NMP.
6. a kind of roll-to-roll manufacturing method of upright graphene according to claim 1, it is characterised in that: described one kind
The roll-to-roll manufacturing method of upright graphene is equally applicable to other two-dimensional material dispersions with class graphene-structured.
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| CN104835555A (en) * | 2015-05-13 | 2015-08-12 | 南京邮电大学 | Preparation method of patterned metal transparent conductive film |
| CN105296958A (en) * | 2015-11-10 | 2016-02-03 | 中国科学院重庆绿色智能技术研究院 | Three-dimensional non-catalytic base load graphene film structure and preparation method thereof in low temperature environment |
| CN105529469A (en) * | 2016-01-29 | 2016-04-27 | 白德旭 | Graphene lithium battery and preparation method thereof |
| CN106444275A (en) * | 2016-09-08 | 2017-02-22 | 深圳先进技术研究院 | Roll-to-roll ultraviolet nano-imprinting device and method for preparing super-hydrophobic surface micro-structure by using roll-to-roll ultraviolet nano-imprinting device |
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Patent Citations (4)
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| CN104835555A (en) * | 2015-05-13 | 2015-08-12 | 南京邮电大学 | Preparation method of patterned metal transparent conductive film |
| CN105296958A (en) * | 2015-11-10 | 2016-02-03 | 中国科学院重庆绿色智能技术研究院 | Three-dimensional non-catalytic base load graphene film structure and preparation method thereof in low temperature environment |
| CN105529469A (en) * | 2016-01-29 | 2016-04-27 | 白德旭 | Graphene lithium battery and preparation method thereof |
| CN106444275A (en) * | 2016-09-08 | 2017-02-22 | 深圳先进技术研究院 | Roll-to-roll ultraviolet nano-imprinting device and method for preparing super-hydrophobic surface micro-structure by using roll-to-roll ultraviolet nano-imprinting device |
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