CN109534314A - The preparation method of carbon nanocapsule thin film/nano-micrometer network combined film and fiber - Google Patents
The preparation method of carbon nanocapsule thin film/nano-micrometer network combined film and fiber Download PDFInfo
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Abstract
The present invention provides a kind of continuous preparation methods of carbon nanocapsule thin film/nano-micrometer network combined film and fiber, are related to nano material and its preparation technical field.Its method includes: to prepare nano-micrometer network on the first substrate；The first substrate for being prepared with nano-micrometer network winding is put into growth chamber, and is heated up under the protection of reducibility gas；In predetermined temperature, carbon source is introduced；Make the first substrate roll-to-roll transmission at a predetermined velocity for being prepared with nano-micrometer network, directly growth obtains carbon nanocapsule thin film/nano-micrometer network/first substrate；Separation is to obtain the network combined film of continuous carbon nanocapsule thin film/nano-micrometer, composite fibre.The laminated film of method preparation provided by the invention can be separated with substrate; realize lossless transfer, and the laminated film after separation is individually present since the supporting role of network does not need other supporting layers still, simplifies production stage; production cost is greatly reduced, there is prepare with scale prospect.
Description
Technical field
The present invention relates to nano material and its preparation technical fields, more particularly to a kind of carbon nanocapsule thin film/nano-micrometer net
The continuous preparation method of network laminated film and fiber.
Background technique
Carbon is to constitute most basic one of the element of nature, the carbon nanomaterial constructed from bottom to top by carbon atom, such as carbon
Nanotube, graphene, self-discovery start, just because its excellent property receives everybody concern.Gradually with preparation method
Development and perfection, carbon nanotube and graphene can only develop to the macro of batch production in the micropreparation in laboratory from initially
Amount preparation.Have benefited from this, carbon nanotube and the outstanding performance of graphene be just able to electrically conducting transparent, energy conversion, ultra high strength fiber,
There is larger range of application in the fields such as protection.
It is existing that graphene is prepared mainly in magnesium-yttrium-transition metal upper surface high-temperature catalytic with chemical vapor deposition (CVD) method
It grows (1000 DEG C), and graphene can not form self-supporting under the disturbance of external environment, so generally requiring by some high
The protection of polymers (such as polymethyl methacrylate, PMMA) is shifted, complex steps and high polymer be difficult to completely remove it is clean,
Many inconvenience are brought for the subsequent applications of graphene.Moreover, because defect (including point defect, line defect) and by shifting
The graphene face resistance of the presence of the breakage of graphene film brought by journey, CVD preparation is still larger, these factors make graphite
Alkene is unable to fully put its excellent property to good use.
Nano-micrometer network refers to the porous network being made of the hole of nanometer to micro-meter scale.It is thin with carbon nano tube network
For film, carbon nano tube network film is the effect shape for passing through intermolecular force, covalent bond or electrostatic force by carbon nanotube
At network structure, according to growth or treatment conditions difference, hole is adjustable in nanometer to micron range.This network by
In its porous feature and superthin structure, there is very high transmitance to visible light.Meanwhile carbon nanotube equally has leading for superelevation
Electrically, mechanical strength and stability.
By nano-micrometer network thin-film in conjunction with carbon nanocapsule thin film, by both materials in conjunction with and the NEW TYPE OF COMPOSITE that is formed is thin
Film or composite fibre may have more excellent property.For example, the carbon nanotube prepared based on high temperature CVD mode/
The laminated film of graphene, on the one hand, since carbon nanotube can give carrier across the crystal boundary and other defect of graphene
Transmission provide additional access, increase electric conductivity compared to graphene；The mechanical property of carbon pipe itself is very high simultaneously,
There is higher mechanical strength compared to graphene after compound.The mode that this variety classes nano material is combined with each other is expected to
It solves the problems, such as that above-mentioned CVD method growth graphene face resistance is big, self-supporting can not be formed, and it is superior multiple to form comprehensive performance
Close film.On the other hand, due to the introducing of graphene, during forming fiber by film, graphene film and carbon pipe are mutual
It is in contact, plays the role of transmitting stress, it can reinforcing fiber integral strength；In addition, compared to carbon nanotube, due to graphene
Surface area it is very big, so providing more attachment sites, be easier to adhere to functionalized species, functionalization can be further enhanced
Substance provides bigger put down to the modifying function of film or fiber for the application and research based on carbon nanocapsule thin film or fiber
Platform.
The laminated film is directly prepared in the prior art using methane as carbon source, since methane decomposition temperature is high, i.e.,
Just in the presence of catalyst substrate, very high temperature is generally required by the formation of the carbon nanocapsule thin film of representative of graphene
(1000℃).It is known that there is many differences in physics, chemical property for nano material and block materials, specifically,
Nano-micrometer network has the characteristics that small size and high-specific surface area, and surface energy is high, specific surface atom number is more and near neighboring coordination
Incomplete, these factors cause fusing point lower compared with block materials, therefore when temperature is higher is easy to fuse itself or decomposition, or even with
Catalyst substrate reacts, therefore the growth for carrying out carbon nanocapsule thin film at the abovementioned high temperatures can undoubtedly reduce original nano-micrometer
The property of network thin-film causes the performance of finally obtained laminated film to be lost.Meanwhile high temperature increase growth cost and
Difficulty, the requirement to equipment is also very high, is unfavorable for large-scale production.Furthermore the process of high temperature is also given directly in flexible liner
Growing mixed film brings very big difficulty on bottom.So the low temperature of the network combined film of carbon nanocapsule thin film/nano-micrometer is big
Scale preparation, collection are particularly important.
Summary of the invention
It is an object of the invention in view of the above defects of the prior art, provide a kind of continuously prepare and collection
The method of the network combined film of carbon nanocapsule thin film/nano-micrometer.
It is a further object of the invention that being based on the above method, the continuous preparation of one kind, collection carbon nanocapsule thin film/receive-are provided
The method of the network combined fiber of micron.
Particularly, the present invention provides a kind of network combined film of carbon nanocapsule thin film/nano-micrometer, fiber and THIN COMPOSITEs
The preparation method of the continuous macroscopic body of film and fiber, comprising the following steps:
Nano-micrometer network is prepared on the first substrate；
The first substrate for being prepared with nano-micrometer network winding is put into growth chamber, and under the protection of reducibility gas
It heats up to the first substrate for being prepared with nano-micrometer network；
In predetermined temperature, carbon source is introduced；
Make the first substrate roll-to-roll transmission at a predetermined velocity for being prepared with nano-micrometer network, directly growth obtains carbon nanometer
Film/nano-micrometer network/the first substrate；
The first substrate and carbon nanocapsule thin film/nano-micrometer network are separated, continuous carbon nanocapsule thin film/nano-micrometer network is obtained
Laminated film, the network combined fiber of continuous carbon nanocapsule thin film/nano-micrometer or the network combined film of carbon nanocapsule thin film/nano-micrometer
With the continuous macroscopic body of fiber.
Optionally, first substrate is that can reduce carbon source to decompose potential barrier and have certain flexibility, collapsible substrate；
The nano-micrometer network has a porous network structure, the pore-size size distribution of the porous network structure in
Nanometer is to micro-meter scale.
Optionally, other elements can be introduced while the introducing carbon source to be modified or adulterate.
Optionally, the carbon source includes gaseous carbon source, liquid carbon source and any one or more of combination of solid-state carbon source,
By selecting different carbon sources, the network combined film of carbon nanocapsule thin film/nano-micrometer can be prepared under different growth temperatures.
Optionally, the carbon nanocapsule thin film is the two-dimensional nano-film of carbon atoms, and the carbon nanocapsule thin film includes single-layer graphene, lacks
Any one of layer graphene, amorphous carbon, glass graphite alkene, nitrogen-doped graphene, boron doping graphene.Optionally, described
Carbon nanocapsule thin film is combined by way of chemical bond and secondary or physical bond with nano-micrometer network.
Optionally, make the first substrate roll-to-roll transmission at a predetermined velocity for being prepared with nano-micrometer network, growth obtains carbon
It can be with In-situ reaction other materials during nano thin-film/nano-micrometer network/first substrate.
Optionally, make the first substrate roll-to-roll transmission at a predetermined velocity for being prepared with nano-micrometer network, growth obtains carbon
During nano thin-film/nano-micrometer network/first substrate, the carbon nanocapsule thin film is filled in the hole of nano-micrometer network,
Form an imporous laminated film.
Optionally, the laminated film is subjected to compact shrinkage and composite fibre is made.
Optionally, a part of the laminated film is subjected to compact shrinkage, is prepared into the continuous of laminated film and fiber
Macroscopic body.
Optionally, the continuous carbon nanocapsule thin film/the network combined film of nano-micrometer, continuous carbon nanocapsule thin film/receive-
The length of the continuous macroscopic body of the network combined fiber of micron or the network combined film of carbon nanocapsule thin film/nano-micrometer and fiber is greater than
1mm。
The present invention provides a kind of preparation methods of carbon nanocapsule thin film/nano-micrometer network combined film and fiber, not only may be used
Directly continuously to prepare the network combined film of carbon nanocapsule thin film/nano-micrometer perhaps composite fibre of the two or the two
The length of the macroscopic body of laminated film and fiber, laminated film, composite fibre and macroscopic body is unlimited, and simplifies production
Step greatly reduces production cost.And there can be scale by selecting the carbon source of low-temperature decomposition to significantly reduce preparation temperature
Preparation prospect.
The present invention provides a kind of preparation method of network combined fiber of carbon nanocapsule thin film/nano-micrometer, prepared, collection
Composite fibre, carbon nanocapsule thin film is filled in nano-micrometer network, and the two passes through chemical bond, intermolecular force and electrostatic force knot
It closes, after being crimped to fiber, carbon nanocapsule thin film is contacted with each other with nano-micrometer network, a kind of structure coated mutually is formed, this
Kind structure facilitates the conduction and release of local stress, enhances the mechanical property of fiber；By this coating function, also enhance
Whole electric conductivity.
Detailed description of the invention
Some specific embodiments of the present invention is described in detail by way of example and not limitation with reference to the accompanying drawings hereinafter.
Identical appended drawing reference denotes same or similar part or part in attached drawing.It should be appreciated by those skilled in the art that these
What attached drawing was not necessarily drawn to scale.In attached drawing:
Fig. 1 is continuously to prepare carbon nanocapsule thin film/nano-micrometer network according to low temperature a kind of in one embodiment of the present of invention to answer
Close the apparatus structure schematic diagram of film (carbon source is introduced by heating method)；
Fig. 2 is the scanning electron according to the graphene/carbon nanotube composite film prepared in one embodiment of the present of invention
Micrograph；
Fig. 3 is continuously to prepare carbon nanocapsule thin film/nano-micrometer network according to low temperature a kind of in one embodiment of the present of invention to answer
Close the apparatus structure schematic diagram of film (wherein, carbon source is introduced by bubbling mode)；
Fig. 4 is before graphene/carbon nanotube composite film prepared by graphene, carbon nano-tube film and embodiment 1 adulterates
(wherein carbon nano-tube film is carbon nano-tube film used in embodiment 1 to surface resistance contrast schematic diagram afterwards, and graphene is
The graphene grown under carbon nano-tube film, the same terms is not prepared in embodiment 1)；
Fig. 5 is the graphene/carbon nanotube composite film and graphene, carbon nanometer prepared according to the embodiment of the present invention 1
(wherein carbon nano-tube film is carbon nano-tube film used in embodiment 1 to the Raman contrast schematic diagram of pipe, and graphene is real
Apply the graphene for not preparing in example 1 and growing under carbon nano-tube film, the same terms)；
Fig. 6 is the light transmittance characterization signal of the graphene/carbon nanotube composite film prepared according to the embodiment of the present invention 1
Figure；
Fig. 7 is continuously to prepare carbon nanocapsule thin film/nano-micrometer network according to high temperature a kind of in one embodiment of the present of invention to answer
Close the apparatus structure schematic diagram of film (wherein, carbon source is introduced directly into)；
Fig. 8 is according to the apparatus structure schematic diagram for continuously collecting composite fibre in one embodiment of the present of invention；
Fig. 9 is the schematic diagram of the copper foil for having golden grid network pattern prepared according to embodiment 12；
Figure 10 is the stream that a kind of low temperature according to the present invention continuously prepares the network combined film of carbon nanocapsule thin film/nano-micrometer
Journey schematic diagram.
Specific embodiment
The invention patent is described further below by drawings and embodiments.But protection orientation of the invention is not
It is confined to following instance, the full content in claims should be included.
The inventors found that: nano-micrometer network since the porous structure of its own can bring some problems, although
The chemical property of nano-micrometer network itself can be very stable, but extraneous molecule (such as water, oxygen, acid, metal) can be across these
The hole of nanometer, micron order size generates corrosiveness to the metal, semiconductor or other materials being in contact with it and even occurs
The situation of short circuit.For example, when nano-micrometer network application is in silicon-based photovoltaic device, external air and hydrone pair
Silicon face has the oxidation of duration, corrosiveness, this will substantially reduce the stability of photovoltaic device.Therefore, it is based on this, invention
People creatively provides the preparation method of a kind of carbon nanocapsule thin film/nano-micrometer network combined film and fiber, to the company of preparation
The continuous network combined film of carbon nanocapsule thin film/nano-micrometer and fiber.
Fig. 1 is continuously to prepare carbon nanocapsule thin film/nano-micrometer network according to low temperature a kind of in one embodiment of the present of invention to answer
Close the apparatus structure schematic diagram of film (carbon source is introduced by heating method).Fig. 2 is to make according in one embodiment of the present of invention
The scanning electron microscopy of standby graphene/carbon nanotube composite film.Fig. 3 is according to a kind of in one embodiment of the present of invention
Low temperature continuously prepares the apparatus structure schematic diagram of the network combined film of carbon nanocapsule thin film/nano-micrometer, and (wherein, carbon source passes through bubbling
Mode introduces).Figure 10 is that a kind of low temperature according to the present invention continuously prepares the network combined film of carbon nanocapsule thin film/nano-micrometer
Flow diagram.
The preparation method of a kind of carbon nanocapsule thin film/nano-micrometer network combined film and fiber provided by the invention, it is general
Ground may include steps of:
(1) nano-micrometer network is prepared on the first substrate；
(2) the first substrate for being prepared with nano-micrometer network winding is put into growth chamber, and in the protection of reducibility gas
Under to be prepared with nano-micrometer network the first substrate heat up；
(3) in predetermined temperature, carbon source is introduced；
(4) make the first substrate roll-to-roll transmission at a predetermined velocity for being prepared with nano-micrometer network, direct growth obtains carbon and receives
Rice film/nano-micrometer network/first substrate；
(5) the first substrate of separation and carbon nanocapsule thin film/nano-micrometer network, obtain continuous carbon nanocapsule thin film/nano-micrometer
Network combined film, the network combined fiber of continuous carbon nanocapsule thin film/nano-micrometer or carbon nanocapsule thin film/nano-micrometer are network combined
The continuous macroscopic body of film and fiber.
Specifically, first substrate, which refers to, can reduce the substrate that carbon source decomposes potential barrier.Including the use of thermal evaporation, magnetic control
What the methods of sputtering, electrochemistry, spin coating, titration were prepared has the substrate for reducing carbon source decomposition barrier compositions；Optionally, first
Substrate includes the one or several kinds of polyimides/copper substrate, copper, nickel, corronil, copper-iron alloy.First substrate is flexible
It is collapsible；
The nano-micrometer network refer to by nanoscale, nanometer to micron order and nanoscale and micron order mixing or
The porous network of the hole composition of micron order scale, the referred to as network are made of the porous network of nanometer to micron size.
Optionally, the nano-micrometer network refers to the porous network being made of the hole of nanoscale；Specifically include
0.1nm-1nm,1nm-100nm,100nm-500nm,500nm-1000nm.Preferably, 1nm or more.
Optionally, the nano-micrometer network refers to the porous network being made of the hole of micro-meter scale；
Specifically, including 1 μm -100 μm；
Specifically, including 100 μm -500 μm；
Specifically, including 500 μm -1000 μm；
Specifically, it is greater than 1000 μm.
Preferably, 1 μm or more.
Optionally, the nano-micrometer network can both have the hole of nanoscale, and there is also the holes of micro-meter scale
Gap.
Further, the porous network in the nano-micrometer network can be rule, be also possible to irregular.
Further, the thickness of the nano-micrometer network can regulate and control；And thickness is unlimited；Can be very thin, thickness is lower than
0.5nm；Can also be thicker, thickness is greater than or equal to 0.5nm；Preferably, thickness is in 1nm or more.
Further, the method for preparing nano-micrometer network can be from top to bottom, be also possible to from bottom to top.For example, often
Method from top to bottom specifically include nano-micrometer network is directly sprawled on substrate, spin coating, Best-Effort request, printing, roller
Extrusion covers, micro-nano technology or above two or a variety of methods it is integrated.Commonly method from bottom to top specifically includes chemistry
Method, electrochemical process, direct growth method or several method it is integrated.Either from top to bottom and the from bottom to top combination of method.
Optionally, the nano-micrometer network includes electrical-conductive nanometer network and non-conductive nanometer network；
Specifically, electrical-conductive nanometer network has metal nano network or semiconductor nano network, optionally, including carbon nanotube
Network, silver nanowires network, nanowires of gold network, alloy nano-wire network, the golden film with nano-micrometer hole, have receive-it is micro-
One or more of the carbon film of metre hole gap；
Specifically, non-conductive nanometer network includes one or more of silica nanometer network, aluminium oxide nano network；
Further, above-mentioned steps (2) described container is the container for holding carbon source and not reacting with carbon source；Preferably,
The container is selected from one of stainless steel quartz, glass, refractory metal, silica, aluminium oxide ceramics or a variety of；
Further, carbon source described in above-mentioned steps (2) is the carbonaceous material with lower decomposition temperature；Optionally, have
One or more of solid-state carbon source, including naphthalene, coronene, polymethyl methacrylate (PMMA), polystyrene (PS)；It can
Selection of land has one or more of liquid carbon source, including benzene, toluene；Optionally, the mixing including solid-state carbon source and liquid carbon source
Object.
Further, by selecting different carbon source, carbon nanocapsule thin film/receive-can be prepared under different growth temperatures
The network combined film of micron.
Specifically, by the carbon source for selecting that there is high decomposition temperature, it is micro- that carbon nanocapsule thin film/receive-can be prepared at high temperature
The network combined film of rice.
Specifically, by the carbon source for selecting that there is low decomposition temperature, it is micro- that low temperature preparation carbon nanocapsule thin film/receive-may be implemented
The network combined film of rice.
Optionally, growth temperature is less than 800 DEG C, growth time t1 as the case may be depending on (such as runner revolving speed, film are thick
Degree, density of film, film length).
Optionally, growth temperature be 800 DEG C -1200 DEG C, growth time t1 as the case may be depending on (such as transmission speed,
Film thickness, density of film, film length).
Particularly, other materials can be introduced while carbon source is introduced in above-mentioned steps (2) to be modified or adulterate；
Further, the method that air is excluded described in above-mentioned steps (2) is emptied including being passed directly into purge gas, including
It is emptied using vacuum pump；
Specifically, the above-mentioned purge gas used is inert gas；Optionally, including argon gas, helium, nitrogen or by them
The mixed gas of composition；
Further, reducibility gas described in above-mentioned steps (3) is the not oxidized gas of guard catalyst, preferably
Ground, including hydrogen, carbon monoxide.
Further, according to the difference of carbon source, the mode that step (3) introduces carbon source includes: to be introduced directly at room temperature as gas
The carbon compound of phase, by carrier gas bubbling evaporate liquid phase carbon compound, volatilized solid carbon-contg chemical combination by heating
The combination of object or these modes.
Specifically, it is introduced directly into and refers to gas phase carbon compound is introduced directly into chamber for the carbon compound of gas phase at room temperature
Body；The gas phase carbon compound includes one of methane, ethane, propane or a variety of；
Specifically, referred to by the liquid phase carbon compound that carrier gas bubbling is taken out of and be passed through liquid carbon source using carrier gas, drum
It steeps and takes liquid carbon source out of；The liquid carbon source includes one of ethyl alcohol, benzene, toluene or a variety of；
Specifically, carbon compound is volatilized heating to refer to directly in the way of heating to cavity introducing carbon
Source；The carbon source can be liquid, such as ethyl alcohol, benzene；Can be it is solid, such as polymethyl methacrylate (PMMA), naphthalene, six
One of benzo benzene, polystyrene (PS) are a variety of.
Further, carbon nanocapsule thin film described in above-mentioned steps (4) refers to the two-dimensional nano-film of carbon atoms, including
Single-layer graphene, few layer graphene, amorphous carbon, glass graphite alkene, nitrogen-doped graphene, boron doping graphene.
Further, in above-mentioned steps (5) before separation can other compound substances, such as polyvinyl alcohol (PVA), poly- methyl-prop
E pioic acid methyl ester (PMMA), poly- 3,4-rthylene dioxythiophene/poly styrene sulfonate (PEDOT:PSS).
Further, separation method described in above-mentioned steps (5) includes chemical Bubbling method and chemical etching method；Specifically
Ground, for the electrochemistry bubbling method using graphite rod as anode electrode, cathode electrode is the first substrate, micro- by nano thin-film/receive-
The bubble generated between rice network and the first substrate, the two is separated.Wherein, electrolyte is 0.2-2mol/L NaOH aqueous solution,
Voltage is 2-4V.
Specifically, the chemical etching method use the first substrate etching liquid, with the first substrate of solution contact portion
Etching, carbon nanocapsule thin film/nano-micrometer network separates with the first substrate, and is collected.
The present invention also provides one kind based on continuous preparation and to collect the network combined film of carbon nanocapsule thin film/nano-micrometer, with even
The continuous method for preparing carbon-based composite fibre, includes the following steps:
(1) growth obtains carbon nanocapsule thin film/nano-micrometer network/first rolls of substrate；
(2) carbon nanocapsule thin film/nano-micrometer network and the first substrate are separated；
(3) carbon nanocapsule thin film after separation/nano-micrometer network is drawn through runner, controls its shrinkage in a liquid, even
The continuous continuous macroscopic body for forming fiber, film or fiber membrane；
(4) the continuous macroscopic body of obtained fiber, film or fiber membrane is collected.
Further, above-mentioned steps (2) separation carbon nanocapsule thin film/nano-micrometer network and the first substrate include chemistry
Bubbling method and chemical etching method.
Specifically, for the electrochemistry bubbling method using graphite rod as anode electrode, cathode electrode is the first substrate, passes through carbon
The bubble for nano thin-film/generated between nano-micrometer network and the first substrate, the two separation.Wherein, electrolyte 0.2-2mol/L
NaOH aqueous solution, voltage 2-4V.
Specifically, the chemical etching method is using the solution that can etch the first substrate, with the etching of contact layer, carbon nanometer
Film/nano-micrometer network is separated with the first substrate, and is collected.
Further, above-mentioned steps (3) runner is by electrical motor driven, and the etching speed phase of its hauling speed and film
Matching.
Further, above-mentioned steps (3) can also carry out the continuous macroscopic body of fiber, film or fiber membrane in situ
It is compound.
The carbon nanocapsule thin film that any preparation method provided through the invention is continuously prepared/nano-micrometer network is multiple
Film is closed, carbon nanocapsule thin film is filled in the hole of nano-micrometer network, forms an imporous laminated film.And laminated film
Thickness is controllable.It is combined by way of secondary or physical bond and chemical bond between carbon nanocapsule thin film and nano-micrometer network.Optionally, it wraps
Include covalent bond, intermolecular force and electrostatic force.
Optionally, the thickness of carbon nanocapsule thin film is controllable in laminated film, can be very thin, is less than 0.5nm；It can also be compared with
Thickness is more than or equal to 0.5nm；The thickness of nano-micrometer network is also adjustable according to selected material, generally higher than 0.1nm；It is preferred that
Ground is greater than 1nm.
The carbon nanocapsule thin film that any preparation method provided through the invention is continuously prepared/nano-micrometer network is multiple
Close the composite fibre of film or the two or the laminated film and fiber or above-mentioned material (or above structure) of the two
With the composite material of other materials, length is unlimited, can be regulated and controled according to demand.
Optionally, the length is 0.1mm or more；
Optionally, the length is 1mm or more；
Preferably, the length is 100mm or more；
Preferably, the length is 1000mm or more；
Preferably, the length is 1500mm or more；
Preferably, the length is 2000mm or more.
The preparation method of a kind of carbon nanocapsule thin film/nano-micrometer network combined film and fiber provided by the invention, not only may be used
Directly continuously to prepare the network combined film of carbon nanocapsule thin film/nano-micrometer perhaps composite fibre of the two or the two
The length of the macroscopic body of laminated film and fiber, laminated film, composite fibre and macroscopic body is unlimited, and simplifies production
Step, and production cost can be greatly reduced by selecting the carbon source of low-temperature decomposition to significantly reduce preparation temperature.
The present invention provides a kind of preparation method of network combined fiber of carbon nanocapsule thin film/nano-micrometer, prepared, collection
Composite fibre, carbon nanocapsule thin film is filled in nano-micrometer network, and the two passes through chemical bond, intermolecular force and electrostatic force knot
It closes, after being crimped to fiber, carbon nanocapsule thin film is contacted with each other with nano-micrometer network, a kind of structure coated mutually is formed, this
Kind structure facilitates the conduction and release of local stress, enhances the mechanical property of fiber；By this coating function, also enhance
Whole electric conductivity.
The preparation method of a kind of carbon nanocapsule thin film/nano-micrometer network combined film and fiber provided by the invention, have with
Lower technical effect:
(1) carbon nanocapsule thin film directly grown compared to CVD method, when the conductive nano-micrometer conductive network of use is as bridge
When with the network combined film of carbon nanocapsule thin film/nano-micrometer of skeleton preparation, by conductive nano-micrometer network to initial carbon nanometer
The modification of film, occurs therebetween electric charge transfer, and the more original carbon nanocapsule thin film of the electrical properties of laminated film obtained has
Large increase, comprehensive electrically conducting transparent performance are greatly improved；
(2) carbon nanocapsule thin film directly grown compared to CVD method, laminated film enhance due to the mechanics of nano-micrometer network
Effect, can be separated laminated film with substrate by some way in the case where not needing supporting layer, to realize lossless
Transfer, and the laminated film after separation is individually present since the supporting role of network does not need other supporting layers still.This is not
The transfer step of carbon nanocapsule thin film under routine operation is only reduced, also can avoid the organic polymers such as the PMMA for being difficult to completely remove
Impurity residual, fundamentally solves such impurity to the scattering of photon and carrier and compound caused film light transmittance and leads
The decline problem of electrical property；And then also ensure that laminated film is intrinsic while guaranteeing the high cleaning on laminated film surface
Excellent properties.
(3) compared to nano-micrometer network thin-film, the laminated film electric conductivity of this method preparation is higher, simultaneously as carbon is received
Rice film is filled between the hole of nano-micrometer network, so its conductive isotropism significantly increases；In addition, when being applied to
When electronic device, this seamless film can prevent the erosion of the substances such as external water, oxygen, compared to nano-micrometer network, tool
There is more excellent protective value.
(4) low-temperature synthetic method mentioned in the present invention selects the hydrocarbon with low bond energy as cryogenic carbon
The carbon source (such as naphthalene) in source, low decomposition temperature has lower decomposition gesture compared to conventional high decomposition temperature carbon source (such as methane)
It builds, reduces the growth temperature of carbon nanocapsule thin film on the whole significantly, and the reduction of temperature is to carbon nanocapsule thin film/nano-micrometer net
Industrialized realize of network laminated film has very great meaning, this greatly reduces energy consumption, reduces production cost, is into one
Step large-scale growth is laid a good foundation.
(5) low-temperature synthetic method mentioned above is conducive to the pattern and superiority that keep nano-micrometer network thin-film script
Matter, this is because nano-micrometer network has the characteristics that small size and high-specific surface area, for block materials, surface energy height,
Specific surface atom number is more and near neighboring coordination is not complete, so fusing point is often lower, therefore when temperature is higher is easy to that itself occurs
Melt or decomposes；On the other hand, it is also likely to be present co-melting between catalyst substrate and nano-micrometer network or reacts and break
Bad original network structure, thus pyroprocess can reduce nano-micrometer reticulated film script excellent properties even destroy receive-it is micro-
Rice reticulated film, leads to the effect to carbon nanocapsule thin film without any modification, so the realization of low-temperature epitaxy is for improving THIN COMPOSITE
The bulk property of film also seems particularly critical.
(6) low-temperature synthetic method mentioned in the present invention, by selection can low-temperature decomposition carbon source, can be down to 200
Growing mixed film under conditions of DEG C, this mode can expand laminated film and grow in the flexible substrate of non-refractory, so that
Network combined film/the flexible substrate of carbon nanocapsule thin film/nano-micrometer has flexibility；Transparent flexible substrate is such as selected, then the product has
Have it is transparent and flexible, and have flexible, transparent conductivity；And then the application prospect of laminated film is expanded.
(7) it can be separated with substrate using the laminated film of method provided by the invention preparation, realize lossless transfer, and
Laminated film after separation is individually present since the supporting role of network does not need other supporting layers still, this in self-supporting
There is no limit in length for laminated film, reachable several meters long, and has extraordinary flexible, high transparency electric conductivity；Using this hair
The composite fibre of the method preparation of bright offer can directly be prepared into self-supporting fiber, and there is no limit in length, reachable several meters long,
And there is good flexible and electric conductivity；The application range of the laminated film and fiber is widened.
It is described in detail below with reference to specific embodiment.Such as nothing should be particularly mentioned that in the embodiment of the present invention, material therefor,
Reagent is commercially available.
Embodiment 1
Step 1: by high-purity copper foil of purchase after electrochemical polish, and cleaning remaining electrolyte on copper foil, dry up.
Step 2: the carbon nano-tube film continuously grown being spread on processed copper foil, and winds and is wound on runner one
End；
Step 3: carbon nano-tube film/copper foil of winding being placed in cavity, solid-state naphthalene is placed in vial simultaneously
With foil sealing, it is drilled with aperture on aluminium foil, and by vial as cavity upstream, as shown in Figure 1.
Step 4: it is passed through purge gas emptying, it is clean to air discharge.In the present embodiment, the purge gas is high-purity
Argon, flow 500sccm.
Step 5: closing purge gas, the cavity 32 that heats up under the protection of hydrogen and argon gas is to target temperature T1.This implementation
Example hydrogen flowing quantity is preferably 30sccm, and argon flow 300sccm, target temperature is 800 DEG C.
Step 6: holding 32 temperature of cavity area is T1, and region 31 is warming up to T2, and operation of electrically driven motor transmits runner, turns
Speed is set as S1.Wherein, T2 is 60 DEG C, and runner revolving speed S1 is preferably 1rpm/min.
The present embodiment finally obtains the graphene/carbon nanotube composite film being continuously grown on copper foil, the graphite of preparation
Alkene/carbon nano-tube coextruded film is under a scanning electron microscope as shown in Fig. 2, graphene is filled up completely in carbon nanotube or carbon
Between the porous network that nanotube bundle is constituted, therebetween without hole, the pore size of carbon nanotube used is 100-
500nm, graphene are mainly single layer (<0.5nm), and having small part is bilayer or multilayer (>0.5nm), compound after overdoping
Film surface resistance can be lower than 100 Ω/sq, the graphene/carbon nanotube composite film length being grown on copper foil in the present embodiment
Greater than 500mm.
Embodiment 2
Melamine powder will be added in naphthalene powder in embodiment 1 and be uniformly mixed, wherein naphthalene powder and melamine
The mass ratio of powder is between 1:1 and 10:1, and other steps are in the same manner as in Example 1.The final graphene/carbon for obtaining N doping
Nanotube composite film.
Embodiment 3
Step 1-2 is identical as step 1-2 in embodiment 1；
Step 3: carbon nano-tube film/copper foil of winding being placed in cavity, and liquid phenenyl is contained in the stainless of Fig. 3
Steel sealing container 41, other parameters, condition are consistent.
Step 4: it is passed through purge gas emptying, it is clean to air discharge.In the present embodiment, the purge gas is high-purity
Argon, flow 500sccm.
Step 5: closing purge gas, the cavity 32 that heats up under the protection of hydrogen and argon gas is to target temperature T1.This implementation
Example hydrogen flowing quantity is preferably 30sccm, and argon flow 300sccm, target temperature T1 are 300 DEG C.
Step 6: holding 32 temperature of cavity area is T1, and the container 41 of Xiang Shengyou benzene is passed through carrier gas to introduce carbon source, simultaneously
Operation of electrically driven motor transmits runner, and revolving speed is set as S1.Wherein, carrier gas is high-purity argon, and flow 10sccm, runner revolving speed S1 are excellent
It is selected as 1rpm/min.
The present embodiment finally obtains the graphene/carbon nanotube composite film being continuously grown on copper foil.
Embodiment 4
Step 1-6 is consistent with the step 1-6 in embodiment 1；
Step 7: the graphene/carbon nanotube composite film being collected on copper foil being taken out from cavity, and using bubbling
The mode of method separates copper foil and laminated film；Wherein, anode electrode is graphite rod, and cathode is that copper foil/graphene/carbon nano-tube is multiple
Structure is closed, electrolyte is 1mol/L NaOH solution, and supply voltage is set as 3V；
Step 8: adjustment makes graphene/carbon nano-tube film shrinkage and the traction by runner 2 in the solution after separation
Continuous fiber is collected, the copper foil 22 after separation is collected in runner 20, as shown in Figure 8.
The present embodiment finally obtains the graphene/carbon nano-tube fiber continuously collected, and prepared fibre length is adjustable, this
Place is preferably 500mm or more.
Embodiment 5
Step 1-6 is consistent with the step 1-6 in embodiment 1；
Step 7: the graphene/carbon nanotube composite film being collected on copper foil being taken out from cavity, using Bubbling method
Mode separate copper foil and laminated film；Wherein, anode electrode is graphite rod, and cathode is that copper foil/graphene/carbon nano-tube is compound
Structure, electrolyte are 1mol/L NaOH solution, and supply voltage is set as 3V；
Step 8: the shrinkage of graphene/carbon nano-tube film in the solution after control separation, and leading by runner 2
Draw to form the continuous macroscopic body that laminated film and fiber coexist, copper foil 22 is collected in runner 20.
The present embodiment finally obtains the continuous macroscopic view that the graphene/carbon nanotube composite film continuously collected and fiber coexist
Body.
Embodiment 6
Step 1-8 is consistent with the 1-8 in embodiment 4；
Step 9: continuous fiber being imported into PVA aqueous solution, and is connected by the guidance of motor and runner and PVA aqueous solution
Continuous In-situ reaction, with the mechanical property of reinforcing fiber, and will be soaked with the FRP rebar of PVA aqueous solution and collection；
Step 10: the fiber collected after finishing being put into curing oven, baking temperature is 40 DEG C, and baking time is set as
12h。
The present embodiment finally obtains the graphene/carbon nano-tube continuous fiber that In-situ reaction has PVA.
Embodiment 7
Step 1-6 is consistent with the step 1-6 in embodiment 1；
Step 7: business heat being mounted into film PET/EVA film alcohol washes, drying, then uses corona treatment 1-
5min, to improve the hydrophily on the surface EVA；By PET/EVA film and carbon nano tube/graphene/copper foil carbon nanotube face paste
Close, and utilize plastic packaging machine hot pressing so that EVA softening bonding carbon nano tube/graphene/copper foil, obtain PET/EVA/ carbon nanotube/
Graphene/copper foil composite construction, wherein typical hot pressing temperature is 100 DEG C.
Step 8: copper foil and laminated film are separated by the way of Bubbling method；Wherein, anode electrode is graphite rod, and cathode is
PET/EVA/ carbon nano tube/graphene/copper foil composite construction, electrolyte are 1mol/L NaOH solution, and supply voltage is set as
3V；Copper foil and PET/EVA/ carbon nano tube/graphene/copper foil laminated film obtained after separation is cleaned with deionized water again,
In, copper foil can reuse；
The present embodiment finally obtains the carbon nano tube/graphene laminated film being collected on PET/EVA.
Embodiment 8
Step 1: by high-purity copper foil of purchase after electrochemical polish, and cleaning electrolyte, dry up.
Step 2: the silver nanowires of purchase is dispersed in isopropanol, its concentration C1 is made, it is ultrasonic in supersonic cleaning machine
Dispersion obtains well dispersed silver nanowires suspension；Preferably silver nanowires concentration is 2mg/ml in the present embodiment, when ultrasonic
Between be 1min.
Step 3: silver nanowires being coated on copper foil and wound, revolving speed is set as between 1000-5000rpm, and revolving speed is
The copper foil for being attached with silver nanowires is then placed in 100 DEG C of heated baking 10min on hot plate by 120s.
Later step is the same as step 3-6 in embodiment 1.
The present embodiment, which finally obtains, continuously to be grown and is collected in the graphene on copper foil/silver nanowires laminated film.
Embodiment 9
Step 1-6 is consistent with the step 1-6 in embodiment 4；
Step 7: business heat being mounted into film PET/EVA film alcohol washes, drying, then uses corona treatment 1-
5min, to improve the hydrophily on the surface EVA；By PET/EVA film and silver nanowires/graphene/copper foil silver nanowires face paste
Close, and utilize plastic packaging machine hot pressing so that EVA softening bonding carbon nano tube/graphene/copper foil, obtain PET/EVA/ silver nanowires/
Graphene/copper foil composite construction, wherein typical hot pressing temperature is 100 DEG C.
Step 8: copper foil and laminated film are separated by the way of Bubbling method；Wherein, anode electrode is graphite rod, and cathode is
PET/EVA/ silver nanowires/graphene/copper foil composite construction, electrolyte are 1mol/L NaOH solution, and supply voltage is set as
3V；Copper foil and PET/EVA/ silver nanowires/graphene/copper foil laminated film obtained after separation is cleaned with deionized water again,
In, copper foil can reuse；
The present embodiment finally obtains the silver nanowires/graphene composite film being collected on PET/PVA.
Embodiment 10
Step 1-2 is identical as the step 1-2 of embodiment 1；
Step 3: carbon nano-tube film/copper foil of winding is placed in cavity.
Step 4: it is passed through purge gas emptying, it is clean to air discharge.In the present embodiment, the purge gas is high-purity
Argon, flow 500sccm.
Step 5: closing purge gas, the cavity 32 that heats up under the protection of hydrogen and argon gas is to target temperature T1.This implementation
Example hydrogen flowing quantity is preferably 30sccm, and argon flow 300sccm, target temperature T1 are 1000 DEG C.
Step 6: holding 32 temperature of cavity area is T1, introduces methane, and operation of electrically driven motor transmits runner, and revolving speed is set as
S1, growth is until the first substrate of catalyst of winding uses completely.In the present embodiment, methane flow 5sccm, runner revolving speed S1
Preferably 1rpm/min.
The present embodiment finally obtains the graphene/carbon nanotube composite film being continuously grown on copper foil under high temperature.
Embodiment 11
Step 1-3 is identical as the step 1-3 of embodiment 1；
Step 4: opening vacuum pump, empty the air in cavity.
Step 5: keeping the open state of vacuum pump, the cavity 32 that heats up under the protection of hydrogen and argon gas is to target temperature
T1.The present embodiment hydrogen flowing quantity is preferably 20sccm, and argon flow 100sccm, target temperature T1 are 1000 DEG C.
Step 6: holding 32 temperature of cavity area is T1, introduces methane, and operation of electrically driven motor transmits runner, and revolving speed is set as
S1, growth is until the first substrate of catalyst of winding uses completely.In the present embodiment, methane flow 1sccm, runner revolving speed S1
Preferably 1rpm/min.
The present embodiment finally obtains the graphene/carbon nanotube composite film being continuously grown on copper foil under high temperature.
Embodiment 12
Step 1: by high-purity copper foil of purchase after electrochemical polish, and cleaning remaining electrolyte on copper foil, dry up.
Step 2: one layer of PMMA is coated in copper foil surface, and according to the mask plate photoetching set, then respectively with IPA
With water development, fixing.For PMMA with a thickness of 200nm, development, fixing time are 60s in the present embodiment.
Step 3: sample is dried up with High Purity Nitrogen, is placed in thermal evaporation apparatus, vapor deposition gold.In the present embodiment, golden thickness
For 50nm.
Step 4: sample is taken out, PMMA is washed with acetone, leave formed after photoetching, thermal evaporation have golden grid network figure
The copper foil of case, as shown in Figure 9.The copper foil for having golden grid network pattern is wound, and places it in one end of quartz ampoule, and by liquid
Benzene is contained in the stainless steel sealing container 41 of Fig. 3, and other parameters, condition are consistent.In the present embodiment, the width of golden grid network
It is 1 μm, pore size is 2 μm.
Step 6: it is passed through purge gas emptying, it is clean to air discharge.In the present embodiment, the purge gas is high-purity
Argon, flow 500sccm.
Step 7: closing purge gas, the cavity that heats up under the protection of hydrogen and argon gas is to target temperature T1.The present embodiment
Hydrogen flowing quantity is preferably 30sccm, and argon flow 300sccm, target temperature is 500 DEG C.
Step 8: stop heating after the completion of growth, takes out sample, sample is swum in etching solution, reaction removal first
Substrate is then rinsed 2-3 times with deionized water, each 10min.Finally laminated film can be transferred to target substrate.This implementation
Example etching solution is ferric chloride solution, concentration 0.1mol/L.
The present embodiment finally obtains graphene/gold grid network laminated film, and graphene/gold grid network laminated film length is big
In 500mm.
It should be noted last that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting.Although ginseng
It is described the invention in detail according to embodiment, those skilled in the art should understand that, to technical side of the invention
Case is modified or replaced equivalently, and without departure from the spirit and scope of technical solution of the present invention, should all be covered in the present invention
Scope of the claims in.
Claims (10)
1. a kind of preparation method of carbon nanocapsule thin film/nano-micrometer network combined film and fiber, which is characterized in that including as follows
Step:
Nano-micrometer network is prepared on the first substrate；
The first substrate for being prepared with nano-micrometer network winding is put into growth chamber, and to system under the protection of reducibility gas
Have the first substrate heating of nano-micrometer network；
In predetermined temperature, carbon source is introduced；
Make the first substrate roll-to-roll transmission at a predetermined velocity for being prepared with nano-micrometer network, directly growth obtain carbon nanocapsule thin film/
Nano-micrometer network/the first substrate；
The first substrate and carbon nanocapsule thin film/nano-micrometer network are separated, it is network combined to obtain continuous carbon nanocapsule thin film/nano-micrometer
Film, the network combined fiber of continuous carbon nanocapsule thin film/nano-micrometer or the network combined film of carbon nanocapsule thin film/nano-micrometer and fibre
The continuous macroscopic body of dimension.
2. preparation method according to claim 1, which is characterized in that first substrate is that can reduce carbon source to decompose gesture
Build and have certain flexibility, collapsible substrate；
The nano-micrometer network has porous network structure, and the pore-size size distribution of the porous network structure is in nanometer
To micro-meter scale.
3. preparation method according to claim 1, which is characterized in that the carbon source include gaseous carbon source, liquid carbon source and
Any one or more of combination of solid-state carbon source can be prepared by selecting different carbon sources under different growth temperatures
The network combined film of carbon nanocapsule thin film/nano-micrometer.
4. preparation method according to claim 1, which is characterized in that other elements can be introduced while the introducing carbon source
It is modified or adulterates.
5. preparation method according to claim 1, which is characterized in that the carbon nanocapsule thin film is two wieners of carbon atoms
Rice film, the carbon nanocapsule thin film include single-layer graphene, few layer graphene, amorphous carbon, glass graphite alkene, N doping graphite
Any one of alkene, boron doping graphene.
6. preparation method according to claim 1, which is characterized in that the carbon nanocapsule thin film passes through with nano-micrometer network
The mode of chemical bond and secondary or physical bond combines.
7. preparation method according to claim 1, which is characterized in that make the first substrate for being prepared with nano-micrometer network
Roll-to-roll transmission at a predetermined velocity, growth can be in situ during obtaining carbon nanocapsule thin film/nano-micrometer network/first substrate
Compound other materials.
8. preparation method according to claim 1, which is characterized in that make the first substrate for being prepared with nano-micrometer network
Roll-to-roll transmission at a predetermined velocity, during growth obtains carbon nanocapsule thin film/nano-micrometer network/first substrate, the carbon is received
Rice film is filled in the hole of nano-micrometer network, forms an imporous laminated film.
9. preparation method according to claim 8, which is characterized in that the laminated film is carried out compact shrinkage and is made again
Condensating fiber.
10. preparation method according to claim 1 to 9, which is characterized in that the continuous carbon nanocapsule thin film/
The network combined film of nano-micrometer, the network combined fiber of continuous carbon nanocapsule thin film/nano-micrometer or carbon nanocapsule thin film/nano-micrometer
The length of the continuous macroscopic body of network combined film and fiber is greater than 1mm.
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