CN104445160A - Method for preparing graphene through molten inorganic salt reaction bed - Google Patents
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- CN104445160A CN104445160A CN201410623638.0A CN201410623638A CN104445160A CN 104445160 A CN104445160 A CN 104445160A CN 201410623638 A CN201410623638 A CN 201410623638A CN 104445160 A CN104445160 A CN 104445160A
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Abstract
The invention discloses a method for preparing graphene through a molten inorganic salt reaction bed. The method comprises the following steps: with a phthalocyanine matter as a reaction raw material, uniformly mixing an inorganic salt with the phthalocyanine matter in the inorganic salt reaction bed, cracking and separating out to a highly plane oriented graphene material in an atmosphere furnace under a protective gas by adopting a program heating method. The method disclosed by the invention can be used for cracking under a non-hydrogen environment to obtain the graphene material, the method is simple, the process is environment-friendly, industrialized production can be achieved, and the obtained graphene has highly plane orientation property.
Description
Technical field
The present invention relates to field of new material preparation, particularly a kind of method preparing grapheme material.
Background technology
Since Geim in 2004 etc. utilize adhesive tape repeatedly to peel off obtained Graphene on natural graphite, Graphene causes unprecedented sensation in scientific circles because of the individual layer sheet hexagonal honeycomb lattice structure of its uniqueness, and its unique excellent properties and huge potential using value cause whole world extensive concern especially.Chemically on bonding pattern, form the carbon atom of Graphene two-dirnentional structure with sp
2mode hydridization, this hybrid form makes carbon atom and adjacent three carbon atoms form stable C-C key by σ key, imparts the mechanical property that Graphene is high.Form large π key in the π-electron delocalization provided perpendicular to carbon atom a large amount of on graphene planes, electronics can move freely wherein simultaneously, and therefore Graphene all has excellent electroconductibility usually.Such as Graphene is a kind of zero gap semiconductor, and electronics wherein movement velocity can reach 1/300 of the light velocity, and Graphene carrier mobility speed is up to 2 × 10
5cm
2v
-1s
-1deng.In addition, Graphene also has good thermal property and magnetic performance.The fields such as the specific surface area that Graphene is higher makes it at ultracapacitor, Chu Qing, unit molecule chemical sensor have huge potential application.
At present, graphite oxide reduction method is prepare the main method of Graphene, and the method is that graphite is carried out Strong oxdiative process, carries out stripping again and prepares graphene oxide, eventually pass reduction treatment and obtain Graphene after obtaining graphene oxide to it.Owing to the structure of havoc graphene sheet layer in Strong oxdiative process, although through reduction treatment, the electron conjugated structure of graphene sheet layer obtains part and recovers, and the property indices of gained grapheme material still exists larger gap with high-quality Graphene.In addition, the oxidising process of graphite needs a large amount of strongly-acid oxygenants as the vitriol oil, concentrated nitric acid and potassium permanganate etc. usually, and also need the toxic chemical substance such as hydrazine hydrate or sodium borohydride in reduction process, not only energy consumption is large, inefficiency, cost are high but also seriously polluted.As patent of invention CN102897756, CN102897757 etc.Epitaxial growth method prepares Graphene needs at high temperature, be filled with carbon-source gas (methane, ethane, acetylene etc.), decomposing gas also forms Graphene in substrate, the method needs the high temperature of more than 1000 degree, and need hydrogen as reducing gas, working condition is required strict, long reaction time, low yield, and the use of a large amount of hazardous gas adds the further application that production cost also limit Graphene.And Graphene is peeled off also very difficult from substrate (as substrates such as copper, nickel, silicon carbide), often adopt the radical approach such as strong acid burn into high-temperature gasification, not only cost is high, environmental pollution greatly, has also damaged Graphene finished product.As patent of invention CN102903616, CN102891074 etc.
This special structure of Graphene makes it have excellent physicochemical property, how to make it in macrostructure or functional materials, be utilized the focus of scientific circles' concern now.But because Graphene disperses bad in the base, be difficult to reach homogeneous; In addition Graphene is generally difficult to form strong interface cohesion with matrix, thus becomes a difficult problem for puzzlement graphene composite material development.
As oriented growth, the Graphene be evenly distributed, can design the oriented graphite alkene array being prepared into different shape as required, can effectively avoid in the application disperseing difficult problem, and the performance of Graphene along plane excellence can be given full play to, make it have wide application prospect.
Therefore, in the urgent need to develop a kind of adopt novel material, method is simple, to equipment without particular requirement, cost is low, efficiency is high, no pollution, zero release, easily promote the use of, can solve that the cost existed in existing graphene preparation technology is high, efficiency is low, of poor quality, the problem such as poor dispersion, poor compatibility, and can obtain the method for the grapheme material with elevation plane orientation.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, provide a kind of molten state inorganic salt reaction bed to prepare the method for Graphene.
For achieving the above object, the technical solution used in the present invention is:
The method of Graphene prepared by a kind of molten state inorganic salt reaction bed; with phthalocyanines material for reaction raw materials; in inorganic salt reaction bed; inorganic salt are mixed with phthalocyanines material; in atmosphere furnace; under a shielding gas, adopt temperature programming method, cracking is also separated out and is obtained elevation plane orientation Graphene class material.
Further, described phthalocyanines material comprises nonmetal phthalocyanine class material, metal phthalocyanine class material, metal oxide phthalocyanines material, the polymer containing phthalocyanine ring structure and the porphyrin polymkeric substance containing class phthalocyanine ring structure.
Further, described inorganic salt reaction bed is resistant to elevated temperatures container filling inorganic salt; Described inorganic salt are the mixing of one or more of sodium salt, sylvite, vitriol, hydrochloride, nitrate.
Further, the mass ratio of phthalocyanines reaction raw materials and inorganic salt is 1:99-10:90.
Further, describedly to be mixed with reaction raw materials by inorganic salt, method is: phthalocyanines material, evenly adds in inorganic salt reaction bed evenly or after inorganic salt melting at intensification forward slip value by phthalocyanines material and inorganic salt.
Further, described shielding gas is one of nitrogen, argon gas, argon gas/hydrogen mixed gas, argon gas/ammonia gas mixture, nitrogen/hydrogen mixed gas, Nitrogen, Ammonia gas mixture, and shielding gas flow rate control is at 10-50cm
3min
-1between.
Further, described gas mixture volume ratio is 0.1:9.9-1:9.
Further, described cracking temperature is 800-1000 DEG C, and pyrolysis time is 4-24h.
Further, scission reaction can be carried out at catalyst-free or under having metal catalysis conditions, and described metal catalyst is Copper Foil, copper mesh, nickel foil, nickel foam, copper alloy or nickelalloy.
Further, in inorganic salt or phthalocyanines material, high-quality Graphene kind is added brilliant.
The method preparing Graphene provided by the invention, using phthalocyanines material as raw material, using molten state inorganic salt as reaction bed, adopts cracking and precipitation technology one step to obtain Graphene class material.The present invention cracking can obtain Graphene class material in non-hydrogen environment, method is simple, technique environmental protection, suitability for industrialized production can be realized, the Graphene class obtained has elevation plane orientation, can be applicable to the aspects such as single-molecule detection technology, field effect transistor and unicircuit thereof, transparency conductive electrode, electrically conductive ink, field emission source and vacuum electron device, ultracapacitor and biological devices.
Accompanying drawing explanation
The Copper Phthalocyanine Molecule structural representation that Fig. 1 provides for the embodiment of the present invention.
Fig. 2 gathers phthalocyanine polymer schematic diagram for the individual layer that the embodiment of the present invention provides.
Fig. 3 for the embodiment of the present invention provide with sodium-chlor be the orientation grapheme material that medium obtains XRD figure spectrum.
Fig. 4 for the embodiment of the present invention provide with Repone K be the orientation grapheme material that medium obtains XRD figure spectrum.
What Fig. 5 provided for the embodiment of the present invention take sodium-chlor as orientation grapheme material transmission electron microscope (TEM) photo that medium obtains.
What Fig. 6 provided for the embodiment of the present invention take Repone K as orientation grapheme material transmission electron microscope (TEM) photo that medium obtains.
Embodiment
The method of Graphene prepared by a kind of molten state inorganic salt reaction bed; with phthalocyanines material for reaction raw materials (not doing other feed purification process directly to use); in inorganic salt reaction bed; inorganic salt are mixed with reaction raw materials; phthalocyanines raw material and inorganic salt mixing quality are than being 1:99-10:90; in atmosphere furnace; under a shielding gas; with reference to the thermochemistry characteristic of raw material; adopt temperature programming method; at catalyst-free or under having metal catalyst effect, the high temperature heat transfer cracking by fused salt is also separated out and is obtained having elevation plane orientation Graphene class material.
Described phthalocyanines material comprises nonmetal phthalocyanine class material, metal phthalocyanine class material, metal oxide phthalocyanines material, the polymer containing phthalocyanine ring structure and the porphyrin polymkeric substance containing class phthalocyanine ring structure.One of preferred magnesium-yttrium-transition metal phthalocyanine-like compound and derivative thereof (as silver-colored in Nickel Phthalocyanine, CuPc, FePC, phthalocyanine molybdenum, Cobalt Phthalocyanine, phthalocyanine gold, phthalocyanine and derivative etc.).
Described inorganic salt reaction bed is resistant to elevated temperatures container filling inorganic salt; Described inorganic salt are the mixing of one or more of sodium salt, sylvite, vitriol, hydrochloride, nitrate.
Describedly mixed with reaction raw materials by inorganic salt, method is: phthalocyanines material, evenly adds in inorganic salt reaction bed evenly or after inorganic salt melting at intensification forward slip value by phthalocyanines material and inorganic salt.
Described shielding gas is one of nitrogen, argon gas, argon gas/hydrogen mixed gas, argon gas/ammonia gas mixture, nitrogen/hydrogen mixed gas, Nitrogen, Ammonia gas mixture, and described gas mixture volume ratio is 0.1:9.9-1:9, and shielding gas flow rate control is at 10-50cm
3min
-1between.
Cracking temperature is different according to the thermochemistry characteristic of raw material, be generally more than 800 degree, preferred cracking temperature is 800-1000 DEG C, under preferred cracking temperature, the time that cracking generates graphene sheet layer is 4-24 hour, shorten or extend pyrolysis time to final grapheme material size, thickness and quality have impact.Scission reaction can be carried out at catalyst-free or under having metal catalysis conditions, and described metal catalyst is Copper Foil, copper mesh, nickel foil, nickel foam, copper alloy or nickelalloy.
In inorganic salt or phthalocyanines material, add high-quality Graphene kind brilliant, growth quality and the speed of Graphene can be improved.
By the size regulating the experiment parameters such as cracking temperature, gas flow, gas flow rate effectively can control Graphene class material, thickness and quality; Different raw materials formulates different temperature programming schemes according to its thermochemistry characteristic; Any compound containing phthalocyanine ring and derivative thereof all can be used as the raw material obtaining azepine Graphene, metallic graphite carbon alkene and Graphene.
In azepine Graphene class material, the acquisition of nitrogen element is from self nitrogen-atoms in phthalocyanine frame, obtaining the nitrogen-atoms of more high-content, can pass into the gas mixture of ammonia and rare gas element in cracking process as needed; For improving material conductivity or other character, increase the final nitrogen content of material by passing into ammonia; In the Graphene class material of containing metal nanoparticle, the acquisition of metal nanoparticle is from metal classification contained by raw material self, for CuPc, obtains the grapheme material containing metallic copper nano particle the most at last.
Phthalocyanine is a class macrocylc compound, and Phthalocyanine center is a 18-π system be made up of carbon nitrogen conjugated double bond, has a cavity, diameter about 2.7 × 10 in ring
-10m.Two hydrogen atoms in center cavity can be replaced by 70 multiple elements, comprise nearly all metallic element and a part of non-metallic element (as shown in Figure 1), and metal oxide etc.And phthalocyanine polymer makes a general reference those polymers containing phthalocyanine ring structure (as Fig. 2).The present invention will, using this compounds as raw material, using molten state salt as reaction bed, adopt cracking and precipitation technology one step to obtain the grapheme material with elevation plane orientation; Adopt the method also can obtain carbon nanotube and soccerballene.
Embodiment 1
With 30.0 grams of commercially available CuPcs (CuPc) for raw material, do not do any purification process, mix with sodium-chlor, the mass ratio of raw material and salt is 1:99.In quartz tube furnace, with under high-purity argon gas protection, argon gas stream speed control is built in 50cm
3min
-1, under following intensification scheme, cracking obtains 20.7 grams of final metallic graphite carbon alkene class materials.Namely be warming up to 300 degree with slow heat-up rate 5 degree of per minutes, stablize 1 hour for 300 degree; Be warming up to 350 degree with 5 degree of per minutes, stablize 1 hour for 350 degree; Be warming up to 400 degree with 5 degree of per minutes, stablize 1 hour for 400 degree; Be warming up to 500 degree with 3 degree of per minutes, stablize 4 hours for 500 degree; Be warming up to 800 degree with 2 degree of per minutes, stablize 8 hours for 800 degree, be finally naturally down to room temperature, product is to wash the class that desalts, and obtain having height-oriented grapheme material, Fig. 3 and Fig. 5 be shown in by its XRD and transmission electron microscope collection of illustrative plates.
Embodiment 2
With 30.0 grams of commercially available CuPcs (CuPc) for raw material, do not do any purification process, mix with Repone K, the mass ratio of raw material and salt is 1:99.In quartz tube furnace, with under high-purity argon gas protection, argon gas stream speed control is built in 50cm
3min
-1, under following intensification scheme, cracking obtains 20.7 grams of final metallic graphite carbon alkene class materials.Namely be warming up to 300 degree with slow heat-up rate 5 degree of per minutes, stablize 1 hour for 300 degree; Be warming up to 350 degree with 5 degree of per minutes, stablize 1 hour for 350 degree; Be warming up to 400 degree with 5 degree of per minutes, stablize 1 hour for 400 degree; Be warming up to 500 degree with 3 degree of per minutes, stablize 4 hours for 500 degree; Be warming up to 800 degree with 2 degree of per minutes, stablize 8 hours for 800 degree, be finally naturally down to room temperature, product is to wash the class that desalts, and obtain having height-oriented grapheme material, Fig. 4 and Fig. 6 be shown in by its XRD and transmission electron microscope collection of illustrative plates.
Embodiment 3
With 30.0 grams of commercially available CuPcs (CuPc) for raw material, do not do any purification process, mix with sodium-chlor, the mass ratio of raw material and salt is 10:90.In quartz tube furnace, with under high-purity argon gas protection, argon gas stream speed control is built in 50cm
3min
-1, under following intensification scheme, cracking obtains 20.7 grams of final metallic graphite carbon alkene class materials.Namely be warming up to 300 degree with slow heat-up rate 5 degree of per minutes, stablize 1 hour for 300 degree; Be warming up to 350 degree with 5 degree of per minutes, stablize 1 hour for 350 degree; Be warming up to 400 degree with 5 degree of per minutes, stablize 1 hour for 400 degree; Be warming up to 500 degree with 3 degree of per minutes, stablize 4 hours for 500 degree; Be warming up to 800 degree with 2 degree of per minutes, stablize 8 hours for 800 degree, be finally naturally down to room temperature, product, to wash the class that desalts, obtains having height-oriented grapheme material.
Embodiment 4
Be (CuPc) raw material with 30.0 grams of commercially available CuPcs, do not do any purification process, mix with Repone K, the mass ratio of raw material and salt is 10:90.In quartz tube furnace, with under high-purity argon gas protection, argon gas stream speed control is built in 50cm
3min
-1, under following intensification scheme, cracking obtains 20.7 grams of final metallic graphite carbon alkene class materials.Namely be warming up to 300 degree with slow heat-up rate 5 degree of per minutes, stablize 1 hour for 300 degree; Be warming up to 350 degree with 5 degree of per minutes, stablize 1 hour for 350 degree; Be warming up to 400 degree with 5 degree of per minutes, stablize 1 hour for 400 degree; Be warming up to 500 degree with 3 degree of per minutes, stablize 4 hours for 500 degree; Be warming up to 800 degree with 2 degree of per minutes, stablize 8 hours for 800 degree, be finally naturally down to room temperature, product, to wash the class that desalts, obtains having height-oriented grapheme material.
Under the different salt medium of table 1, different salt and material rate
Obtain grapheme material specific surface area to compare
Embodiment 5
With 30.0 grams of laboratories synthetic phthalocyanine nickel (NiPc) for raw material, mix with sodium-chlor, the mass ratio of raw material and salt is 1:99.In quartz tube furnace, with under high-purity argon gas protection, argon gas stream speed control is built in 50cm
3min
-1, under following intensification scheme, cracking obtains 20.7 grams of final metallic graphite carbon alkene class materials.Namely be warming up to 300 degree with slow heat-up rate 5 degree of per minutes, stablize 1 hour for 300 degree; Be warming up to 350 degree with 5 degree of per minutes, stablize 1 hour for 350 degree; Be warming up to 400 degree with 5 degree of per minutes, stablize 1 hour for 400 degree; Be warming up to 500 degree with 3 degree of per minutes, stablize 4 hours for 500 degree; Be warming up to 800 degree with 2 degree of per minutes, stablize 8 hours for 800 degree, be finally naturally down to room temperature, product, to wash the class that desalts, obtains having height-oriented grapheme material.
Embodiment 6
With 30.0 grams of laboratories synthetic phthalocyanine nickel (NiPc) for raw material, mix with Repone K, the mass ratio of raw material and salt is 1:99.In quartz tube furnace, with under high-purity argon gas protection, argon gas stream speed control is built in 50cm
3min
-1, under following intensification scheme, cracking obtains 20.7 grams of final metallic graphite carbon alkene class materials.Namely be warming up to 300 degree with slow heat-up rate 5 degree of per minutes, stablize 1 hour for 300 degree; Be warming up to 350 degree with 5 degree of per minutes, stablize 1 hour for 350 degree; Be warming up to 400 degree with 5 degree of per minutes, stablize 1 hour for 400 degree; Be warming up to 500 degree with 3 degree of per minutes, stablize 4 hours for 500 degree; Be warming up to 800 degree with 2 degree of per minutes, stablize 8 hours for 800 degree, be finally naturally down to room temperature, product, to wash the class that desalts, obtains having height-oriented grapheme material.
Embodiment 7
With 30.0 grams of laboratories synthetic phthalocyanine nickel (NiPc) for raw material, mix with sodium-chlor, the mass ratio of raw material and salt is 10:90.In quartz tube furnace, with under high-purity argon gas protection, argon gas stream speed control is built in 50cm
3min
-1, under following intensification scheme, cracking obtains 20.7 grams of final metallic graphite carbon alkene class materials.Namely be warming up to 300 degree with slow heat-up rate 5 degree of per minutes, stablize 1 hour for 300 degree; Be warming up to 350 degree with 5 degree of per minutes, stablize 1 hour for 350 degree; Be warming up to 400 degree with 5 degree of per minutes, stablize 1 hour for 400 degree; Be warming up to 500 degree with 3 degree of per minutes, stablize 4 hours for 500 degree; Be warming up to 800 degree with 2 degree of per minutes, stablize 8 hours for 800 degree, be finally naturally down to room temperature, product, to wash the class that desalts, obtains having height-oriented grapheme material.
Embodiment 8
With 30.0 grams of laboratories synthetic phthalocyanine nickel (NiPc) for raw material, mix with Repone K, the mass ratio of raw material and salt is 10:90.In quartz tube furnace, with under high-purity argon gas protection, argon gas stream speed control is built in 50cm
3min
-1, under following intensification scheme, cracking obtains 20.7 grams of final metallic graphite carbon alkene class materials.Namely be warming up to 300 degree with slow heat-up rate 5 degree of per minutes, stablize 1 hour for 300 degree; Be warming up to 350 degree with 5 degree of per minutes, stablize 1 hour for 350 degree; Be warming up to 400 degree with 5 degree of per minutes, stablize 1 hour for 400 degree; Be warming up to 500 degree with 3 degree of per minutes, stablize 4 hours for 500 degree; Be warming up to 800 degree with 2 degree of per minutes, stablize 8 hours for 800 degree, be finally naturally down to room temperature, product, to wash the class that desalts, obtains having height-oriented grapheme material.
Under the different salt medium of table 2, different salt and material rate
Obtain grapheme material specific surface area to compare
Embodiment 9
With 30.0 grams of commercially available CuPcs (CuPc) for raw material, do not do any purification process, mix with sodium-chlor, the mass ratio of raw material and salt is 1:99.In quartz tube furnace, with under high pure nitrogen protection, nitrogen flow rate controls at 50cm
3min
-1, under following intensification scheme, cracking obtains 20.7 grams of final metallic graphite carbon alkene class materials.Namely be warming up to 300 degree with slow heat-up rate 5 degree of per minutes, stablize 1 hour for 300 degree; Be warming up to 350 degree with 5 degree of per minutes, stablize 1 hour for 350 degree; Be warming up to 400 degree with 5 degree of per minutes, stablize 1 hour for 400 degree; Be warming up to 500 degree with 3 degree of per minutes, stablize 4 hours for 500 degree; Be warming up to 800 degree with 2 degree of per minutes, stablize 8 hours for 800 degree, be finally naturally down to room temperature, product, to wash the class that desalts, obtains having height-oriented grapheme material.Its specific surface area is 197.8m
2g
-1.
Embodiment 10
With 30.0 grams of commercially available CuPcs (CuPc) for raw material, do not do any purification process, add small amounts Graphene crystal seed, raw material mixes with sodium-chlor with graphene oxide, and the mass ratio between three is 1:1:98.In quartz tube furnace, with under high-purity argon gas protection, argon gas stream speed control is built in 50cm
3min
-1, under following intensification scheme, cracking obtains 20.7 grams of final metallic graphite carbon alkene class materials.Namely be warming up to 300 degree with slow heat-up rate 5 degree of per minutes, stablize 1 hour for 300 degree; Be warming up to 350 degree with 5 degree of per minutes, stablize 1 hour for 350 degree; Be warming up to 400 degree with 5 degree of per minutes, stablize 1 hour for 400 degree; Be warming up to 500 degree with 3 degree of per minutes, stablize 4 hours for 500 degree; Be warming up to 800 degree with 2 degree of per minutes, stablize 8 hours for 800 degree, be finally naturally down to room temperature, product, to wash the class that desalts, obtains having height-oriented grapheme material.Its specific surface area is 210.8m
2g
-1.Reference examples
The step of the synthetic method of the nitrating Graphene of Chinese invention patent CN201110204957 is: first cleaning, drying substrates; At the solution of substrate surface coating containing catalyzer, this catalyzer is water-soluble metal salt; Under anaerobic, the substrate temperature being coated with catalyzer is risen to 500 ~ 1300 DEG C, then passes into reducing gas, reducing catalyst, the nitrogen source compound of the organic carbon source compound and gaseous state that then pass into gaseous state reacts, and obtains described nitrating Graphene, and its itrogen content of getter with nitrogen doped is 3.7%.
It should be noted last that, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to example to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to technical scheme of the present invention or equivalent replacement, and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of right of the present invention.
Claims (10)
1. a method for Graphene prepared by molten state inorganic salt reaction bed, it is characterized in that:
With phthalocyanines material for reaction raw materials, in inorganic salt reaction bed, mixed by inorganic salt with phthalocyanines material, in atmosphere furnace, under a shielding gas, adopt temperature programming method, cracking is also separated out and is obtained elevation plane orientation Graphene class material.
2. the method for claim 1, is characterized in that: described phthalocyanines material comprises nonmetal phthalocyanine class material, metal phthalocyanine class material, metal oxide phthalocyanines material, the polymer containing phthalocyanine ring structure and the porphyrin polymkeric substance containing class phthalocyanine ring structure.
3. the method for claim 1, is characterized in that: described inorganic salt reaction bed is resistant to elevated temperatures container filling inorganic salt; Described inorganic salt are the mixing of one or more of sodium salt, sylvite, vitriol, hydrochloride, nitrate.
4. the method for claim 1, is characterized in that: the mass ratio of phthalocyanines reaction raw materials and inorganic salt is 1:99-10:90.
5. the method for claim 1, it is characterized in that: described inorganic salt to be mixed with reaction raw materials, method is: phthalocyanines material, evenly adds in inorganic salt reaction bed evenly or after inorganic salt melting at intensification forward slip value by phthalocyanines material and inorganic salt.
6. the method for claim 1, is characterized in that: described shielding gas is one of nitrogen, argon gas, argon gas/hydrogen mixed gas, argon gas/ammonia gas mixture, nitrogen/hydrogen mixed gas, Nitrogen, Ammonia gas mixture, and shielding gas flow rate control is at 10-50cm
3min
-1between.
7. method as claimed in claim 6, is characterized in that: described gas mixture volume ratio is 0.1:9.9-1:9.
8. the method for claim 1, is characterized in that: described cracking temperature is 800-1000 DEG C, and pyrolysis time is 4-24h.
9. the method for claim 1, is characterized in that: scission reaction can be carried out at catalyst-free or under having metal catalysis conditions, and described metal catalyst is Copper Foil, copper mesh, nickel foil, nickel foam, copper alloy or nickelalloy.
10. the method for claim 1, is characterized in that: in described inorganic salt or described phthalocyanines material, add high-quality Graphene kind crystalline substance.
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