CN104220369A

CN104220369A - Graphene compositions

Info

Publication number: CN104220369A
Application number: CN201280066990.8A
Authority: CN
Inventors: K.雷德蒙; D.谢菲尔
Original assignee: Vorbeck Materials Corp
Current assignee: Vorbeck Materials Corp
Priority date: 2011-11-14
Filing date: 2012-11-14
Publication date: 2014-12-17
Also published as: WO2013074709A1; WO2013074712A1; WO2013074710A1; EP2780282A4; EP2780281A4; EP2780282A1; EP2780281A1; CN104640808B; CN104640808A

Abstract

Compositions comprising graphene sheets, at least one aromatic compound. The compositions may optionally contain a polymer and/or acid catalysts. The may be in the form of inks or coatings. The aromatic compounds used in the present invention comprise at least one aromatic ring. They may comprise two or more aromatic rings. When two or more aromatic rings are present, they may be fused, bonded directly to each other, bonded using a spacer of one or more atoms, etc. The aromatic rings can be all-carbon based or can contain heteroatoms (heteroaromatics). Examples of rings systems the aromatic compounds can be based on (derivatives of) include benzene, naphthalene, anthracene, tetracene, pentacene, phenanthrene, pyrene, pyrene, benzo[a]pyrene, coronene, chryrsene, triphenylene, perylene, corannulene, ovalene, acenaphthylene, fluorine, biphenyl, bisphenols, etc. Examples of heteroaromatic ring systems the aromatic compounds can be based on include furan, thiophene, pyrrole, pyridine, indole, imidazole, pynmidine, purine, etc.

Description

Graphene composition

related application is quoted

The application requires the right of priority of following application: the U.S. Provisional Application 61/559715 that on November 14th, 2011 submits to, 61/596216 of submission on February 7th, 2012,61/596220 of submission on February 7th, 2012, with 61/596224 of submission on February 8th, 2012, its all content is incorporated at this by reference.

Invention field

The present invention relates to comprise Graphene and at least one sour composition.

statement about the research and development of federal funding

The present invention uses the government that license number that NSF provides is IIP-1152700 and IIP-1046880 to support.Government has some right of the present invention.

background

Due to its many good character, Graphene is more and more for many practical applications: electrically conductive ink and coating, polymer complex, sensor (such as gas sensor, biosensor etc.), electrode, hot transfer printing application, energy storage device (such as battery and ultracapacitor), solar cell etc.In some cases, Graphene for example, is used with the composition of the component with other (polymer-binder, it can improve the mechanical property of described composition, also has other advantages).Even if successfully Graphene has had many such application, or expectation obtains the Graphene composition of the character (such as specific conductivity, thermal conductivity, mechanical property etc.) with enhancing.

Brief summary of the invention

Disclose and ask for protection a kind of composition herein, it comprises graphene film and at least one aromatic substance.Also disclose and ask for protection a kind of ink or coating, it comprises the composition that contains graphene film and at least one aromatic substance.

detailed Description Of The Invention

For aromatic substance of the present invention, comprise at least one aromatic ring.They can comprise two or more aromatic rings.When there are two or more aromatic rings, they can with condense each other, the interval parts bonding of Direct Bonding, the one or more atoms of use etc. etc.Described aromatic ring can be all maybe can comprise heteroatoms (heteroaromatic thing) based on carbon.The example of member ring systems aromatic substance can be based on following (following derivative): comprise benzene, naphthalene, anthracene, tetracene, pentacene, phenanthrene, pyrene, pyrene, benzo [a] Bi, guan, (chryrsene), triphenylene, perylene, bowl alkene, ovalene, acenaphthylene, fluorine, biphenyl, bis-phenol etc.The example of hetero-aromatic ring system aromatic substance can be based on comprising furans, thiophene, pyrroles, pyridine, indoles, imidazoles, pyrimidine, purine etc.They preferably have the molecular weight that is less than approximately 2000, or are more preferably less than approximately 1000, are also more preferably less than approximately 500.

Described aromatic ring system can be the functionalized or polyfunctional compound who is replaced by, two or more functional groups.Functional group is preferably nucleophilic or close electricity.In some cases, they can with hydroxyl, carboxylic acid or carboxylic acid derivative and/or epoxy reaction.The example of functional group includes but not limited to hydroxyl, hydroperoxyl radical and peroxy, carboxylic acid, carboxylate salt (salt such as Li, Na, K, Mg, Ca, Zn), ester, acid anhydride, acyl halide (comprising chloride of acid), aldehyde (such as formyl radical), acetal, ortho ester, carbonic ether, amino, acid amides, imines, imide, trinitride, cyanate, isocyanic ester, thiol group, sulfo group, sulfino, thiocyanic ester, epoxide, ether etc.In some cases, in functionalized aromatic substance, there are one, two, three, four or more functional group.

Example comprises the compound of following general formula:

One or more substituting group (the R that wherein exist in all cases ¹-R ⁵and R ₁-R ₆) can be Huo Bei functional group of functional group and replace.Other substituting group can be H, alkyl (comprising alkyl, thiazolinyl, alkynyl, aryl, the group such as alicyclic), halogenide (such as muriate, bromide, iodide, fluorochemical) etc.Described functional group can be bonded directly to aromatic ring.In some embodiments, when having two or more aromatic rings, on two different rings, can there is at least one functional group to exist.

The example of aromatic substance comprises phenylformic acid and benzoic acid derivative, hydroxy-benzoic acid (comprising 4-HBA), hydroxy benzaldehyde (comprising 4-hydroxy benzaldehyde), carbamoyl benzoate (comprising 4-carbamoyl benzoate), terephthalaldehyde, m-terephthal aldehyde, o-phthalaldehyde(OPA), terephthalic acid is (with ester terephthalic acid methyl esters for example, dimethyl terephthalate (DMT) etc.), m-phthalic acid is (with ester m-phthalic acid methyl esters for example, dimethyl isophthalate etc.), phthalic acid is (with ester Methyl Benzene-o-dicarboxylate for example, dimethyl phthalate etc.), Tetra hydro Phthalic anhydride, bis-phenol (for example dihydroxyphenyl propane), biphenyl, 4,4'-'-biphenyl diphenol, 3,3'-'-biphenyl diphenol, 2,2'-'-biphenyl diphenol, 4-xenol, 3-xenol, 2-xenol, naphthalene, hydroxyl naphthalene, dihydroxy naphthlene (comprises 2,6-dihydroxy naphthlene, 1,5-dihydroxy naphthlene, 2,3-dihydroxy naphthlene, 1,7-dihydroxy naphthlene, Isosorbide-5-Nitrae-dihydroxy naphthlene, 1,2-dihydroxy naphthlene, 1,3-dihydroxy naphthlene, 2,7 dihydroxy naphthalene and 1,6-dihydroxy naphthlene), naphthalene monocarboxylic acid, naphthalene monocarboxylic acid ester, naphthalene dicarboxylic acids, naphthalene dicarboxylic acids ester, anthracene, pyrene, pentacene phenol, quinhydrones, pyrocatechol, Resorcinol etc.

In some cases, aromatic substance can exist by following weight ratio with respect to graphene film: the about 75:25 of about 0.1:99.9-, or the about 75:25 of about 0.5:99.5-, or the about 50:50 of about 0.5:99.5-, or the about 25:75 of about 0.5:99.5-, or the about 15:85 of about 0.5:99.5-, or the about 10:90 of about 0.5:99.5-, or the about 5:95 of about 0.5:99.5-, or the about 75:25 of about 1:99-, or the about 50:50 of about 1:99-, or the about 25:75 of about 1:99-, or the about 15:85 of about 1:99-, or the about 10:90 of about 1:99-, or the about 5:95 of about 1:99-, or the about 75:25 of about 2:98-, or the about 50:50 of about 2:98-, or the about 25:75 of about 2:98-, or the about 15:85 of about 2:98-, or the about 10:90 of about 2:98-, or the about 5:95 of about 2:98-, the about 50:50 of about 5:95-, the about 25:75 of about 5:95-, the about 75:25 of about 10:90-, the about 50:50 of about 10:90-, the about 25:75 of about 10:90-.

In some cases, aromatic substance can be reacted with any polymeric binder of graphene film and/or existence.In these cases, aromatic substance can be used to graphene film and self and/or tackiness agent crosslinked, and/or by polymeric binder and self-crosslinking.Said preparation can have improved electroconductibility and mechanical properties (for example, when forming ink or coating and printing, having improved adhesive power).

Described composition also can comprise one or more acid catalysts.Described acid can be organic acid or mineral acid.The pKa of described acid in water is preferably less than approximately 4, or is more preferably less than approximately 3, or is also more preferably less than approximately 2.5.PKa in water can be less than approximately 2, or is less than approximately 1, or is less than approximately 0.Described acid can be the form of sealing (blocked).Under these circumstances, pKa is based on untight acid.Described acid can be curing catalysts.

The example of mineral acid comprises sulfuric acid, hydrochloric acid, nitric acid, nitrous acid, phosphoric acid, boric acid, Hydrogen bromide, perchloric acid etc.

The example of acid comprises the acid based on sulphur, for example sulfonic acid, poly-sulfonic acid (for example disulfonic acid),-sulfinic acid, comprise monomer and polymerization organic sulfonic acid, for example Phenylsulfonic acid, alkyl benzene sulphonate (ABS), alkyl and aliphatic sulfonic acid, toluenesulphonic acids and naphthene sulfonic acid of aromatic sulfonic acid for example.The example of sulfonic acid comprises tosic acid, Phenylsulfonic acid, cresol sulfonic acid, 4-ethyl phenenyl azochlorosulfonate acid, xylene monosulfonic acid, acid dimethyl, phenolsulfonic acid, dinonylnaphthalene sulfonic acid (DNNSA), dinonylnaphthalene disulfonic acid (DNNDSA), Witco 1298 Soft Acid (DDBSA), methylsulfonic acid etc.Example also comprises for example poly-(styrene sulfonic acid), sulfonation fluoropolymer (sulfonation tetrafluoroethylene (Nafion for example for example of sulfonate resin ^?)) etc.

Described acid can be the acid based on phosphorus, for example phosphoric acid and its derivative, phosphorous acid and its derivative, the acid based on organophosphorus and phosphoric acid ester, such as alkyl and dialkyl group phosphate ester acid etc.Example comprises acid phosphoric acid pentyl ester, acid di(2-ethylhexyl)phosphate pentyl ester, acid butyl phosphate, dibutyl acid phosphate, acid phosphate ester, acid diethyl phosphoric acid, acid octyl phosphate, acid dioctylphosphoric acid ester etc.They can be the sour metal-salt based on phosphorus, for example metal-salt of phosphoric acid and phosphoric acid ester.

In some embodiments, described acid can be present in composition by following amount: about 5-approximately 95 % by weight or about 10-approximately 90 % by weight or about 10-approximately 70 % by weight or about 20-approximately 70 % by weight or about 30-approximately 70 % by weight or about 40-approximately 60 % by weight, the gross weight based on acid and aromatic substance.

In some cases, acid can exist by following weight ratio with respect to graphene film: the about 75:25 of about 0.1:99.9-, or the about 75:25 of about 0.5:99.5-, or the about 50:50 of about 0.5:99.5-, or the about 25:75 of about 0.5:99.5-, or the about 15:85 of about 0.5:99.5-, or the about 10:90 of about 0.5:99.5-, or the about 5:95 of about 0.5:99.5-, or the about 75:25 of about 1:99-, or the about 50:50 of about 1:99-, or the about 25:75 of about 1:99-, or the about 15:85 of about 1:99-, or the about 10:90 of about 1:99-, or the about 5:95 of about 1:99-, or the about 75:25 of about 2:98-, or the about 50:50 of about 2:98-, or the about 25:75 of about 2:98-, or the about 15:85 of about 2:98-, or the about 10:90 of about 2:98-, or the about 5:95 of about 2:98-, or the about 50:50 of about 5:95-, the about 25:75 of about 5:95-, the about 75:25 of about 10:90-, the about 50:50 of about 10:90-, the about 25:75 of about 10:90-.

Graphene film is for preferably having the about 2630m of about 100- ²the graphite flake of the surface-area of/g.In some embodiments, graphene film mainly, almost entirely or fully comprises complete exfoliate plumbago single slice (these be approximately≤1nm thick and be commonly referred to " Graphene "), and in other embodiments, at least partly graphene film can comprise the exfoliate graphite flake of part, wherein two or more graphite flakes not each other sheet peel off.Graphene film can comprise fully and the mixture of exfoliate graphite flake partly.Graphene film is different from carbon nanotube.Graphene film can have " sheet (platey) " (for example two dimension) structure and not have the needle-like form of carbon nanotube.Can respectively do for oneself the shortest size (being thickness) large, or large, or large, or large, or large, or large at least about 10,000 times at least about 5000 times at least about 1000 times at least about 100 times at least about 50 times at least about 10 times of described of two longest dimensions of graphene film.

Can use any applicable method to manufacture graphene film.For example, they can be by acquisitions such as graphite, graphite oxide, expansible black lead, expanded graphites.They can peel off acquisition by the physics of graphite, by for example graphene film being peeled off, ground or mills.They can by inorganic precursor for example silicon carbide manufacture.They can for example, by chemical vapour deposition manufacture (reacting on metallic surface by methane and hydrogen).They can be by for example, going back carbinol as ethanol with metal (basic metal is as sodium), and the follow-up pyrolysis of alkoxide product and manufacture (Nature Nanotechnology (2009), 4,30-33 reports this method).They can be by graphite in dispersion scale off or graphite oxide scaling off and reducing subsequently exfoliate graphite oxide in dispersion made.Graphene film can be by making below: expansible black lead scaled off, then inserts, and other means of supersound process or the separated sheet through inserting (referring to, for example, Nature Nanotechnology (2008), 3,538-542).They can be by graphite insertion and follow-uply product heat in suspension is scaled off etc. manufacture.

Graphene film can be made by graphite oxide (also referred to as graphitic acid or graphene oxide).Graphite available oxidant and/or intercalating agent are processed and through scaling off.Graphite also available intercalating agent is processed and through electrochemical oxidation with scale off.Graphene film can be by by graphite and/or graphite oxide, ultrasonic the scaling off of suspension in liquid (it can comprise tensio-active agent and/or intercalating agent) forms.Dispersion liquid or the suspension of graphite oxide of scaling off can be reduced into graphene film subsequently.Graphene film also can for example, form by the mechanical treatment (grind or mill) to exfoliated graphite or graphite oxide (it is reduced into graphene film subsequently).

Graphite oxide is reduced into Graphene can and can carry out the graphite oxide of dry form by means of chemical reduction among dispersion liquid etc.The example of useful chemical reducing agent includes but not limited to hydrazine (for example hydrazine, N, N-dimethylhydrazine etc.), sodium borohydride, citric acid, quinhydrones, isocyanic ester (such as phenylcarbimide), hydrogen, hydrogen plasma etc.Scale off for example, dispersion liquid in carrier (mixture of water, organic solvent or solvent) of graphite oxide or suspension can be used any applicable method manufacture (for example supersound process and/or mechanical mill or mill) and be reduced into graphene film.

Graphite oxide can be produced by any method known in the art, for example, by a kind of method, it comprise with one or more chemical oxidizing agents and optional intercalating agent for example sulfuric acid carry out graphite oxide.The example of oxygenant comprises nitric acid, nitrate (for example saltpetre and SODIUMNITRATE), perchlorate, Potcrate, sodium chlorate, chromic acid, potassiumchromate, Sodium chromate, potassium bichromate, sodium dichromate 99, hydrogen peroxide, sodium permanganate and potassium permanganate, phosphoric acid (H ₃pO ₄), Vanadium Pentoxide in FLAKES, hydrosulphite etc.Preferred oxygenant comprises KClO ₄, HNO ₃and KClO ₃; KMnO ₄and/or NaMnO ₄; KMnO ₄and NaNO ₃; K ₂s ₂o ₈and P ₂o ₅and KMnO ₄; KMnO ₄and HNO ₃; And HNO ₃.Preferred intercalating agent comprises sulfuric acid.Graphite also available intercalating agent is processed and through electrochemical oxidation.The example of manufacturing the method for graphite oxide comprises Staudenmaier(Ber. Stsch. Chem. Ges. (1898), 31,1481) and those of Hummers (J.Am.Chem.Soc. (1958), 80,1339) description.

Prepare the example of method of graphene film for graphite oxidation is become to graphite oxide, then its heat is scaled off to form graphene film (also referred to as the exfoliate graphite oxide of heat), as described in US 2007/0092432, its disclosure is incorporated to herein at this by reference.It is few or not corresponding to the signal of graphite or graphite oxide that the graphene film so forming can show in their X-ray diffraction pattern.

Described heat scales off and can be undertaken by continuous, the semicontinuous method such as in batches.

Heating can batch processes or continuation method is carried out and can in different atmosphere, carry out, and comprises inertia and reducing atmosphere (for example nitrogen, argon and/or nitrogen atmosphere).Can, from below several seconds or several hours or High variation more, depend on the temperature of use and the characteristic of expecting in final hot exfoliate graphite oxide heat-up time.Heating can be carried out in any suitable container, containers such as vitreosil, mineral, metal, carbon (such as graphite), pottery.Can use photoflash lamp or microwave to heat.During heating, graphite oxide can be included in substantially constant position in single batch reactions container, or can be during reaction with the continuous or one or more containers of batch mode transmission process.Can use any suitable means to heat, comprise and use stove and Infrared heaters.

The heat that can carry out graphite oxide scales off and/or the example of the temperature of reducing be at least about 150 ℃, at least about 200 ℃, at least about 300 ℃, at least about 400 ℃, at least about 450 ℃, at least about 500 ℃, at least about 600 ℃, at least about 700 ℃, at least about 750 ℃, at least about 800 ℃, at least about 850 ℃, at least about 900 ℃, at least about 950 ℃, at least about 1000 ℃, at least about 1100 ℃, at least about 1500 ℃, at least about 2000 ℃ with at least about 2500 ℃.Preferred scope comprises approximately 2500 ℃ of approximately 750 ℃-Yue 3000 ℃, about 850-2500 ℃, approximately 2500 ℃ of about 950-, approximately 1500 ℃ of about 950-, approximately 3100 ℃ of about 750-, about 850-2500 ℃ or about 950-.

Heat-up time can be for being less than one second to many minutes.For example, can be less than approximately 0.5 second heat-up time, be less than approximately 1 second, be less than approximately 5 seconds, be less than approximately 10 seconds, be less than approximately 20 seconds, be less than approximately 30 seconds or be less than approximately 1 minute.Heat-up time can be at least about 1 minute, at least about 2 minutes, at least about 5 minutes, at least about 15 minutes, at least about 30 minutes, at least about 45 minutes, at least about 60 minutes, at least about 90 minutes, at least about 120 minutes, at least about 150 minutes, at least about 240 minutes, approximately 0.01 second-Yue 240 minutes, approximately 0.5 second-Yue 240 minutes, approximately 1 second-Yue 240 minutes, approximately 1 minute-Yue 240 minutes, approximately 0.01 second-Yue 60 minutes, approximately 0.5 second-Yue 60 minutes, approximately 1 second-Yue 60 minutes, approximately 1 minute-Yue 60 minutes, approximately 0.01 second-Yue 10 minutes, approximately 0.5 second-Yue 10 minutes, approximately 1 second-Yue 10 minutes, approximately 1 minute-Yue 10 minutes, approximately 0.01 second-Yue 1 minute, approximately 0.5 second-Yue 1 minute, approximately 1 second-Yue 1 minute, be no more than approximately 600 minutes, be no more than approximately 450 minutes, be no more than approximately 300 minutes, be no more than approximately 180 minutes, be no more than approximately 120 minutes, be no more than approximately 90 minutes, be no more than approximately 60 minutes, be no more than approximately 30 minutes, be no more than approximately 15 minutes, be no more than approximately 10 minutes, be no more than approximately 5 minutes, be no more than approximately 1 minute, be no more than approximately 30 seconds, be no more than approximately 10 seconds or be no more than approximately 1 second.During heat-processed, temperature can change.

The example of heating rate comprise at least about 120 ℃/min, at least about 200 ℃/min, at least about 300 ℃/min, at least about 400 ℃/min, at least about 600 ℃/min, approximately 800 ℃/min, at least about 1000 ℃/min, at least about 1200 ℃/min, at least about 1500 ℃/min, at least about 1800 ℃/min with at least about 2000 ℃/min.

Graphene film can or be reduced into through calcination has more high-carbon: the graphene film of oxygen ratio, and for example, by heating (, in the system purging with rare gas element or hydrogen) under reducing atmosphere condition.Reduction/annealing temperature is preferably at least about 300 ℃ or at least about 350 ℃ or at least about 400 ℃ or at least about 500 ℃ or at least about 600 ℃ or at least about 750 ℃ or at least about 850 ℃ or at least about 950 ℃ or at least about 1000 ℃.The temperature of using can be, and for example approximately 3000 ℃ of about 750-or about 850-2500 ℃ or about 950-are approximately 2500 ℃.

Heat-up time can be for example, at least about 1 second or at least about 10 seconds or at least about 1 minute or at least about 2 minutes or at least about 5 minutes.In some embodiments, be at least about 15 minutes heat-up time or approximately 30 minutes or approximately 45 minutes or approximately 60 minutes or approximately 90 minutes or approximately 120 minutes or approximately 150 minutes.During annealing/reduction process, temperature can change within these scopes.

Heating can be carried out under multiple condition, is for example included in, in inert atmosphere (argon or nitrogen) or reducing atmosphere, and hydrogen (comprise and be diluted in for example hydrogen in argon or nitrogen of rare gas element) for example, or under vacuum.Heating can be carried out in any suitable container, for example vitreosil or mineral or earthenware porcelain receptacle or metal vessel.Heated material (comprising any initial material and spawn or intermediate) can be included in substantially constant position in single batch reactions container, or can in continuous or batch reactions, during reaction transmit through one or more containers.Heating can be used any suitable means to carry out, and comprises the use of stove and Infrared heaters.

Graphene film preferably has following table area: at least about 100m ²/ g to or at least about 200m ²/ g or at least about 300m ²/ g or at least about 350m ²/ g or at least about 400m ²/ g or at least about 500m ²/ g or at least about 600m ²/ g or at least about 700m ²/ g or at least about 800m ²/ g or at least about 900m ²/ g or at least about 700m ²/ g.Described surface-area can be the about 1100m of about 400- ²/ g.The long-pending 2630m that can be as calculated of theoretical maximized surface ²/ g.Surface-area comprises all values and the subvalue between them, especially comprises 400,500,600,700,800,900,1000,1100,1200,1300,1400,1500,1600,1700,1800,1900,2000,2100,2200,2300,2400,2500 and 2630m ²/ g.

Graphene film can have the equal long-width ratio of following number: about 100-approximately 100,000 or about 100-approximately 50,000 or about 100-approximately 25,000 or about 100-approximately 10,000 (wherein " aspect ratio " is defined as the longest dimension of described and the ratio of short size).

Surface-area can be used nitrogen absorption/BET method or the methylene blue in liquor (MB) staining under 77K to measure.

Staining is carried out as follows: the graphene film of known quantity is added in flask.Then by every gram of graphene film at least the MB of 1.5g join in flask.Ethanol is added in flask and by mixture supersound process approximately 15 minutes.Then by ethanol evaporation and by the water of known quantity, add in flask to dissolve again free MB.Make insoluble material sedimentation, preferably pass through sample centrifugation.The concentration of MB in solution is used ultraviolet-visible spectrophotometer to measure, by measuring at λ _maxthe absorption absorbing with respect to normal concentration under=298nm.

Difference between the amount of the initial MB adding and the amount existing in solution of measuring by ultraviolet visible spectrophotometry thinks to be adsorbed on the amount of the lip-deep MB of graphene film.Then the surface-area of graphene film is used the MB of every 1mg absorption to cover 2.54m ²the value of surface-area is calculated.

Graphene film can have about 0.01-at least about 200kg/m ³volume density.Volume density comprises all values and the subvalue between them, especially comprises 0.05,0.1,0.5,1,5,10,15,20,25,30,35,50,75,100,125,150 and 175kg/m ³.

Graphene film can be used following functionalized: for example oxygen-containing functional group (comprises, for example hydroxyl, carboxyl and epoxy group(ing)) and conventionally have at least about 1:1 or more preferably at least about the overall carbon of 3:2: oxygen mol ratio (C/O ratio), by ontology element analysis, measure.Carbon: the example of oxygen ratio comprises: the about 85:15 of about 3:2-, the about 20:1 of about 3:2-, the about 30:1 of about 3:2-, the about 40:1 of about 3:2-, the about 60:1 of about 3:2-, the about 80:1 of about 3:2-, the about 100:1 of about 3:2-, the about 200:1 of about 3:2-, the about 500:1 of about 3:2-, the about 1000:1 of about 3:2-, about 3:2-is greater than 1000:1, the about 30:1 of about 10:1-, the about 100:1 of about 80:1-, the about 100:1 of about 20:1-, the about 500:1 of about 20:1-, the about 1000:1 of about 20:1-, the about 300:1 of about 50:1-, the about 500:1 of about 50:1-, with the about 1000:1 of about 50:1-.In some embodiments, carbon: oxygen ratio is at least about 10:1 or at least about 15:1 or at least about 20:1 or at least about 35:1 or at least about 50:1 or at least about 75:1 or at least about 100:1 or at least about 200:1 or at least about 300:1 or at least about 400:1 or 500:1 or at least about 750:1 or at least about 1000:1 or at least about 1500:1 or at least about 2000:1 at least.Carbon: oxygen is than also comprising all values and the subvalue between these scopes.

Graphene film can comprise the kink of atomic scale.These kinks can existence or the chemical functionalization of lattice imperfection cause in the two-dimentional hexagonal lattice structure of graphite-based facial planes.

Described composition also can comprise graphite (comprise natural, crystallization, and synthetic, annealing, pyrolysis, height-oriented pyrolysis etc. graphite).Graphite: the weight ratio of graphene film can be the about 98:2 of about 2:98-or the about 95:5 of about 5:95-or the about 90:10 of about 10:90-or the about 80:20 of about 20:80-or about 30:70-70:30 or the about 90:10 of about 40:60-or the about 85:15 of about 50:50-or the about 85:15 of about 60:40-or the about 85:15 of about 70:30-.

Graphene film can comprise the two or more graphene powders with different-grain diameter distribution and/or pattern.Graphite also can comprise the two or more powdered graphites with different size distribution and/or pattern.

Graphene film and aromatic substance can be with combination of polymers to prepare mixture (comprising polymer complex) etc.They can be dispersed in one or more solvents under being with or without polymer binder.They can be used for hot transfer printing application.They can be used on electrode, such as for following those: solar cell (comprising dye sensitization solar battery, organic solar batteries etc.), photodiode, battery (such as the electrode for batteries such as rechargeable, lithium ion, lighium polymer, lithium air), electrical condenser (comprising ultracapacitor) etc.Polymer complex can be used for choke application.Rubber composite can be used for tire applications.Composition can be the form of tackiness agent.

Composition can be the form of ink and coating.Term " ink " and " coating " mean the composition that its form is suitable for being coated to substrate, and its be coated to after substrate, when it is coated to substrate and any coating aftertreatment (such as evaporation, crosslinked, solidify etc.) before and latter two situation under material.The component of ink and coating composition can change during these stages.Ink and coating can optionally also comprise polymeric binder.

Graphene film and aromatic substance can be used any applicable method and combination of polymers, comprise melt (using such as single screw rod or twin screw extruder, blender, kneader, banbury mixers etc.) and solution/dispersion blend.Polymkeric substance can be used as binding agent.When using, polymkeric substance can be the polymkeric substance of heat curing-type, thermoplastics type, non-melt processible etc.Polymkeric substance also can comprise monomer, its can by applying coating to before substrate, during or polymerization afterwards.Polymer-binder can be through crosslinked or curing after described coating has been coated on substrate.The example of polymkeric substance includes but not limited to polyolefine (polyethylene for example, LLDPE (LLDPE), Low Density Polyethylene (LDPE), high density polyethylene(HDPE), polypropylene and olefin copolymer), styrene/butadiene rubbers (SBR), styrene/ethylene/butadiene/styrene copolymers (SEBS), isoprene-isobutylene rubber, ethylene/propene copolymer (EPR), ethylene/propylene/diene monomer multipolymer (EPDM), polystyrene (comprising high impact polystyrene), poly-(vinyl-acetic ester), ethylene/vinyl acetate (EVA), poly-(vinyl alcohol), ethylene/vinyl alcohol copolymer (EVOH), gather (vinyl butyral) (PVB), poly-(vinyl alcohol formal), poly-(methyl methacrylate) and other acrylic ester polymer and multipolymer (methyl methacrylate polymer for example, alkylmethacrylate polymer, polymkeric substance derived from one or more acrylate, methacrylic ester, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, butyl acrylate, butyl methacrylate, glycidyl acrylate and methacrylic ester etc.), alkene and styrol copolymer, acrylonitrile/butadiene/styrene (ABS), styrene/acrylonitrile polymer (SAN), phenylethylene/maleic anhydride copolymer, iso-butylene/copolymer-maleic anhydride, ethylene/acrylic acid copolymer, poly-(vinyl cyanide), poly-(vinyl-acetic ester) and poly-(vinyl-acetic ester) multipolymer, PVP and PVP multipolymer, vinyl-acetic ester and vinylpyrrolidone copolymer, polycarbonate (PC), polymeric amide, polyester, liquid crystalline polymers (LCP), gather (lactic acid) (PLA), gather (oxidation phenylene) (PPO), PPO-polyamide alloy, polysulfones (PSU), polysulphide, polyetherketone (PEK), polyether-ether-ketone (PEEK), polyimide, polyoxymethylene (POM) homopolymer and multipolymer, polyetherimide, fluorinated ethylene-propylene polymer (FEP), poly-(vinyl fluoride), poly-(vinylidene), poly-(vinylidene chloride), gather (vinylchlorid) (PVC), urethane (thermoplasticity and thermoset (comprising crosslinked urethane such as those crosslinked amine etc.), aromatic poly amide (Kevlar for example ^?and Nomex ^?), polysulphide, tetrafluoroethylene (PTFE), polysiloxane (comprises poly-dimethylene siloxanes, dimethyl siloxane/vinyl methylsiloxane multipolymer, poly-(dimethyl siloxane) of vinyl-dimethyl radical siloxane end-blocking etc.), elastomerics, epoxy polymer (comprises that crosslinked epoxy polymer for example uses polysulfones, those that amine etc. are crosslinked), polyureas, Synolac, cellulose polymer compound (soluble cotton for example, ethyl cellulose, Type 3U, carboxymethyl cellulose, cellulose acetate, cellulose acetate propionate and cellulose acetate butyrate), polyethers (for example poly-(ethylene oxide), poly-(propylene oxide), poly-(propylene glycol), oxide compound/propylene oxide copolymer etc.), acrylic latex polymkeric substance, polyester acrylic ester oligomer and polymkeric substance, polyester glycol diacrylate ester polymer, UV-cured resin etc.

Elastomeric example includes but not limited to: urethane, copolyether ester, rubber (comprising isoprene-isobutylene rubber and natural rubber), styrene/butadiene copolymers, styrene/ethylene/butadiene/styrene copolymers (SEBS), polyisoprene, ethylene/propene copolymer (EPR), ethylene/propylene/diene monomer multipolymer (EPDM), polysiloxane and polyethers (for example poly-(ethylene oxide), poly-(propylene oxide) and their multipolymer).

The example of polymeric amide includes but not limited to aliphatic polyamide, and (for example polymeric amide 4,6; Polyamide 6,6; Polyamide 6; Polymeric amide 11; Polymeric amide 12; Polyamide 6,9; Polyamide 6,10; Polyamide 6,12; Polymeric amide 10,10; Polymeric amide 10,12; With polymeric amide 12,12), alicyclic ring polymeric amide and aromatic poly amide (for example gather (an xylylene adipamide) (polymeric amide MXD, 6)) and polyterephthalamide poly-(ten dimethylene terephthalamides) (polymeric amide 12 for example, T), poly-(decamethylene terephthalamide) (polymeric amide 10, T), poly-(nine methylene radical terephthalamides) (polymeric amide 9, T), the polymeric amide of polymeric amide, hexa-methylene terephthalamide and the 2-methyl pentamethylene terephthalamide of hexa-methylene terephthalamide and hexa-methylene adipamide etc.Polymeric amide can be polymkeric substance and the multipolymer (polymeric amide with at least two different repeating units) with about 120-255 ℃ fusing point, it comprise have approximately 230 ℃ or more low melting point aliphatic copolyamide, have approximately 210 ℃ or more low melting point aliphatic copolyamide, have approximately 200 ℃ or more low melting point aliphatic copolyamide, there is approximately 180 ℃ or the aliphatic copolyamide etc. of low melting point more.These example comprises those that sold by Henkel and sold by Cognis by Versamid by trade name Macromelt.

The example of acrylic ester polymer comprises those that for example, manufacture by the polymerization of one or more vinylformic acid (comprising vinylformic acid, methacrylic acid etc.) and their derivative (ester).Example comprises methyl acrylate polymer, methyl methacrylate polymer and alkylmethacrylate polymer.Example comprises derived from following polymkeric substance: one or more acrylate, methacrylic ester, vinylformic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, butyl acrylate, butyl methacrylate, glycidyl acrylate, glycidyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylic ester, Hydroxyethyl acrylate, (methyl) Hydroxyethyl acrylate, vinyl cyanide etc.Polymkeric substance can comprise the repeating unit derived from other monomer, such as alkene (such as ethene, propylene etc.), vinyl-acetic ester, vinyl alcohol, vinyl pyrrolidone etc.They can comprise acrylic ester polymer and the multipolymer (for example ionomer resin) of part neutralization.

The example of polymkeric substance comprises the International by Lucite, the Elvacite that Inc provides ^?polymkeric substance, comprises Elvacite ^?2009,2010,2013,2014,2016,2028,2042,2045,2046,2550,2552,2614,2669,2697,2776,2823,2895,2927,3001,3003,3004,4018,4021,4026,4028,4044,4059,4400,4075,4060,4102 etc.Other type of polymer comprises Bynel ^?polymkeric substance (the Bynel that for example DuPont provides ^?2022) and Joncryl ^?polymkeric substance (Joncryl for example ^?678 and 682).

The example of polyester include but not limited to gather (butylidene terephthalate) (PBT), poly-(ethylidene terephthalate) (PET), poly-(trimethylene terephthalate) (PPT), poly-(ethylidene is to naphthalate) (PEN), poly-(cyclohexanedimethanol terephthalate) (PCT)) etc.

In some embodiments, polymkeric substance has following acid number: at least about 5 or at least about 10 or at least about 15 or at least about 20.

In some embodiments, the glass transition temperature of at least one polymkeric substance is not more than approximately 100 ℃, 90 ℃ or be not more than approximately 80 ℃ or be not more than approximately 70 ℃ or be not more than approximately 60 ℃ or be not more than approximately 50 ℃ or be not more than approximately 40 ℃.

In some cases, when using tackiness agent, it can exist by following amount with respect to graphene film and graphite (when using): about 1-approximately 99 % by weight, or about 1-approximately 50 % by weight, or about 1-approximately 30 % by weight, or about 1-approximately 20 % by weight, or about 5-approximately 80 % by weight, or about 5-approximately 60 % by weight, or about 5-approximately 30 % by weight, or about 15-approximately 85 % by weight, or about 15-approximately 60 % by weight, or about 15-approximately 30 % by weight, or about 25-approximately 80 % by weight, or about 25-approximately 50 % by weight, or about 40-approximately 90 % by weight, or about 50-approximately 90 % by weight, or about 70-approximately 95 % by weight, the gross weight that adds graphite (when existing) based on tackiness agent and Graphene.

The example that graphene film and aromatic substance dispersible solvent therein comprises that isoparaffin water, distillation or synthetic is (as Isopar ^?and Norpar ^?(both manufacture by Exxon) and Dowanol ^?(by Dow, being manufactured), oranges and tangerines terpenes and the mixture that comprises oranges and tangerines terpenes (Purogen for example, Electron and Positron (all by Ecolink, being manufactured)), terpenes and terpenol (comprise terpinol, comprise α-terpinol), limonene, aliphatic series petroleum fractions, alcohol (methyl alcohol for example, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, amylalcohol, primary isoamyl alcohol, hexanol, enanthol, octanol, diacetone alcohol, butyl glycol etc.), ketone (acetone for example, methyl ethyl ketone, pimelinketone, isobutyl ketone, 2, 6, 8, trimethylammonium-4-nonanone etc.), ester (methyl acetate for example, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, tert.-butyl acetate, Ethyl carbitol acetate etc.), glycol ether, ester and alcohol (2-(2-ethoxy ethoxy) ethanol for example, propylene glycol monomethyl ether and other propylene glycol, ethylene glycol monobutyl ether, 2-methoxy ethyl ether (diglyme), propylene glycol monomethyl ether (PGME), with other glycol ether, glycol ether acetate and propylene glycol acetic ester, diethylene glycol monoethyl ether acetic ester, 1-methoxy-2-propanol acetic ester (PGMEA), and hexylene glycol (for example Hexasol (being provided by SpecialChem)), diester (Succinic acid dimethylester for example, Methyl glutarate, dimethyl adipate), dimethyl sulfoxide (DMSO) (DMSO), 1, 3-dimethyl-3, 4, 5, 6-tetrahydrochysene-2 (1H)-pyrimidone (DMPU), imide, acid amides (dimethyl formamide (DMF) for example, N,N-DIMETHYLACETAMIDE etc.), cyclic amide (for example N-Methyl pyrrolidone and 2-Pyrrolidone), lactone (beta-propiolactone for example, γ-valerolactone, δ-valerolactone, gamma-butyrolactone, 6-caprolactone), cyclin imide (imidazolidone N for example for example, N '-methylimidazole alkane ketone (1, 3-dimethyl-2-imidazolidone)), aromatic solvent aromatic solvent mixture (toluene for example, dimethylbenzene, sym-trimethylbenzene, isopropyl benzene etc.), petroleum fractions, the mixture of petroleum naphtha (for example VM & P petroleum naphtha) and above-mentioned two or more, and the mixture of above-mentioned one or more and other carrier.Solvent can be low VOC or VOC free solvent, non-hazardness atmospheric pollution solvent and non-halogenated solvent.

Composition can comprise following additive: such as dispersing auxiliary (comprising tensio-active agent, emulsifying agent and wetting aid), bonding agent, thickening material (comprising clay), defoamer and foam inhibiting agent, biocide, additional filler, flow enhancing agent, stablizer, crosslinked and solidifying agent, conductive additive etc.

The example of dispersing auxiliary comprise glycol ether (for example poly-(ethylene oxide), derived from the segmented copolymer of ethylene oxide and propylene oxide (for example by BASF by Pluronic ^?those that trade name is sold), acetylenic glycol (for example 2,5,8,11-tetramethyl--6-dodecyne-5,8-diol ethoxylate and by Air Products with trade name Surfynol ^?and Dynol ^?other that sell), carboxylate salt (comprising basic metal and ammonium salt) and polysiloxane.

The example of grinding aid comprise stearate (for example Al, Ca, Mg and Zn stearate) and alkynes state glycol (for example by Air Products with trade name Surfynol ^?and Dynol ^?those that sell).

The example of bonding agent comprise titanium chelate and other titanium compound for example titanium phosphate complex compound (comprising butyl phosphoric acid titanium), titanic acid ester, diisopropoxy titanium two (ethyl-3-oxygen base butyric ester, titanium isopropoxide pendant acetoacetonate moieties and by Johnson-Matthey Catalysts by other of trade mark Vertec sale.

Composition optionally comprises at least one " multichain lipid ", and this term refers to natural generation or the synthetic lipid with polarity head end group and connected at least two nonpolar tail end groups.The example of polarity head end group comprise containing containing aerobic, sulphur and halogen, phosphoric acid ester, acid amides, ammonium, amino acid (comprising α-amino acid), carbohydrate, polysaccharide, ester (comprising glyceryl ester), zwitter-ion group etc.

Tail end group can be identical or different.The example of tail end group comprises alkane, alkene, alkynes, aromatic substance etc.They can be hydrocarbon, functionalized hydrocarbon etc.Tail end group can be saturated or undersaturated.They can be linearity or branching.Tail end group can be derived from lipid acid, such as oleic acid, palmitinic acid, stearic acid, eicosanoic acid, sinapinic acid, arachidonic acid, linolic acid, linolenic acid, oleic acid etc.

The example of multichain lipid includes but not limited to Yelkin TTS and other phosphatide (for example phosphatidylcholine, glycerophospholipids (comprising phosphatidylserine, phosphatidylinositols, phosphatidyl ethanolamine (kephalin) and phosphatidyl glycerol) and sphingophospholipid); Glycolipid (for example glucosyl-cerebroside); Glycolipid; Sphingolipid (for example ceramide, triglyceride and triglyceride level, phosphoric acid sphingolipid and glycosphingolipid); Deng.They can be both sexes, comprise zwitterionic.

The example of thickening material comprise glycol ether (for example poly-(ethylene oxide), derived from the segmented copolymer of ethylene oxide and propylene oxide (for example by BASF by trade name Pluronic ^?those that sell), long-chain carboxylic acid's salt (as the stearate of aluminium, calcium, zinc etc., oleate, palmitate etc.), silico-aluminate are (for example, by Unimin Specialty Minerals Minex by name ^?and press Aerosil by Evonik Degussa ^?9200 sell those), pyrolytic silicon dioxide, natural and synthetic zeolite etc.

Composition can comprise electricity and/or thermal conduction component, such as metal (comprising metal alloy), conductive metal oxides, conductive carbon, polymkeric substance, metal coated material etc.These components can adopt various ways, comprise particle, powder, thin slice, paper tinsel, pin etc.

Metal example includes but not limited to silver, copper, aluminium, platinum, palladium, nickel, chromium, gold, zinc, tin, iron, gold, lead, steel, stainless steel, rhodium, titanium, tungsten, magnesium, brass, bronze, colloidal metal etc.The example of metal oxide comprises antimony tin and tin indium oxide and is for example coated with the material of the filler of metal oxide.Metal and metal oxide coated material include but not limited to that the carbon of metal coated and graphite fibre, the glass fibre of metal coated are, the stupalith of the granulated glass sphere of metal coated, metal coated (such as bead) etc.These materials can be coated with various metals, comprise nickel.

The example of conductive polymers include but not limited to polyacetylene, poly-ethylidene dioxy base thiophene (PEDOT), poly-(styrene sulfonate) (PSS), PEDOT:PSS multipolymer, Polythiophene and Polythiophene, poly-(3-alkylthrophene), poly-(2,5-bis-(3-tetradecyl thiophene-2-yl) thieno-[3,2-b] thiophene) (PBTTT), poly-(phenylene vinylidene), poly-pyrene, polycarbazole, poly-Azulene, poly-azepine , poly-fluorenes, poly-naphthalene, poly-different naphthalene, polyaniline, polypyrrole, poly-(sulfuration phenylene), polycarbazole (polycarbozole), poly-indoles, polyhenylene, above-mentioned one or more multipolymer etc., and their derivative and multipolymer.Conductive polymers can be doping or unadulterated.The doping such as their available boron, phosphorus, iodine.

The example of conductive carbon includes but not limited to graphite (comprise natural, crystallization and synthetic, annealing, pyrolysis, height-oriented pyrolysis etc. graphite), graphitized carbon, mesoporous carbon, carbon black, carbon fiber and protofibril, carbon whisker, the carbon nanofiber of vapor phase growth, the carbon fiber of metal coated, carbon nanotube (comprising single wall and many walls nanotube), soccerballene, activated carbon, carbon fiber, expanded graphite, expansible black lead, graphite oxide, hollow carbon balls, foamy carbon etc.

Ink and coating can be by forming graphene film and aromatic substance and at least one solvent and/or tackiness agent and optional other additive blend.Blend can be used one or more aforesaid methods to complete.Composition can be used the preparation of any applicable method, comprise wet or drying method and in batches, semicontinuous and continuation method.The dispersion liquid of graphene film and one or more aromatic substance (comprising ink and formulation for coating material), suspension, solution etc. can for example, by being used applicable mixing, dispersion and/or mixed technology manufacture or processing (, mill/grinding, blend, dispersion, suspension etc.).

For example, the component of composition, graphene film for example, aromatic substance, graphite (if use), binding agent, one or more in carrier and/or other component can be treated (for example, mill/grind, blend etc., by applicable mixing, dispersion and/or mixed technology and equipment, comprise ultrasonic device, high shear mixer, ball mill, pulverising apparatus, sand mill, two roller mills, three-roll mill, freeze grinding crusher, forcing machine, kneading machine, double planetary mixer, three planetary-type mixers, high pressure homogenizer, horizontal and vertical wet lapping grinding machine etc.).That (the comprising grinding) technology of processing can be wet type or dry type and can be continuous or discrete.The applicable material that is used as grinding medium comprises the ceramic dielectic (such as the stable zirconium white of cerium yttrium) of metal, carbon steel, stainless steel, pottery, stabilization, PTFE, glass, wolfram varbide etc.For example these method can be used for changing granularity and/or the pattern of graphite, graphene film, other component and blend or two or more components.

Component can be jointly or individual curing and can experience multi task process (the comprising mixing/blend) stage, and each relates to one or more components (comprising blend).

Be not particularly limited graphene film, graphite (if use), aromatic substance and other component is treated and the mode of combination.For example graphene film and/or graphite can be processed into respectively given size distribution and/or pattern then be with or without annexing ingredient exist under combination for further processing.Untreated graphene film and/or graphite can combine with the graphene film of processing and/or graphite, and are having or do not having under annexing ingredient further treated.Treated and/or untreated graphene film and/or treated and/or untreated graphite can with other combination of components, for example one or more binding agents, are then combined with treated and/or untreated graphene film and/or treated and/or untreated graphite.Can further combine or process with the treated and/or untreated graphene film of other combination of components and/or two or more combinations of treated and/or untreated graphite.Any aforementioned processing step can be carried out under the existence of at least one aromatic substance.

In one embodiment, if use multichain lipid, before processing, can be joined graphene film (and/or graphite, if existed).

After blend and/or grinding steps, annexing ingredient can join in composition, includes but not limited to thickening material, viscosity modifier, binding agent etc.Also can carry out diluted composition by adding more multichip carrier.

Ink and coating can be coated on diversified substrate, include but not limited to: pliable and tough and/or stretchable material, silicone and other elastomerics and other polymeric material, metal (aluminium for example, copper, steel, stainless steel etc.), tackiness agent, heat-sealable material (Mierocrystalline cellulose for example, Biaially oriented polypropylene (BOPP), poly-(lactic acid), urethane etc.), fabric (comprising cloth) and textiles are (for example cotton, wool, polyester, regenerated fiber etc.), cloth, glass and other mineral, pottery, silicon face, timber, paper, card board kai, cardboard, cellulose-based material, glassine paper, label, silicon and other semi-conductor, veneer sheet, corrugated material, concrete, brick and other material of construction etc.Substrate can be following form: film, paper, wafer, larger three-dimensional body etc.

Before ink and applying coating, substrate can for example, by other coating (paint) or similar material processing.Example comprises the substrate (for example PET) that is coated with tin indium oxide, antimony tin etc.They can be woven, non-woven, are net form formula etc.They can be woven, non-woven, are net form formula etc.

Substrate can be generally the material (comprising paper, cardboard, card board kai, glassine paper etc.) based on paper.Material based on paper can be through surface treatment.Surface-treated example comprises that coating is for example polymer coated, and it can comprise PET, polyethylene, polypropylene, acetic ester, nitrocotton etc.Coating can be tackiness agent.Material based on paper can selected size.

The example of polymeric material include but not limited to following those: it comprises thermoplastics and thermoset(ting)plastic, comprises elastomerics and rubber (comprising thermoplastics and thermoset(ting)plastic), silicone, fluoridize polysiloxane, natural rubber, isoprene-isobutylene rubber, chlorosulfonated polyethylene, chlorinatedpolyethylene, styrene/butadiene copolymers (SBR), styrene/ethylene/butadiene/styrene copolymers (SEBS), styrene/ethylene/butadiene/styrene copolymers with maleic anhydride graft, styrene/isoprene/styrene multipolymer (SIS), polyisoprene, paracril, hydrogenated nitrile-butadiene rubber, chloroprene rubber, ethylene/propene copolymer (EPR), ethylene/propylene/diene copolymers (EPDM), ethylene/vinyl acetate (EVA), R 1216/vinylidene/TFE copolymer, tetrafluoroethylene/propylene copolymer, fluoroelastomer, polyester (for example poly-(ethylene glycol terephthalate), poly-(butylene terephthalate), poly-(to naphthalic acid second diester), liquid crystal polyester, poly-(lactic acid) etc.), polystyrene, polymeric amide (comprising polyterephthalamide), polyimide (Kapton for example ^?), aromatic poly amide (Kevlar for example ^?and Nomex ^?), fluoropolymer (such as fluorinated ethylene propylene (FEP), tetrafluoroethylene (PTFE), poly-(vinyl fluoride), poly-(vinylidene) etc.), polyetherimide, poly-(vinylchlorid), poly-(vinylidene chloride), urethane (thermoplastic polyurethane (TPU) for example, Spandex (spandex), cellulose polymer compound (such as nitrocotton, cellulose acetate etc.), styrene/acrylonitrile polymer (SAN), acrylonitrile/butadiene/styrene polymkeric substance (ABS), polycarbonate, polyacrylic ester, poly-(methyl methacrylate), ethylene/vinyl acetate, thermoset epoxy compound and urethane, polyolefine is (such as polyethylene (comprising Low Density Polyethylene, high density polyethylene(HDPE), ultrahigh molecular weight polyethylene(UHMWPE) etc.), polypropylene (such as Biaially oriented polypropylene etc.), wheat is drawn (Mylar), Deng.They can be nonwoven material, for example DuPont Tyvek ^?.They can be jointing material or back of the body jointing material (for example carrying on the back pasted paper or paper surrogate).They can be the paper surrogate of base and mineral, for example, from the Teslin of PPG Industries ^?.Substrate can be transparent or translucent or optical material, for example glass, quartz, polymkeric substance (for example polycarbonate or poly-(methyl) acrylate (for example poly-(methyl methacrylate)).

Ink and coating can be used any applicable method to be coated on substrate, include but not limited to: smear, come down in torrents, rotation curtain coating, solution casting, dip coated, powder coated, by syringe or transfer pipet, spraying, curtain coating, lamination, coextrusion, EFI deposition, ink jet printing, spin coating, hot transfer printing (comprising laser transfer) method, scraping blade printing, silk screen printing, rotary screen printing, intaglio printing (gravure printing), lithography, intaglio printing (intaglio printing), digital printed, capillary printing, offset printing, electrohydrodynamic (EHD) printing (method of describing in WO 2007/053621, it is incorporated to herein by reference at this), micro-printing, intaglio plate bat printing, bat printing (tampon printing), stencilization, coiling rod coating (wire rod coating), draw, flexographic printing, punching press, xeroprinting, micro-contact printing, dip in a nano imprint, laser printing, via pen or similar means etc.Composition can be by multilayer coated.

After they are coated on substrate, ink and coating can be used any applicable technical cure, comprise dry and oven drying (in air or other inertia or atmosphere reactive), ultra-violet curing, infrared curing, dry, crosslinked, thermofixation, laser curing, infrared curing, microwave curing or be dried, sintering etc.

Curing ink and coating can have different thickness.For example, they optionally have at least about 2nm or at least about the thickness of 5nm.In various embodiments, coating optionally has following thickness: about 2nm-2mm, about 5nm-1mm, the about 100nm of about 2nm-, the about 200nm of about 2nm-, the about 500nm of about 2nm-, approximately 1 micron of about 2nm-, the about 200nm of about 5nm-, the about 500nm of about 5nm-, approximately 1 micron of about 5nm-, approximately 50 microns of about 5nm-, approximately 200 microns of about 5nm-, the about 200nm of about 10nm-, the about 500nm of about 50nm-, approximately 1 micron of about 50nm-, approximately 10 microns of about 100nm-, approximately 1 micron-2mm Yue, approximately 1 micron-1mm Yue, approximately 1 micron-Yue 500 microns, approximately 1 micron-Yue 200 microns, approximately 1 micron-Yue 100 microns, approximately 50 microns-1mm Yue, approximately 100 microns-2mm Yue, approximately 100 microns-1mm Yue, approximately 100 microns-Yue 750 microns, approximately 100 microns-Yue 500 microns, approximately 500 microns-2mm Yue, or approximately 500 microns-1mm Yue.

When being coated on substrate, ink and coating can have different forms.They can be used as film or line, pattern, letter, numeral, circuit, sign, identification tag and other shape and form.Ink and coating can completely or partially be covered by other material, such as seal coat, varnish, polymkeric substance, fabric etc.

Ink and coating can be on different points be coated on same substrate with the thickness changing, and are used in and in substrate, build three-dimensional structure.

Ink and coating can be used for surperficial passivation, such as metal (such as steel, aluminium etc.) surface, comprise that external application structure example is as bridge and buildings.The example of other purposes of ink and coating comprises: ultraviolet light resistant long-lived coating, wear-resistant coating, liquid (such as hydrocarbon, alcohol, water etc.) and/or gas are had to coating, conductive coating, electrostatic dissipation coating and the resistance to quick-fried and impact-resistant coating of osmotic resistance.They can be used for the fabric that preparation has electroconductibility.Ink and coating can be used for solar cell application; Sun power trapping application; Sign, flat-panel monitor; Flexible display, comprises photodiode, Organic Light Emitting Diode and polymer led display; Backboard and front panel display; And illumination, comprise electroluminescent and OLED illumination.Indicating meter can be used as the element of mancarried electronic aid, mancarried electronic aid such as computer, cellular phone, game machine, gps receiver, personal digital assistant, music player, game machine, counter, artificial " paper " and reading device etc.

They can be used for packing and/or prepare label.They can be used for stock controls and Application in Anti-counterfeiting (for example medicine), comprises packaging label.They can be used for manufacturing intelligence Package and label (such as for sale and advertisement, information search, stock's control, information demonstration etc.).They are used in packing and form Faraday's cage, for example, for electronic component.

Ink and coating can be used for Electrical and Electronic equipment and element, such as shell etc., so that EMI shield property to be provided.For example manufacture them, for microdevice (microscopic electro-mechanical systems (MEMS) device), comprise for anti-static coating is provided.

They can be used for manufacturing the element of shell, antenna and other mancarried electronic aid, mancarried electronic aid such as computer, cellular phone, game machine, navigationsystem, personal digital assistant, music player, game machine, counter, receiving set, artificial " paper " and reading device etc.

Ink and coating are used in and in substrate, form heat conductance passage or formation has the flowing property of expectation and the film of porosity.These materials can have alterable height and adjustable porosity also can form porosity gradient.Ink and coating can be used for forming the goods with anisotropic heat and/or specific conductivity.Coating can be used for forming the prototype of three dimensional printing.

Ink and coating can be used for the electronics (also referred to as " printed electronic product ") of preparation printing, the device that its form can be, the part of device or sub-element, electronic component etc.

Printed electronic product can, by ink and applying coating are prepared in substrate, adopt the pattern that comprises conductive channel, is designed to obtain the electronics of expecting.Described passage can be solid, major part is solid, liquid or gel form etc.

Printed electronic product can adopt diversified form and for a large amount of application.They can comprise electronic component (for example circuit) and/or the substrate of many layers.All or part of printed layers can cover or coating with another kind of material, such as seal coat, varnish, tectum, mulch film, dielectric coat, ionogen and other electro-conductive material etc.Between substrate and printed wiring, also can there be one or more materials.Layer may comprise semi-conductor, tinsel, dielectric materials etc.

Printed electronic product can further comprise other element, such as treater, memory chip, other microchip, battery, resistor, diode, electrical condenser, transistor etc.

Other application includes but not limited to: passive and active equipment and element; Electric power and electronic circuit, unicircuit; Flexible printed circuit board; Transistor; Field-effect transistor(FET); Microscopic electro-mechanical systems (MEMS) device; Microwave circuit; Antenna; Diffraction grating; Telltale; Chipless label (such as for preventing the theft in shop, Library etc.); Safety and ata for retail, Library and other environment; Keyboard; Smart card; Sensor (comprising gas and biosensor); Liquid-crystal display (LCD); Sign; Illumination; Flat-panel monitor; Flexible display, comprises photodiode, Organic Light Emitting Diode and polymer led display; Backboard and header board for indicating meter; Electroluminescent and OLED illumination; Photovoltaic devices, comprises backboard; Product identification chip and equipment; Membrane switch, battery, comprises hull cell; Electrode; Telltale; Printed wiring in mancarried electronic aid (such as cellular phone, computer, personal digital assistant, global positioning system apparatus, music player, game machine, counter etc.); The electronics linker that passes articulated section or other removable/flexible connection section and make in electronics, described electronics such as cellular phone, portable computer, Foldable keyboard etc.); Wearable electronics; With the circuit in vehicle, medicine equipment, diagnositc equipment, instrument etc.

Electronics can be RF identification (RFID) device and/or their element and/or radio-frequency communication device.Example includes but not limited to RFID label, chip and antenna.RFID device can be ultrahigh frequency RFID device, and it moves in the frequency of the about 928MHz of about 868-conventionally.The example of RFID purposes is for following the trail of the product in freight container, shop, the product in transportation, and for the manufacture of the parts of process; Passport; Bar code alternate application; Stock controls application; Pet identification; Livestock is controlled; Non-contact smart card; Automobile key buckles etc.

Electronics also can be elastomerics (for example silicone) touch panel and keyboard.These devices can be used in mancarried electronic aid, such as counter, cellular phone, GPS device, keyboard, music player, game machine etc.They also can be used for many other electronic application, such as remote control, touch screen, automobile push button and switch etc.

Composition, comprise that form is those of polymer complex, dispersion liquid, ink and coating etc., can be conduction and/or heat conduction.In some embodiments, composition can have at least about 10 ^-8the specific conductivity of S/m.It can have approximately 10 ^-6s/m-approximately 10 ⁵s/m, or approximately 10 ^-5s/m-approximately 10 ⁵the specific conductivity of S/m.In other embodiment of the present invention, described coating has following specific conductivity: at least about 0.001S/m, at least about 0.01S/m, at least about 0.1S/m, at least about 1S/m, at least about 10S/m, at least about 100S/m, at least about 1000S/m or at least about 10,000S/m or at least about 20,000S/m or at least about 30,000S/m or at least about 40,000S/m or at least about 50,000S/m or at least about 60,000S/m or at least about 75,000S/m or at least about 10 ⁵s/m or at least about 10 ⁶s/m.

In some embodiments, composition (comprises polymer complex, curing ink and coating etc.) surface resistivity can be not more than approximately 10000 Ω/side/mils, or be not more than approximately 5000 Ω/side/mils, or be not more than approximately 1000 Ω/side/mils or be not more than approximately 700 Ω/side/mils, or be not more than approximately 500 Ω/side/mils, or be not more than approximately 350 Ω/side/mils, or be not more than approximately 200 Ω/side/mils, or be not more than approximately 200 Ω/side/mils, or be not more than approximately 150 Ω/side/mils, or be not more than approximately 100 Ω/side/mils, or be not more than approximately 75 Ω/side/mils, or be not more than approximately 50 Ω/side/mils, or be not more than approximately 30 Ω/side/mils, or be not more than approximately 20 Ω/side/mils, or be not more than approximately 10 Ω/side/mils, or be not more than approximately 5 Ω/side/mils, or be not more than approximately 1 Ω/side/mil, or be not more than approximately 0.1 Ω/side/mil, or be not more than approximately 0.01 Ω/side/mil, or be not more than approximately 0.001 Ω/side/mil.

In some embodiments, composition can have following thermal conductivity: the about 50W/mK of about 0.1-, or the about 30W/mK of about 0.5-, or the about 0.5W/mK of about 0.1-, or the about 1W/mK of about 0.1-, or the about 5W/mK of about 0.1-, or the about 2W/mK of about 0.5-, or the about 5W/mK of about 1-, or the about 0.5W/mK of about 0.1-, or the about 50W/mK of about 0.1-, or the about 30W/mK of about 1-, or the about 20W/mK of about 1-, or the about 10W/mK of about 1-, or the about 5W/mK of about 1-, or the about 25W/mK of about 2-, or the about 25W/mK of about 5-, or at least about 0.7W/mK, or 1W/mK at least, or 1.5W/mK at least, or 3W/mK at least, or 5W/mK at least, or 7W/mK at least, or 10W/mK at least, or 15W/mK at least.

Embodiment

Comparative example 1 and embodiment 1-9

In table 1 and 2, the pigment (graphene film and graphite) of explanation, tackiness agent (poly-(vinyl butyral)), aromatic substance combine to form coating in the solvent system of hexanol and N-Methyl pyrrolidone with catalyzer (tosic acid).Solid ingredient accounts for approximately 10 % by weight of coating.Non-waving property component relative to each other exists with the amount providing in table 1 and 2 by weight.

Comparative example 2 and embodiment 10 and 11

Pigment (graphene film and graphite), 4,4' dihydroxy diphenyl and catalyzer (tosic acid) combine to form coating in the solvent system of hexanol and N-Methyl pyrrolidone.Nonvolatile element accounts for approximately 2.5 % by weight of coating.Solid ingredient relative to each other exists with the amount providing in table 3 by weight.

Comparative example 3 and embodiment 12-15

In table 4, the pigment (graphene film and graphite) of explanation, tackiness agent (poly-(vinyl butyral)) and aromatic substance combine to form coating in the solvent system of hexanol and N-Methyl pyrrolidone.Solid ingredient accounts for approximately 9 % by weight of coating.Non-waving property component relative to each other exists with the amount providing in table 4 by weight.Embodiment 12-15 has shown the significantly better adhesive power than comparative example 3.

Printing and measurement

Use #28 coiling rod by applying coating in PET film.Every kind of applying coating is two-layer and curing and curing after secondary coating between being coated with at 130 ℃.

The surface resistivity of the curing print obtaining is used four-point probe measurment.Result provides in table 1-3.

The adhesive power of described print (tractive) is measured by following: by a slice 3M Scotch ^?#810 band is firmly administered to print surface and uses the pulling campaign perpendicular to print surface rapidly this band to be pulled away to surface.The adhesive power of print based on tractive after the outward appearance of this band, by the scale classification of 1-5 (wherein 1 is best).To almost not having ink transfer to the sample of this band to provide 1 grade.To wherein after described print tractive this band be entirely dark-coloured sample and provide 5 grades.

The adhesive power of print (peeling off) is measured by following: by a slice 3M Scotch ^?#810 band is firmly applied in the surface of print and is pulled away from lightly in the direction parallel with described print surface.The surface resistivity of described print was measured and is measured again after this band is pulled away from before this band is used.By this, the per-cent with resistivity after tractive provides in being increased in table 3.

Table 1

Become component percentage ratio meter by weight, the gross weight based on providing composition.

Table 2

Table 3

Table 4

。

Claims

1. a composition, it comprises graphene film and at least one aromatic substance.

2. the composition of claim 1, it further comprises at least one polymkeric substance.

3. the composition of claim 1, it further comprises at least one catalyzer.

4. the composition of claim 1, wherein said polymkeric substance is selected from poly-(vinyl butyral), poly-(vinyl alcohol formal) and polyacrylic ester.

5. the composition of claim 3, wherein said catalyzer is sulfonic acid.

6. the composition of claim 3, wherein said catalyzer is tosic acid.

7. the composition of claim 1, wherein said graphene film has at least about 300m ²the surface-area of/g.

8. the composition of claim 1, wherein said aromatic substance is through functionalized.

9. the composition of claim 1, wherein said aromatic substance be selected from following one or more: hydroxy-benzoic acid, phenylformic acid (benzoix acid), phenyl aldehyde, carbamoyl benzoate, terephthalaldehyde, m-terephthal aldehyde, o-phthalaldehyde(OPA), terephthalic acid, dimethyl terephthalate (DMT), m-phthalic acid, dimethyl isophthalate, phthalic acid, dimethyl phthalate, Tetra hydro Phthalic anhydride, bis-phenol, 4, 4'-'-biphenyl diphenol, 3, 3'-'-biphenyl diphenol, 2, 2'-'-biphenyl diphenol, xenol, dihydroxy naphthlene, quinhydrones, pyrocatechol and Resorcinol.

10. the composition of claim 1, wherein said aromatic substance is benzene derivative.

The composition of 11. claims 1, wherein said aromatic substance is biphenyl derivatives.

The composition of 12. claims 1, wherein said graphene film has the carbon at least about 25:1: oxygen mol ratio.

The composition of 13. claims 1, wherein said graphene film has the carbon at least about 75:1: oxygen mol ratio.

The composition of 14. claims 1, it further comprises graphite.

15. 1 kinds of ink or coating, it comprises the composition that contains graphene film and at least one aromatic substance.

The ink of 16. claims 15 or coating, wherein said composition further comprises at least one tackiness agent.

The ink of 17. claims 15 or coating, wherein said composition further comprises at least one catalyzer.

The ink of 18. claims 15 or coating, wherein said composition further comprises graphite.

The ink of 19. claims 15 or coating, wherein said graphene film has the carbon at least about 25:1: oxygen mol ratio.

The goods of 20. 1 kinds of ink by claim 15 or coating coating.