TW200936499A - Highly dispersible carbon nanospheres in a polar solvent and methods for making same - Google Patents

Abstract

The particle sizes of agglomerates of carbon nanospheres are reduced by dispersing the carbon nanospheres in a polar solvent. The carbon nanospheres are multi-walled, hollow, graphitic structures with an average diameter in a range from about 10 nm to about 200 nm, more preferably about 20 nm to about 100 nm. Spectral data shows that prior to being dispersed, the carbon nanospheres are agglomerated into clusters that range in size from 500 nm to 5 microns. The clusters of nanospheres are reduced in size by dispersing the carbon nanospheres in the polar solvent (e. g., water) using a surface modifying agent (e. g., glucose) and ultrasonication. The combination of polar solvent, surface modifying agent, and ultrasonication breaks up and disperses agglomerates of carbon nanospheres.

Description

200936499 VI. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION [0001] The present invention relates generally to the manufacture of broken nanomaterials. More specifically, the present invention relates to a method for producing highly dispersible carbon nanospheres in a polar solvent. [Prior Art] [0002] Carbon materials have been used in many different applications in various fields. Examples of the current use of carbon materials include pigments, fillers, catalyst supports, and fuel cells. Pyrolysis of organic compounds is a known method for preparing carbon materials. For example, a carbon material can be produced by pyrolysis of a diphenoyl furfural gel at a temperature of 60 (TC or more). [OOf] Mostly obtained by pyrolysis of an organic compound at a temperature of 6 〇〇 14 〇〇 aC. The material tends to be amorphous or has an irregular structure. Because of the unique properties exhibited by graphite, it is advantageous to obtain a highly crystalline or graphitic carbon material. For example, the graphite material can be thermally or electrically conductive. [00=4] Highly regular carbon structures such as carbon nanotubes have been developed

The ίίϋϋMenami structure is a carbonized carbon or carbon resin in the presence of metal. The catalyzing agent is typically a salt of "Ινΐί四ϊΐί" mixed with a carbon precursor. The carbonized core carbon nanostructure is grown from a static period to produce a good regular structure. The metal catalyst is vigorously "oxygen = carbon na[iota] The rice material is removed. Amorphous carbon can be used, such as high [Abstract] 3-f, by dispersing the carbon nanospheres in a polar solvent to reduce the diameter from about (four) meters to about about Schneider, before the carbon nanospheres. The spectral data is shown in the range of the dispersion pattern t from 5 〇〇 to 5 μm:: ODMA\PCDOCS\TPEDMS\412〇l\i 4 200936499 Family? Method of Invention 'The cluster of nanospheres Depends on the polar solvent (such as i surface modifier (such as 'glucose) and ultrasonic dispersion carbon Hi = size. Polar solvent, surface modifier and ultrasonic combination can be: tender f * loose carbon nanosphere Agglomerates. Unexpectedly, carbon nanosphere aggregates having from 5 〇 0 nm to private average granules can be produced using the method of the present invention to produce an average particle size of less than about 300 nm using light scattering measurements. (better H * ^ small _ 15G nano) nanosphere and / or nai ball aggregate. [〇〇 =] the record _, table domain f agent and ultrasonic combination can be in the polar solvent ❹ 31 very Dispersion of Stable Carbon Nanospheres. Stones dispersed by the method of the present invention can be stabilized in polar solvents for hours, days, months or even more. Unexpectedly, the particle size distribution can be very narrow. ◎ Compared to the sound wave treatment only in water, the carbon nanosphere is supersonic in a polar solvent in the presence of a surface modifier. Processed, and & can produce a carbon nanomaterial having an unexpectedly narrow particle size distribution using dynamic light scattering measurements. In an embodiment, at least the tantalum carbon nanomaterial has less than 500 nanometers The average particle size, preferably less than 3 nanometers, and most preferably less than 200 nanometers. More preferably, at least 9G% of the carbon nanomaterial has an average particle size within one or more of the above particle sizes. Φ [ 0007] The small particle size, the narrow particle size distribution, and the stability of the suspended carbon nanospheres in the solvent are particularly advantageous for the carbon nanomaterials dispersed in various types of materials, including but not limited to fillers and pigments. Supercapacitor and high performance electrode. [0008] The surface modifier used in the present invention is an organic molecule which is soluble in a polar solvent and has one or more functional groups bondable with carbon nanospheres. The surface agent may be a surfactant, an organic acid, a carbohydrate, an amino acid, and the like. Examples of suitable functional groups include a carboxyl group, an amine, a sulfonate, and/or a hydroxyl group. It can be used as a surface modifier. Specific examples of compounds include glucose, glycolic acid, glycine Ascorbic acid, 12 sulphate; phenyl benzoate, hexanoic acid, trifluoroethylene. In one embodiment, the surface modifier is a biocompatible organic molecule such as, but not limited to, glucose, glycolic acid, glycine Amino acid, or ascorbic acid. Use bio-phase::ODMA\PCDOCS\TPEDMS\41201\1 5 200936499 The particle size distribution is expected to be good for the use of carbon = m fine 'the carbon nano-wei contains _ position to change the surface The facial green can be used in the purification of the carbon nanosphere. The surface oxygen concentration of Weidang is used: the surface oxygen is preferably at least about 5% by weight, and the good is preferably at least about 15 Wt%. According to the invention, the ruthenium-containing irregular surface facilitates the dispersion of the nano-nanospheres in the neon towel. 'S ^ and help slaves [(8) == face change _ is dissolved in the general, in water, ethanol, tetrahydro _ two =: agent: a particularly good solvent for carbon nanotubes. ^ When mixing into a hydrophilic material, the aqueous solvent is a good knife. The scattered Chennai unfinished material f ^ ^ adsorption and / or surface modifier agent damage f super chopping period 'chemistry = Xie Miqiu smaller polynai = Lihe table (four) #矿杂__科超音iii shooting, surface Coffee, butterfly _=== dissolve [0013] found that using the method of the invention, the advantageous structure of the rice ball, = scatter two high: 'the system is beneficial to provide strength, conductivity; heat =: ::ODMA\ PCD〇CS\TPEDMS\412〇l\i 6 200936499 The above and other advantages are fully expressed in the following description, and the description of the present invention will be given by the reference to the example of 3, (4) = actual compensation. It can be understood that the specific examples of the present invention are explained, as well as the specific and detailed descriptions of the present invention, and the introduction of the Japanese version of Ke Tengjing by the rider, and the other embodiments [introduction] The average particle size of carbon nanotubes. To reduce the measurement by dynamic light scattering ,; , jujube month method, the average particle size from more than about 500 nm flat to find ^ ^ fine nanometer, more preferably less than about fine nano. The dispersed carbon captures the ball due to its size and its distribution in the polar solvent. It has a unique = ^, [= 7] in order to bribe this 'carbon nano material' average practice = scattering mosquito and corresponding to light scattering spectrum The data is ❹. The over-obvious peak 'average particle size' should mean a weighted average based on the peak of the two peaks. Intensity, unless otherwise specified.丨' Π. A component used to make dispersed carbon nanospheres. A. A nano-material containing carbon nanospheres ==== Multi-carbon wall nr-space =:r; range from about ^ to please range. The multi-walled structure has a hollow structure. [0019] Typically, the carbon nanotubes on the side have a less than about ratio (ie, a width ratio of less than 3:1), preferably less than about 2: 1.75. Preferably less than about 1>5: Bu-in the embodiment, carbon-neutral ^::ODMA\PCDOCS\TPEDMS\41201\1 7 200936499 - Irregular surface. The irregular surface has a trap that causes the spherical shape. Graphite defects are considered to be factors that partially contribute to the imperfections of imperfections. The carbon nanosphere is high in graphite, and its Qi carbon nanosphere has excellent electrical conductivity and thermal conductivity. , , ', ° 疋 5 衩 衩 nanomaterial [0020] Typically, the thickness of the carbon nanosphere wall is between meters. Thin, thick or (4) _ can be used to measure the thickness from the inner diameter of the wall to the outer diameter of the wall. The wall having a structure of _f φ ❹ 50 between about 2 and about 1 () () of the graphite layer, more preferably between about 5 and about 2 〇 3 = 5 and about $ 层The number can be discussed as follows.赖奴优_ has a silk-faced structure set. The county shape and township quality can also provide thieves, so that carbon ϊ ΐ ί ίίίί ΐϊ ΐϊ 成 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不Dimensions, Naiqiu's test is important for maintaining the operational miscellaneous overtime = the nucleus property also allows the surface to be functionalized, and at the same time the ^r r center provides the hole 2 of the same. In the embodiment, the surface area is from about m2/g to about 4 Å to about 1 Å [〇〇22]. The carbon nanomaterial is usually provided as a circled particle as a carbon nanosphere. When the individual carbon nanotubes have a diameter smaller than the nanometer, the carbon nanosphere tends to agglomerate to form a secret having an average particle diameter of more than 5 GG nanometer (i.e., agglomerated nanospheres). The number of spectral lions indicates that the carbon nanospheres agglomerate before dispersing into clusters ranging in size from about 5 GG nm to 5 microns. As shown in the figure, the average particle size is about 14 microns using dynamic light scattering measurements. [0023] Figures 2A and 2B are SEM images of clusters of nanospheres. In Figures 2A and 2C, in at least some embodiments, the image shows that the carbon nanosphere clusters form a grape-like secondary structure at: ::〇DMA\PCDOCS\TPEDMS\41201 \1 8 200936499. The second figure is a close-up mirror of some clusters with a clever cluster to expose a plurality of carbon nanospheres. The image of Figure 2C is more clustered and consists of a plurality of smaller nanospheres. The se^ TEM image shows that the nanostructures are hollow and generally spheroidal. [0024] In the embodiment, the carbon nanosphere may be one of the components of the carbon nanomaterial. A higher proportion of carbon nanospheres is generally preferred, thus benefiting from the unique properties of the carbon nanosphere carbon nanospheres. In one embodiment, the nanospheres are at least about 1% by weight of nanomaterial, preferably at least about 5% by weight, more preferably about 75% by weight, very preferably Ο

^ less than about 90 wt ° / 〇, optimally at least about 98 wt%. A carbon nanotube material that is not a carbon nanosphere is preferably a graphite material such as a graphite sheet or other graphite nanostructure. The carbon nanomaterial may comprise non-graphite amorphous carbon. However, it is generally advantageous to minimize the percentage of non-graphitic amorphous carbon (e.g., #transition due to purification and/or conversion of non-graphite amorphous carbon to graphite by additional heat treatment steps). [0025] Carbon nanospheres typically comprise an oxygen-containing surface functional group that provides a bonding site for a surface modifying agent. According to the present invention, it has been found that oxygen-containing functional groups can be extremely advantageous. For dispersing carbon nanospheres' when using XPS to measure surface oxygen concentration of at least about 2 wt%, preferably at least about 5 wt%, more preferably at least about 1% cut, and using xps to measure surface oxygen at least optimally. About 15 wt%. [^0026] The carbon nanospheres can be treated to introduce oxygen-containing functional groups on the surface. Examples of suitable oxidizing agents include sulfuric acid, KMnOA, H2〇2, 5M or more concentrated nitric acid and Wang. The above oxidizing agent tends to be introduced into the surface of the carbon nanospheres using an XPS measurement of less than about 9 wt% oxygen. Higher wt% oxygenated functional groups can be achieved using strong oxidizing agents, as desired. Introduction of the oxygen-containing functional group can be an amount that facilitates providing a desired location at which the surface modifying agent can bond to the carbon nanosphere. Examples of suitable strong oxidizing agents include a mixture of acetic acid and sulfuric acid, (ii) a hydrogen peroxide solution, and (iii) a mixture of sulfuric acid and hydrogen peroxide. Specific examples of suitable concentrations of strong oxidizing agents include, without limitation, mixtures of sulfuric acid and nitric acid (70%) in a ratio of 3:1 v/v; 30% hydrogen peroxide solution; or >5 dangerous acid (98%) and Hydrogen peroxide (30%) was a mixture of 4:1 v/v 9 ::ODMA\PCD〇CS\TPEDMS\41201\1 200936499. B. Surface modifier

[0027] The surface modification used in the present invention is an organic molecule which is soluble in a polar solvent and has one or more functional groups capable of bonding with carbon nanospheres. Surface modifiers can be - surfactants, niacin, carbohydrates, amino acids, and the like. Examples of functional groups suitable for bonding to the surface of carbon nanospheres include carboxyl groups, amines, acid salts and/or hydroxyl groups. In some embodiments, the functional moiety (e.g., carboxyl or hydroxyl) is selected to bond to an oxygen-containing moiety on the surface of the carbon nanosphere. 1 A specific example of a compound which is used as a surface modifier, and comprises glucose, glycine, glycine, anti-bad domain n-base acid, acid, trifluoroacetic acid and the like. C. Polar Solvent [0028] When the carbon nanosphere is coated with a surface modifier, the solvent may be any solvent which is capable of dissolving the surface modifier and dispersing the carbon to be converted. Examples of suitable polar solvents include, but are not limited to, water, ethanol, tetrahydroanthracene (ΤΗρ), and the like. Unexpectedly, the material of the county is the best solvent for the dispersion of carbonaceous materials. Because the organism of the aqueous solvent should be (4) secret and mixed with the dispersed carbon material to form a composite of hydrophilic materials, miscible_better. III. Dispersion method of the nanospheres [=0^ In the green of the present invention, the κ of the nanosphere is dispersed by the nanosphere in the extreme like water, and is reduced by using a surface modifying agent (such as glucose) and ultrasonic waves. The size of the rf] / method usually contains the choice - can be mixed with the oxygen on the surface of the carbon nanosphere (4) (four) can be transferred (four) to change the polarity of the agent, the mixture of the four (four) and carbon nanosphere to disperse The carbon is not a ball. The cereal, the surface modifier and the nanosphere can be mixed together in any order. In the embodiment, the concentration of the surface of the spray is from about G5 wt= to::ODMA\PCDOCS\ TPEDMS\412〇l\l 10 200936499 is in the range of about 20 wt ° / 〇, more preferably in the range of about 5 wt % to about 1 〇 wt %. The carbon nanomaterial containing carbon nanospheres typically contains a concentration range from From about 1 wt% to about 20 wt% 'better from about 1 wt〇/❶ to about 1% by weight. [0031] The 1⁄4 nanosphere is dispersed in a solvent using ultrasonic waves. Ultrasonic waves can use any suitable technique. Performing, such as an ultrasonic bath, oscillating carbon nanospheres at ultrasonic frequencies. An example of an ultrasonic device suitable for dispersing carbon nanospheres is CR£ST ULTRASONICS TRU- SWEEPTM (frequency 68 kHz and 5 watts). ❹ ❿ [0032] Ultrasonic waves are usually continued for at least 3 minutes, preferably at least about 丨 hours, and more preferably at least about 2 hours. The process includes from about 30 minutes to about 6 hours, and preferably from about! hours to about 3 hours. The sonication step can be carried out at room temperature or other suitable temperature. The boat-like ridge can be broken and scattered. Carcass. Unexpectedly, agglomerates of carbon nanospheres with an average particle size and micron size can be produced using the present method. The average particle size of the measured particle size is less than about 3 (8) nm, preferably smaller. And the best secret 15G nano-nano and / or nai tree agglomerate. The dynamic light scattering data of the PMI ball shows that the use of this diameter is significantly reduced. Figure 3 shows the richness of the example 2 in detail. As shown in Fig. 3, in an embodiment, the method of the present invention produces dispersed carbon nanospheres having a two-average particle diameter of 147 nm. Sections 4 and 4, according to the present invention The distribution of the carbon spheroids of the county is accompanied by the T of the T surface. This edition is better than the use of the method of the present invention. The dispersed carbon nanosphere also tends to have a side, and the range after the surface is from: 〇DMA\PCD〇CS\TPEDMS\41201\1 200936499 [0036] According to the nature of the present invention, such as multi-wall, middle knife 2 The Sini nanosphere advantageously retains its advantageous original dimensions. Figure 4B Figure 2 P: f closed structure, graphite properties and the 2C figure before the dispersion of the primary structure The carbon nanospheres with the same dispersion are displayed. The height of the primary structure similar to that of the nanospheres is stable for several months. The stone of the present invention can be at room temperature for about one hour, and more preferably, the carbon nanosphere can be stably maintained for at least ❹ ν ν, ', spoon for 1 day' and optimally for at least about 1 month.嶋佩佩#丝. Because the carbon nano-a gift ball can be mixed with other materials to form a composite. Benton, Conductive "The narrow particle size distribution of the inventive carbon nanosphere and the intrinsic properties including the strength of electrical conductivity with thermal conductivity, porosity and surface area. IV. Manufacture of carbon nanospheres [0039] for use in the method of the invention The carbon nanosphere can be fabricated by the technique of a carbon nanosphere of a desired nature. In the embodiment, a precursor mixture is formed, which comprises a carbon precursor and a plurality of catalytic particles [2) carbonized to convert the precursor compound into - an intermediate tantalum material comprising a nana structure, an amorphous carbon and a catalytic metal, (3) purifying the inter t carbon (4) by removing at least a portion of the amorphous carbon and optionally employing at least a portion of the catalytic metal. The manufacturing steps of the carbon nanospheres according to the present invention are described. A. Components for forming carbon nanospheres (1) Carbon precursors [0040] Any type of carbon material can be used as the carbon precursor of the present invention. As long as it can disperse the template particles and carbonize the template particles based on heat treatment. Suitable compounds include single and polycyclic aromatic compounds such as those having polymerizable functional groups:: ODMA\PCDOCS\TPEDMS\41201 \1 12 200936499 Benzene and naphthalene derivatives. Also included are ring compounds which are heated to form single and polycyclic aromatic compounds. The functional groups which can participate in the polymerization include c〇〇H, 00, OH, OC, S〇3, NH2. SOH, N=C=〇 and the like. [0041] The carbon precursor may be a single type of molecule (for example, a compound that can be polymerized with itself), or the carbon precursor may be copolymerized together or more. ^ A combination of different compounds. For example, 'in an embodiment' carbon drive: may be a meta-phenylene sulfonate gel. In the embodiment of the two compounds, A is polymerized by hydroxyl groups with resorcinol molecules. As a cross-linking agent between resorcinol molecules. [0042] Other examples of suitable carbon precursors include resorcinol, phenolic resin, triterpene melamine gel, poly(sterol), poly (Cyanonitrile), fine, petroleum, and the like. Other polymerizable benzene, benzoquinone and similar compounds can also be used as carbon precursors and are well known to those skilled in the art. [0043] In one implementation For example, a carbon precursor is a hydrothermally polymerized organic compound. Suitable organic compounds include citric acid, acrylic acid, benzoic acid, acrylic acid acrylate, butadiene, styrene, cinnamic acid, and the like. (2) Catalytic Template Nanoparticles [0044] Catalytic Template Nanoparticles are used as Forming a φ template into a nanostructure. When mixed with a carbon precursor, the template nanoparticle provides a nucleation site where carbonization and/or polymerization can begin or increase. Since the template nanoparticle is made from a catalytic atom, the template particle It can be advantageously used as a nucleation site and as a catalyst for carbonization and/or ruthenium polymerization. [0045] The catalytic template particles can be formed in more than one method. As described below, in one embodiment, the template particles are formed from agglomerates of particles. Formed by a metal salt. Alternatively, the catalytic atom can be combined with a dispersant to control the formation of the particles. The template nanoparticles using a dispersant tend to have a more uniform size and shape than the template particles formed without the use of a dispersant. (i) Catalyst Atom :: ODMA\PCDOCS\TPEDMS\41201 \1 13 200936499 [0046] The catalyst atom used to form the template nanoparticle may be any material which promotes the polymerization of carbonization and/or carbon precursor. In the following, the catalyst system-transition metal catalysts include, but are not limited to, iron, and the transition metal catalysts are particularly useful for catalyzing a plurality of polymerization and/or carbonization reactions involving tops:. 】 drive (8) dispersant

Optionally, a dispersant can be combined with the catalyst atoms to control the formation of particles. The dispersion is selected to promote the formation of nanocatalyst particles having a slit-qualification, a size, and a uniformity. Dispersed organic molecules, polymers and filaments within the scope of the invention. The dispersant can interact with the catalyst atoms in the dissolved or dispersed carrier by various mechanisms including bonding, covalent bonding, van der Waals interaction/bonding, ion-pair electron bonding or hydrogen bonding. Function and bonding.迥田岭齐丨次 [0048] To provide a bond between the dispersant and the catalyst atoms, the dispersant comprises - or a plurality of suitable functional groups. Preferred dispersants comprise functional groups having an electro- or a plurality of ion pairs which can be used in the composite, or which can form other types of linkages such as hydrogen bonding. The officially based dispersants have a strong bond that interacts with the catalyst atoms. Allowed [0049] The dispersing agent can be an audible: or synthetic compound. In the case where the catalyst atom is a metal and the fine fraction is an organic compound τ, such a catalyst complex ' may be an organometallic composite. [0050] In one embodiment, the functional group that disperses ruthenium comprises a group selected from the group consisting of a hydroxyl group, a carboxyl group, a carbonyl group, an amine group, a guanamine, an acrylonitrile, a nitrogen having a free individual electron pair, an amino acid, a thiol, a sulfonic acid, One or more constituent molecules of the group of sulphonate or dentate. The dispersant may be a monofunctional, difunctional or polyfunctional group. [2〇51] Examples of suitable monofunctional dispersants include alcohols such as ethanol and propanol and neon, such as formic acid and acetic acid. The (10) difunctional dispersant comprises a monoacid such as oxalic acid, malic acid, malonic acid, succinic acid and the like; diol:: ODMA\PCD〇CS\TPEDMS\41201 \1 14 200936499 such as ethylene glycol, Propylene glycol, 1,3-propanediol and the like; hydroxy acids such as glycerol, lactic acid and the like. Useful polyfunctional dispersants include, sugars such as glucose, polyfunctional hydroxy acids such as citric acid, pectin, cellulose, and the like. Other useful dispersing agents include ethanolamine, thiolethanol, 2-sulfuric acid acetate, amino acids such as glycine and sulfonic acids such as sulfophenyl alcohol, sulfobenzoic acid, sulfophenylthiol and sulfanilide. The dispersant may even comprise an inorganic component (for example, a mercapto group). Suitable polymers and oligomers within the scope of the invention include, but are not limited to, polypropylene esters, polyvinyl benzoate, polyvinyl sulfonium salts, polyethylene sulfates, polyvinyl sulfonates containing sulfonates Styrene, polydiphenol carbonate, polybenzimidazole, poly Φ ° ratio ° 疋, 化 对 对 本 。 。 。 。 。 。 。. Other suitable polymers include polyvinyl alcohol, polyethylene glycol, polypropylene, and the like. In addition to the characteristics of the dispersant, it is also advantageous to control the molar ratio of the dispersant to the catalyst atoms in the catalyst suspension. A more useful measurement is the dispersant, based on the molar ratio of the catalyst atoms to the molar ratio. For example, in the case of covalent metal ions, a two-mole equivalent of a monovalent functional group would be necessary to provide a theoretical stoichiometric ratio. In a preferred embodiment, the molar ratio of the dispersant functional group to the catalyst atom is preferably in the range of from about 0.01:1 to about 100:丨, more preferably in the range of from about 、5, :i to about 50 _1. , and the best in the 〇 〇: 丨 to about 2 〇: 丨 range. φ [0054] The dispersant of the present invention allows for the formation of very small and uniform particles. Typically, the nanoparticle catalyst particles formed in the presence of a dispersant are small in size. Preferably, the nanoparticle system is less than 1 nanometer, more preferably less than about 5 nanometers and the best is less than about 2 nanometers. The dispersant prevents agglomeration and deactivation of the catalyst particles during pyrolysis of the carbon precursor. This ability to prevent deactivation can increase the lifetime of the nanocatalyst and/or increase the lifetime of the nanocatalyst under extreme conditions of pyrolysis. Even if the dispersant contains only a few milliseconds, or even a few microseconds, of catalyst activity, the increased time of the catalyst can be advantageous at a given carbonization kinetics at elevated temperatures. ::ODMA\PCDOCS\TPEDMS\41201\l 15 200936499 (iii) Solvents and Other Additives Solvents may be optionally employed to prepare catalyst atoms for mixing with dispersants and/or carbon precursors. The liquid medium in which the catalytic template nanoparticle is prepared may contain various solvents including water and an organic solvent. The solvent participates in the formation of the granules by providing a liquid medium for interaction with the catalyst atoms and dispersants. In some cases, the solvent can be combined as a primary dispersant with a primary dispersant that is not a solvent. In one embodiment, the solvent also allows the nanoparticles to be opened into a suspension. Suitable solvents include water, methanol, ethanol, n-propanol, iso-ol, acetonitrile, acetone, tetrahydrofuran, ethylene glycol, dimethyl decylamine, dimethyl sulfoxide, chlorin, and the like. And including mixtures thereof. [0057] The catalyst composition may also comprise an additive that assists in the formation of nanoparticles of catalyst particles. For example, mineral acids and test compounds may be added, preferably in small amounts (e.g., > less than 5 wt%). Examples of mineral acids that can be used include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, and the like. Examples of basic compounds include sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium hydroxide and the like. It is also possible to add solid matter to assist in the formation of nanoparticles. For example, an ion parent handle can be added to the solution during catalyst formation. The ion exchange resin can be substituted for the acid or base described above. The solid material can be easily separated from the final iron catalyst solution or suspension using a simple technique such as centrifugation and filtration. ~ (3) Trial production for purification of intermediate carbon materials [0059] Amorphous carbons and/or catalysis can be removed from the carbon nanostructures using various reagents to purify the intermediate materials. Purification can be carried out using any reagent or combination of reagents' which selectively removes amorphous carbon (or selectively catalyzes the metal) while leaving the graphite material. [=060] The reagent for removing amorphous carbon contains an oxidizing acid, an oxidizing agent, and a milk composition thereof. Examples suitable for removing amorphous carbon include hno3 and aqua regia containing sulfuric acid, ΚΜη04, H2〇2, 5M or more. ::ODMA\PCDOCS\TPEDMS\412〇1\i 16 200936499 [=1] The catalytic metal can be removed using any reagent that selectively dissolves as a catalyst but does not damage the carbon nanostructure. Nitrate, acid is suitable for n ΐ 属 such as, but not limited to, iron, brocade. Other _ Reagents Ϊ ^ ^ 骤 转化 转化 转化 转化 转化 转化 转化 转化 转化 转化 转化 转化 转化 转化 转化 转化 转化 转化 转化 转化 转化 转化 转化 转化 转化 转化 转化 转化 转化 转化 转化 转化 转化 转化 转化

[The carbon nanostructure of ΓΪΙΐΐ明 can use all or part of the following steps: = formation = mixture 'contains carbon precursors and a plurality of template nanometers / .20 allow or cause carbon precursors to catalyze template nanoparticles a surrounding ΐ 'dicarbonized precursor mixture formed - an intermediate carbon material comprising a plurality of nanostructures (eg, "nine glutinous rice balls"), amorphous carbon and catalytic metals, and by removing at least a portion of the amorphous carbon and The lion-partially catalyzed gold 。 ΐϊ ΐϊ 。. The purification step may also include removing the energy at the amorphous carbon removal stage or adding additional oxygen-containing functional groups to impart greater hydrophilicity to the carbon nanosphere. 1) Formation of a precursor mixture [00=3] The precursor mixture is formed by a plurality of catalytic template nanoparticles in a lion carbon precursor and a dispersed carbon precursor. [0064] Catalytic decomposition of β in a carbon precursor The template nanoparticle can be provided in several different ways. The template nanoparticle is formed in a carbon precursor towel (ie, on the spot) or formed in a separate reaction mixture and then mixed with a carbon precursor. In some cases, the particle formation can be Part of the reaction occurs after the correction and is completed, when the template particles are mixed and/or heated in the carbon precursor towel (for example, at the beginning of the precursor polymerization step 2). The template nano particles can also be controlled - or multiple The dispersion of fine particles formed by the morphology of the particles is formed by the metal salt. [0065] The solid-green _ 'template green chloroform system from the metal qingcheng in the carbon precursor:: ODMA\PCDOCS\TPEDMSV41201\ 1 17 200936499 Precursor ί上:=金粒: It can be selected by selecting - or multiple can be combined with carbon or with a carbon precursor and a dispersing agent. Next, the catalytic _ sub (for example, silk metal i Ge 2 and a dispersant (such as 'Jude or its salt type) two counter-reagent complexes. Catalysts are usually laid out by the first sub-system to form a powder to control the particle size. _ type of catalytic scheme and / or more

Sub-distribution age-suitable #solubilization and then allow the reminder ==!: formation points can be 』 before the pre-age set and secrets plus other components of the 'real side, the ingredients of the spectator Nai-nong are made by, 1 hour Allows or induces shaped, non-rice particles to a period of about 14 days. This mixing is typically in the temperature range from about 〇t to about 2 (8). In the case of C, the temperature does not exceed i (xrc. Particle formation can also be induced by using "1 。. For example, in some cases, the formation of particles or intermediate particles can be caused by bubble hydrogen through the catalyst complex solution. [0068] The template nanoparticle of the present invention is capable of catalyzing the polymerization and/or carbonization of a carbon precursor. The concentration of the catalytic template nanoparticle in the inverse is generally selected to be the number of the largest carbon nanotube structure. The amount of catalytic template particles varies with the type of carbon scraping used. In an exemplary embodiment, the carbon precursor to the catalytic atom has a molar ratio of about 0.1:1 to 1 〇〇:1, more preferably From about 1:1 to about 3:1. (2) Polymerizing the precursor mixture [0069] The precursor mixture typically allows for sufficient time for hardening, such that a plurality of intermediate %i nanostructures are formed around the template nanoparticle. Since the template nanoparticle is catalytically active, the template nanoparticle can preferentially accelerate and/or initiate polymerization of the carbon precursor near the surface of the template nanoparticle. ::ODMA\PCDOCS\TPEDMS\41201\1 18 200936499 Tff miscellaneous frequency needs coffee temperature The degree of grain and grain type depends on the type of PH and the type of carbon precursor used. In the case of poly 5 / month 's (four) nanostructures can be broken for individual organic structures or during carbonization And/or the combination of the nanostructures of the amorphous carbon removed. " The ammonia added to the force 1 can also affect the polymerization by increasing the amount of the polymer and increasing the amount of the parent that occurs between the precursors.

[0072] With regard to hydrothermally polymerizable carbon precursors, polymerization typically occurs at elevated temperatures. In a preferred embodiment, the carbon precursor is heated to a temperature of from about this to about 2 Torr, and more preferably at about 25. (: with an approximate condition of about 120. ( between: [0_ meta-benzoic acid (for example, having iron particles and solution cation is M4)), the temperature of the solution is about &£>c to It is about 9 Torr and the hardening time is less than 1 hour to about 72 hours. Those skilled in the art can easily determine the conditions required to harden other carbon precursors under the same or different parameters. [0074^ - Example, the polymerization is not It is allowed to continue in succession. Terminating the hardening procedure prior to polymerization of the entire solution helps to form a plurality of intermediate nanostructures that will result in individual nanostructures rather than a single carbonized material stack. However, the present invention includes the formation of a stone counterbore An embodiment of a plurality of inter-linked or partially-linked intermediate carbon nanostructures. In this embodiment, individual nanostructures are formed during carbonization and/or during amorphous carbon removal. [0075] From Template Nano The dispersion of particles forms an intermediate carbon nanostructure resulting in the formation of a plurality of intermediate carbon nanostructures having unique shapes and sizes. Finally, the properties of the nanostructure can be at least partially influenced by the shape and size of the intermediate carbon nanostructure. It is decided that because of the unique shape and size of the intermediate carbon nanostructure, the final nanostructure can have advantageous properties such as, in particular, high surface area and high porosity. (3) Carbon 彳b The former mixture of precursors [0076] Precursor The mixture is carbonized by heating to form an intermediate carbon material comprising a plurality of carbon nanostructures, amorphous carbon and a catalytic metal. The precursor is mixed with 19::ODMA\PCD〇CS\TPEDMS\41201\1 200936499 By heating the mixture to a temperature of about 50 (rc to about 25 Å < t and carbon = < during the t heat program, such as oxygen and nitrogen atom volatilization or from the middle nano-plate nanoparticle The carbon is removed, and the carbon atoms are re-arranged or connected to form a carbon-based structure. [=7] and the carbonization step usually produces a stone S-nine structure. The graphite-based nano-J has a system of -SP2 Mixing the carbon atoms in the structural thin film of the atom'. The layer #石# can provide impurities and favorable properties such as electrical conductivity and strength and/or stiffness. 4 (4) Purifying the intermediate carbon material by removing at least part of Non-graphite amorphous carbon pure = the purification step increases (four) carbon material The weight percentage of the carbon (4) structure is typically removed by oxygen decanting. It is used to remove the amorphized ship's rhyme selection, so as to oxidize the pi bond of the bond structure of the non-ink amorphous carbon. Low reactivity. Non-recommended _ application of oxidant or mixture to - or multiple successive purification steps to select 'substantially or partially - catalytic metal can be removed. 催 m疋IS and the removed catalytic metal Purity will depend on the plate nanoparticle in the final product using a plate such as nitric acid, hydrogen, or a hydroxide plate, the m-scaler carbon shifting process mode 5 particles (eg, iron particles or atoms) can usually be The composite nanometer = is removed in a 5.0 Μ nitric acid solution for about 3-6 hours. Yes, __ plate nano particles and / or amorphous 妷 /, ~ ~ removal of long order will not completely damage the carbon nanostructure. In some cases;: ODMA\PCDOCS\TPEDMS\41201 \1 20 200936499 two = the object can be captured from (four) Naiqiqiu part of the removal of the chemical lying, oxygen and acid have the water money ionic group and oxygen 1 匕; All = not limited to citrate, lysine and or sulfhydryl groups introduced to 395; = oxygen; and conditions below 9 ❹ = [= 4] selected heterogeneous, pure sequence can also be used outside the surface temperature and The ί ί step, which converts the residual amorphous selection = step, since the substantial part of the amorphous carbon has been removed, and to the residual part, the residual carbon system is easier to turn. The base can be introduced to the surface of the carbon nanosphere by using a strong oxidizing agent. Generally and ancient, the amount of gas z, ten: material ( (ie 'whether - the previous carbonization of the carbon = = agent of the Yue ^ r salty: force r with oxidation; crystal in the real For example, the oxidation treatment is carried out for about 2 hours to about a certain period of time. To aid oxidation, the oxidation treatment can be carried out using ultrasonic waves. [_5] The carbonaceous material produced by Green is made 1 = 睁t = r. It is apparent that the present invention can be carried out using a nanometer V. Example [0086] manufactured by using a method different from the foregoing method. (Example 1) Surface preparation, , Wei, average particle using dynamic light scattering measurement:: ODM A \PCDOCS\TPEDMS\41201 \ 1 21 200936499 The diameter is greater than 1 micron. (a) Preparation of iron solution (01Μ) [0088] 0. 1 bismuth iron solution uses 84 grams of iron powder, 289 grams of citric acid and 15 liters of water $ The iron-containing mixture was mixed in a closed flask on a shaking table for 3 days 'short towel break or 2: owed' to remove the vapor space of the flask with air before continuing mixing. (b) Preparation of the mixtureΟ

[0089] 916.6 grams of meta-phenylene was placed in a round bottom flask with 135 grams of hydrazine (37% in water). The solution was stirred until the resorcinol was completely dissolved. From step (a) 1 15 liters of iron solution was slowly added and stirred. Thereafter, 1 〇 25 ml of ammonium hydroxide (28-30% aqueous solution) was added dropwise and vigorously stirred to obtain a pH of 0.16. The slurry was hardened at 8 Torr to 9 Torr: (water bath) for 1 hour. The solid carbon precursor mixture is collected by the job and the secret silk. (c) Carbonization [0090] The polymeric precursor mixture is placed in a paste with a cover to be transferred to a furnace. The ship program is squirting at a rate of ρχ 2〇 °C/min, from room temperature to coffee, and returning to room temperature after deleting g a π * hours. The carbonization step produces an intermediate carbon material having a carbon nanostructure, non-spike, and iron. Purification of household (d) to remove amorphous carbon and iron [0091] The carbonized carbon product (ie, intermediate carbon material) is purified as follows = ηνο3 refluxing carbonization product for about 12 hours, using deionized water (10) run = 'use ΚΜη 〇4, 氏4 and Η2〇 莫尔〇〇1 : 〇2 treatment (maintained at about 9 ° C for about 12 hours), using de-erosion (^2〇) Run fishing 'use 4MHC1 treatment (in , about 9 〇 ° C for 12 hours = 33 (2 〇) brewing, collecting the product and at about (10). c for:: 〇 DMA \ PCDOCS \ TPEDMS \ 41201 \ 1 22 200936499 (Example 2) [= 92] Example 2 describes a method for preparing (4) heterogeneous, water and ultrasonic waves to prepare dispersed carbon nanospheres. [^3] Adding 1 ml of a glucose solution having a concentration of 6 wt% to 3 g of carbon nevus in a glass container Rice material (greater than 98% carbon nanosphere). The solution was then treated with ultrasonic for 2 hours. The ultrasonic system that affects the dispersion of nanospheres was carried out using CR£ST USTRASONICSTRU-SWEEPTM (68 kHz and 5 〇〇 watt). Liquid blackened 7F carbon nanospheres dispersed in water. After 3 months, 2 3 wt% of the carbon nanotubes remained stable and dispersed in water. 4A 4BFig. SEM and TEM image of the carbon nanosphere produced according to Example 2. The SEM and TEM images and the undispersed carbon nanomaterial shown in Fig. 2A-2C, An improvement in the dispersion of the dispersion is shown. [0094] Figure 3 provides a diagram of dynamic light scattering of the dispersed carbon nanospheres of Example 2. The dynamic light scattering data was collected using MALVERN ZetaSizer (Nan〇senes). Quartz colorimetric tube analysis with a draw time of 36 sec. As shown, the dispersed carbon nanosphere of Example 2 has an average particle diameter of 147 nm. In contrast, the carbon nanosphere before dispersion has the same The average particle size shown in the figure is 1.4 μm. ® _5] The 5th shows that the carbon nanosphere is only supersonic in the water towel. Unexpectedly, the particle-controlled distribution after 2 hours of ultrasonic in water is only shown at 5 microns. The peak and another 254 micron peak. This result is unexpected, as the result of the non-ultrasonic wave does not show a peak of 5 microns. Therefore, it is shown in some cases, such as the use of pure water, ultrasonic waves can cause particle size Reduced and agglomerated. In contrast, used in accordance with the present invention Ultrasonic and surface modifiers can produce significantly smaller particle sizes, but are not larger agglomerates of 5 microns. (Example 3) [〇〇96] Example 3 describes the preparation of dispersed carbon nanotubes using glycine and water. The method of the ball. ::ODMA\PCD〇CS\TPEDMS\41201\1 23 200936499 ί The lack of water (10) is identified as being in the glass valley for 3 grams of stone and unrecognized (more than 98% carbon. The ultrasonic system that affects the dispersion of nanospheres is measured using C Teng 1SWEEPTM (68 service frequency and shouting) ^ Dongli: ^^ Not too much ^ The ball is dispersed in the water. After using the amount of dynamic light scattering, the blue-dispersed carbon nanometer === can be converted to the ride or the present #上_征 ❿ , ^, without limiting the scope of the invention. Thus, the scope of the invention is expressed as $ Γ ι ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί All changes that come within the meaning and range of the scope of the invention are intended to be embraced. [Simple description of the map] The dynamics of the prefectures in the prefectures of the county are mixed into the high-resolution bliM images. The 2B image shows that the individual clusters of the carbon nanospheres in Fig. 2A are closer to the high image' and the display-explosion is followed to reveal the plurality of carbon nanospheres constituting the group. ^ 2C image is the high-resolution image of the carbon nanotube material of the 2nd Α®, which is the multi-walled and hollow nature of carbon nanospheres that are concentrated in and exposed to fine clusters. . Figure 3 is a spectrum diagram of the dynamic grading of dispersed carbon nanospheres in accordance with the present invention. Fig. 4 is a SEM image of carbon nanotubes dispersed in a polar solvent according to an embodiment of the present invention. The fourth picture is the image of the carbon nanosphere in Figure 4. Figure 5 shows a comparison of the light scattering spectra of the carbon nanotubes in the water towel for 2 hours. ::ODMA\PCD〇CS\TPEDMS\41201\1 24 200936499 [Key component symbol description] Benefit * *»>

::ODMA\PCDOCS\TPEDMS\41201 \1 25

Claims (1)

200936499 VII. Patent application scope: L - A method for producing a carbon nanomaterial dispersion, comprising: (1) providing a carbon nanomaterial comprising a plurality of multi-walled, graphite carbon nanospheres, wherein the carbon The nanosphere is at least partially agglomerated into a plurality of clusters of carbon nanospheres; forming a solution comprising a polar solvent and an organic surface modifier; Mixing the nanomaterial with the solution and ultrasonically treating the solution to agglomerate the carbon nanospheres to produce a method as described in claim 1, wherein the step is suspended in the polar solvent. (i) The stone-resistant material has an average particle size greater than meters using dynamic light scattering measurements. The method of claim 1, wherein the stone anti-rice material in step (iii) has an average particle size of less than 500 mils using dynamic light scattering measurements. The method of claim 1, wherein the stone material in the step (out) has an average particle diameter of less than 300 = ± using dynamic light scattering measurement. No. 5. The method described in item 1 of the patent specification, wherein the f-water-free material of the step (5) has an average particle diameter of less than 200 m. using dynamic light scattering measurement. The method described in the scope of the invention, which comprises the polar water, ethanol, THF or a combination thereof. (1) 匕3 i self-feeding according to the method described in item 1, the towel level modifier is ϊίΐΐ surfactant, organic acid, carbohydrate, amino acid and combination thereof: ODMA\PCD〇CS\ TPEDMS\41201\1 26 200936499 8. The method of claim 1, wherein the surface modification agent is the method of claim 1, wherein the carbon nanomaterial The surface has at least 2% by weight of oxygen measured using X-ray photoelectron spectroscopy (XPS). The method of claim 1, wherein the carbon nanowave is treated for at least 30 minutes. The carbon nanosphere according to Item 11 is formed by forming a precursor mixture comprising a carbon precursor and a plurality of template nano particles, and polymerizing the carbon precursor, the template nanoparticle comprising a catalytic metal p * carbonizing the precursor mixture to form an intermediate carbon material comprising a plurality of carbon nanostructures, amorphous carbon and selectively residual catalytic metal; and by removing at least a portion of the amorphous carbon and optionally a portion of any residual = The metal is purified from the (four) carbon material to produce a carbon nanomaterial comprising a plurality of structures. The method of claim 11, wherein the towel nanoparticle is prepared by the following steps: (a) reacting a plurality of precursor catalyst atoms with a plurality of organic components to form a composite catalyst molecule; (b) allowing or causing the composite catalyst molecule to form the template nanoparticle.八八:ΪΙΓϋΪΙΓϋ目帛1 item Linfa system only carbon nano-materials 蚪刀散液,,,匕3 is a plurality of carbon nanostructures dispersed in a polar solvent. 14) A method for producing a carbon nanomaterial dispersion, comprising: a mountain-f for agglomerated carbon nanomaterial, comprising a plurality of multi-walled, graphite stone anti-meter balls, wherein the carbon nanospheres have an average粒# ranges from 1〇 nanometer to 2〇〇奈 ::ODMA\PCDOCS\TPEDMS\41201\1 27 200936499 meters and has an irregular surface; (11) forms a polar solvent, organic surface modifier and a solution of the carbon nanomaterial; and (iii) ultrasonically treating the solution to cause at least a portion of the surface modifier to bond to the nanosphere, and suspending the carbon nanosphere in the polar solvent. ❹ 15. The method of claim 14, wherein the step of providing the carbon nanomaterial has an average particle size ranging from 5 〇〇 'nm to 5 nm using dynamic light scattering measurement, and wherein The average particle size of the carbon-neutral light scattering measurement of the step (诅) is less than 300 nm. Bamboo/other use 1$. For the method described in claim 14, the carbon nanomaterials provided in the steps include the average grain size of the bribes, the nephew; and the corrective steps (5) The carbon nanomaterial has an average particle size of less than 200 nm as measured by i-state first scattering. ^•. The method of claim 14, wherein the polar solvent comprises the method of claim 14, wherein the surface modifying agent comprises or the s-energy group is selected from the group consisting of a carboxyl group and an amine group. The method of claim 14, wherein the surface modification is selected from the group consisting of glucose, glycolic acid, glycine, ascorbic acid, dodecane, and sulphate a group consisting of trifluoroacetic acid and combinations thereof. Soil* 20. A carbon nanosphere dispersion comprising: a polar solvent; and a ball of residual material, the carbon in the crucible: a plurality of surface modifiers of a plurality of carbon nano surfaces in a polar solvent Minute? .颂,,. To the table:: ODMA\PCDOCS\TPEDMS\41201\1 28 200936499 21 Nano-carbon i semi-patented fine 2G narration of carbon nanospheres, the carbon in the τ has the use of dynamic light scattering The average particle size measured is less than 200 nm. 23. The carbon nanosphere dispersion according to claim 2, wherein the surface modifier is selected from the group consisting of glucose, glycolic acid, glycine, ascorbic acid, sodium dodecyl benzoate, a group consisting of phosphotungstic acid, trifluoroacetic acid, and combinations thereof. G 24. The carbon nanosphere dispersion of claim 2, wherein the polar solvent comprises water. 25. A composite material comprising carbon nanomaterials in the scope of claim 20 is dispersed in a material. ❹ ::〇DMA\PCDOCS\TPEDMS\41201\1