CN103241777B - The preparation method of a kind of carbon material, carbon-ferriferrous oxide composite material - Google Patents
The preparation method of a kind of carbon material, carbon-ferriferrous oxide composite material Download PDFInfo
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Abstract
The invention provides the preparation method of a kind of carbon material, carbon-ferriferrous oxide composite material.Method provided by the invention with chlorinated polyvinyl chloride and iron cpd for raw material, chlorinated polyvinyl chloride-the iron complexes obtained or chlorinated polyvinyl chloride fibre-iron complexes are heated, complete to chlorinated polyvinyl chloride burning, obtain carbon ball-iron composite material or carbon fiber-iron composite material after cooling.Above-mentioned carbon ball-iron composite material of preparing or carbon fiber-iron composite material, in order to obtain carbon material, mix with acidic solution by the present invention, carry out precipitate and separate, obtain carbon ball or carbon fiber after leaving standstill.Method provided by the invention is using chlorinated polyvinyl chloride as the carbon source material synthesizing carbon material or carbon-iron cpd matrix material, under the quick catalysis of iron cpd, in combustion reactions process, chlorinated polyvinyl chloride carries out dehydrochlorination and crosslinked action, synthesis carbon-ferriferrous oxide composite material or carbon material.Method technique provided by the invention is simple, and productive rate is higher.
Description
Technical field
The present invention relates to technical field of nano material, particularly relate to the preparation method of a kind of carbon material, carbon-ferriferrous oxide composite material.
Background technology
The diameter that typically refers to of nanometer, carbon micron-spheres and carbon fiber is the carbon materials of tens nanometers to hundreds of micron.Nanometer, carbon micron-spheres and carbon fiber have good chemical stability, thermostability, excellent conduction and thermal conductivity and larger specific surface area, are a kind of carbon materials with wide application prospect.Current nanometer, carbon micron-spheres and carbon fiber have been widely used in supported catalyst, absorb polluted matter and have prepared ultracapacitor and lithium ion battery etc.
Usually, nanometer, carbon micron-spheres adopt the preparation of electric arc power generating method, laser evaporization method, electrochemical vapor deposition and catalysis synthesis process.The normally organic hydrocarbon small molecules of carbon source in these methods, as: methane, acetylene, ethene etc., seldom have the carbon source material adopting organic polymer as preparation nanometer, carbon micron-spheres.As the publication number Chinese patent that is CN10183547A discloses a kind of preparation method of carbon micron-spheres; the method adopts heteropolyacid to be catalyzer; with furane resin; resol or bituminous resins of living are carbon source; using high-purity argon gas as protection gas; with ethanol or dimethyl sulfoxide (DMSO) for solvent, prepare carbon micron-spheres.This method expensive starting materials and a large amount of use solvent limit it and prepare carbon micron-spheres on a large scale.For another example publication number is a kind of method that the Chinese patent of CN10774577A discloses carbon micron-spheres; the method uses fluidized-bed reactor or spray-dryer to prepare phenolic resin microspheres; then using high-purity argon gas as protection gas; carbon micron-spheres prepared by carbonized phenolic resin microballoon, and the method equipment used is complicated and technique is loaded down with trivial details.
Meanwhile, the mixture of nanometer, carbon micron-spheres and carbon fiber and Z 250 thereof also causes the attention of people gradually, this kind of material combines the performance of nanometer, carbon micron-spheres and carbon fiber excellence and the advantage of Z 250 catalytic activity and magnetic, photocatalysis degradation organic contaminant, magnetic absorption separation of heavy metal ions and organic pollutant and with polymkeric substance compound etc. in there is potential application prospect.
Current prepare nanometer, carbon micron-spheres/Z 250 method less.RongboZheng etc. have reported and have adopted the method for ultrasonic spray pyrolysis to prepare the carbon micron-spheres (RongboZheng that load has ferriferrous oxide nano-particle, XianweiMeng, FangqiongTang.High-DensityMagnetiteNanoparticlesLocatedi nCarbonHollowMicrosphereswithGoodDispersibilityandDurabi lity:TheirOne-PotPreparationandMagneticProperties.Europe anJournalofInorganicChemistry, 20:3003 ~ 3007.), utilize iron protochloride and citric acid as raw material, the method of ultrasonic spray pyrolysis is adopted to prepare the carbon micron-spheres that area load has ferriferrous oxide nano-particle.This method preparation time is longer, and productive rate is lower.For another example polyvinyl chloride or chlorinated polyvinyl chloride is utilized to be how fast dehydrochlorination makes its cross-linking carbonization as the key issue of precursor power nanometer, micron carbon fiber at present.W.M.Qiao etc. report a kind of method (W.M.Qiao preparing carbon fiber, S.H.Yoon, Y.Korai, I.Mochida, S.Inoue, T.Sakurai, T.Shimohara.Preparationofactivatedcarbonfibersfrompolyvi nylchloride.Carbon, 7 (24): 1327 ~ 1331.), the method for the method two step dechlorination, prepares carbon fiber.But the technics comparing of this scientific and technical literature report is loaded down with trivial details, and Measures compare is complicated, and productive rate is lower.
Summary of the invention
The object of the invention is to the preparation method of carbon material, carbon-ferriferrous oxide composite material, the productive rate of the carbon material that method provided by the invention obtains, carbon-ferriferrous oxide composite material is high.
The invention provides the preparation method of a kind of carbon ball-ferriferrous oxide composite material, comprise the following steps:
By chlorinated polyvinyl chloride and iron cpd mixing, obtain chlorinated polyvinyl chloride-iron mixture;
Described chlorinated polyvinyl chloride-iron mixture is carried out reacting by heating, complete to chlorinated polyvinyl chloride burning, obtain carbon ball-ferriferrous oxide composite material.
The invention provides a kind of preparation method of carbon fiber-ferriferrous oxide composite material, comprise the following steps:
Chlorinated polyvinyl chloride and iron cpd are mixed in organic solvent, the mixing solutions obtained is carried out solvent spinning, obtains chlorinated polyvinyl chloride fibre-iron mixture;
Described chlorinated polyvinyl chloride fibre-iron mixture is carried out reacting by heating, complete to chlorinated polyvinyl chloride burning, obtain carbon fiber-ferriferrous oxide composite material.
Preferably, the mass ratio of described chlorinated polyvinyl chloride and iron cpd is (85 ~ 99.5): (0.5 ~ 15).
Preferably, the temperature of described heating is 250 DEG C ~ 950 DEG C.
Preferably, described iron cpd is one or more in iron protoxide, ferric oxide, Z 250, ferrous hydroxide and ironic hydroxide.
Preferably, described organic solvent is tetrahydrofuran (THF), DMF, orthodichlorobenzene, one or more in dimethyl sulfoxide (DMSO) and acetone.
Preferably, the voltage of described solvent spinning is 5KV ~ 40KV;
In described solvent spinning, the distance of spinning nozzle and collector is 5 centimetres ~ 30 centimetres.
The invention provides a kind of preparation method of carbon ball, comprise the following steps:
Carbon ball-ferriferrous oxide composite material preparation method described in technique scheme obtained mixes with acidic solution, leaves standstill postprecipitation and is separated, obtain carbon ball.
The invention provides a kind of preparation method of carbon fiber, comprise the following steps:
Carbon fiber-ferriferrous oxide composite material preparation method described in technique scheme obtained mixes with acidic solution, leaves standstill postprecipitation and is separated, obtain carbon fiber.
Preferably, the volumetric molar concentration of described acidic solution is 0.5mol/L ~ 2.0mol/L.
The invention provides the preparation method of a kind of carbon material, carbon-ferriferrous oxide composite material.Chlorinated polyvinyl chloride for raw material with chlorinated polyvinyl chloride and iron cpd, directly mixes with iron cpd, obtains chlorinated polyvinyl chloride-iron complexes by method provided by the invention; Or chlorinated polyvinyl chloride and iron cpd are dissolved in organic solvent, then the mixing solutions obtained is carried out solvent spinning, obtain chlorinated polyvinyl chloride fibre-iron complexes; Then chlorinated polyvinyl chloride-the iron complexes obtained or chlorinated polyvinyl chloride fibre-iron complexes are carried out reacting by heating, complete to chlorinated polyvinyl chloride burning, obtain carbon ball-iron composite material or carbon fiber-iron composite material after cooling.Above-mentioned carbon ball-iron composite material of preparing or carbon fiber-iron composite material, in order to obtain carbon material, mix with acidic solution by the present invention, carry out precipitate and separate, obtain carbon ball or carbon fiber after leaving standstill.Method provided by the invention is using chlorinated polyvinyl chloride as the carbon source material synthesizing carbon material or carbon-iron cpd matrix material, under the quick catalysis of iron cpd, in combustion reactions process, chlorinated polyvinyl chloride carries out dehydrochlorination and crosslinked action, synthesis carbon-ferriferrous oxide composite material or carbon material.Method technique provided by the invention is simple, and productive rate is higher.Embodiment of the present invention result shows, method provided by the invention prepares the yield of carbon fiber-ferriferrous oxide composite material can up to 42.0%, and the yield preparing carbon ball can up to 32.8%.
Embodiment
A preparation method for carbon ball-ferriferrous oxide composite material, comprises the following steps:
By chlorinated polyvinyl chloride and iron cpd mixing, obtain chlorinated polyvinyl chloride-iron mixture;
Described chlorinated polyvinyl chloride-iron mixture is carried out reacting by heating, complete to chlorinated polyvinyl chloride burning, obtain carbon ball-ferriferrous oxide composite material.
Method provided by the invention take chlorinated polyvinyl chloride as carbon source, under the katalysis of iron cpd, carries out combustion reactions, dehydrochlorination and carry out crosslinking reaction, obtains carbon-ferriferrous oxide composite material.The invention provides method technique and simple to operate, the carbon obtained-Z 250 yield is high.
The present invention, by chlorinated polyvinyl chloride and iron cpd mixing, obtains chlorinated polyvinyl chloride-iron mixture.The method of the present invention to described chlorinated polyvinyl chloride and iron cpd mixing does not have special restriction, adopts the technical scheme that solid materials well known to those skilled in the art mixes.Chlorinated polyvinyl chloride and iron cpd are preferably placed in ball mill by the present invention, are uniformly mixed, and obtain chlorinated polyvinyl chloride-iron mixture.In the present invention, the particle diameter of described chlorinated polyvinyl chloride is preferably 50 nanometer ~ 500 micron, is more preferably 70 nanometer ~ 480 micron, most preferably is 100 nanometer ~ 450 micron; Described iron cpd is preferably one or more in iron protoxide, ferric oxide, Z 250, ferrous hydroxide and ironic hydroxide; The particle diameter of described iron cpd is preferably 5 nanometer ~ 50 micron, is more preferably 10 nanometer ~ 45 micron, most preferably is 20 nanometer ~ 40 micron; The mass ratio of described chlorinated polyvinyl chloride and iron cpd is preferably (85 ~ 99.5): (0.5 ~ 15), is more preferably (87 ~ 98): (2 ~ 13), most preferably is (90 ~ 95): (5 ~ 10).In the present invention, the speed that described chlorinated polyvinyl chloride and iron cpd are uniformly mixed is preferably 50 revs/min ~ 100 revs/min, is more preferably 60 revs/min ~ 90 revs/min, most preferably is 70 revs/min ~ 85 revs/min; The time that described chlorinated polyvinyl chloride and iron cpd are uniformly mixed is preferably 5 minutes ~ 20 minutes, is more preferably 8 minutes ~ 18 minutes, most preferably is 10 minutes ~ 15 minutes.
After obtaining the mixture of chlorinated polyvinyl chloride-iron, described chlorinated polyvinyl chloride-iron mixture is carried out reacting by heating by the present invention, complete to chlorinated polyvinyl chloride burning, obtains carbon ball-ferriferrous oxide composite material.Described chlorinated polyvinyl chloride-iron mixture is preferably placed in ceramic crucible by the present invention, and heat after adding a cover, chlorinated polyvinyl chloride takes fire, until chlorinated polyvinyl chloride burning completely, produce without flame above ceramic crucible, be cooled to room temperature, obtain carbon ball-ferriferrous oxide composite material.In the present invention, the temperature of described heating is preferably 250 DEG C ~ 950 DEG C, is more preferably 280 DEG C ~ 920 DEG C, most preferably is 300 DEG C ~ 900 DEG C.
The invention provides a kind of preparation method of carbon fiber-Z 250, comprise the following steps:
Chlorinated polyvinyl chloride and iron cpd are mixed in organic solvent, the mixing solutions obtained is carried out solvent spinning, obtains chlorinated polyvinyl chloride fibre-iron mixture;
Described chlorinated polyvinyl chloride fibre-iron mixture is carried out reacting by heating, complete to chlorinated polyvinyl chloride burning, obtain carbon fiber-ferriferrous oxide composite material.
Chlorinated polyvinyl chloride and iron cpd mix by the present invention in organic solvent, then the mixing solutions obtained are carried out solvent spinning, obtain chlorinated polyvinyl chloride fibre-iron mixture.In the present invention, the particle diameter of described chlorinated polyvinyl chloride is preferably 50 nanometer ~ 500 micron, is more preferably 70 nanometer ~ 480 micron, most preferably is 100 nanometer ~ 450 micron; Described iron cpd is preferably one or more in iron protoxide, ferric oxide, Z 250, ferrous hydroxide and ironic hydroxide; The particle diameter of described iron cpd is preferably 5 nanometer ~ 50 micron, is more preferably 10 nanometer ~ 45 micron, most preferably is 20 nanometer ~ 40 micron; The mass ratio of described chlorinated polyvinyl chloride and iron cpd is preferably (85 ~ 99.5): (0.5 ~ 15), is more preferably (87 ~ 98): (2 ~ 13), most preferably is (90 ~ 95): (5 ~ 10);
In the present invention, described organic solvent is tetrahydrofuran (THF), N, dinethylformamide, orthodichlorobenzene, one or more in dimethyl sulfoxide (DMSO) and acetone, be more preferably tetrahydrofuran (THF), N, dinethylformamide, orthodichlorobenzene, one or both in dimethyl sulfoxide (DMSO) and acetone, when described organic solvent is tetrahydrofuran (THF), N, dinethylformamide, orthodichlorobenzene, during in dimethyl sulfoxide (DMSO) and acetone two kinds, two component mass ratioes in organic solvent are preferably (5 ~ 95): (95 ~ 5), be more preferably (10 ~ 90): (90 ~ 10), most preferably be (20 ~ 80): (80 ~ 20), the consumption of the present invention to described organic solvent does not have special restriction, above-mentioned chlorinated polyvinyl chloride and iron cpd can be dissolved completely, in the present invention, the mass ratio of described organic solvent and chlorinated polyvinyl chloride is preferably (70 ~ 97.5): (2.5 ~ 30), be more preferably (75 ~ 95): (5 ~ 25), most preferably be (80 ~ 90): (10 ~ 20).
The method of the present invention to described solvent spinning does not have special restriction, adopts the technical scheme of solvent spinning well known to those skilled in the art.The mixing solutions of the chlorinated polyvinyl chloride obtained and iron cpd is preferably placed in plastic injector by the present invention, described syringe is being received in high-voltage power supply, the positive pole of power supply connects spinning nozzle, the negative pole of power supply connects copper sheet collector, described collector ground connection simultaneously, after spinning for some time, the fiber obtained is peeled off from copper sheet collector, after dry removing residual solvent, obtain thermovyl-iron mixture.In the present invention, the voltage of supply of described solvent spinning is preferably 5KV ~ 40KV, is more preferably 10KV ~ 35KV, most preferably is 15KV ~ 30KV; Distance between described spinning nozzle and collector is preferably 5 centimetres ~ 30 centimetres, is more preferably 10 centimetres ~ 25 centimetres, most preferably is 15 centimetres ~ 20 centimetres; The present invention does not have special restriction the time to spinning, and those skilled in the art according to the quality of the matrix material of the amount of mixing solutions and needs, can select the rational spinning time.The method of the present invention to described drying does not have special restriction, adopts the technical scheme of drying well known to those skilled in the art, in the present invention, described drying is preferably vacuum-drying, the temperature of described drying is preferably 70 DEG C ~ 90 DEG C, is more preferably 75 DEG C ~ 85 DEG C, most preferably is 80 DEG C; The time of described drying is preferably 18 hours ~ 30 hours, is more preferably 21 hours ~ 27 hours, most preferably is 24 hours.
After obtaining chlorinated polyvinyl chloride fibre-iron complexes, the present invention obtains the technical scheme of carbon ball-ferriferrous oxide composite material according to the chlorinated polyvinyl chloride-iron complexes described in technique scheme, prepares carbon fiber-ferriferrous oxide composite material.No longer the process that chlorinated polyvinyl chloride fibre-iron complexes prepares carbon fiber-ferriferrous oxide composite material is repeated at this.
The invention provides a kind of preparation method of carbon material, the Z 250 in removing carbon ball-ferriferrous oxide composite material of preparing of technique scheme or carbon fiber-ferriferrous oxide composite material, can obtain corresponding carbon ball or carbon fiber.
The invention provides a kind of preparation method of carbon ball, comprise the following steps:
Carbon ball-ferriferrous oxide composite material preparation method described in technique scheme obtained mixes with acidic solution, leaves standstill postprecipitation and is separated, obtain carbon ball.
The present invention, according to the technical scheme preparing carbon ball-ferriferrous oxide composite material described in technique scheme, prepares carbon ball-ferriferrous oxide composite material.Mixed with acidic solution by the carbon obtained ball-Z 250, Z 250 wherein and acidic solution react, and dissolve in the solution, by precipitate and separate after leaving standstill, obtain carbon ball.The present invention is preferably extremely neutral by being separated the solid washed with de-ionized water obtained, and obtains carbon ball.In the present invention, described acidic solution is preferably one or more in hydrochloric acid, nitric acid or sulfuric acid, is more preferably hydrochloric acid; The volumetric molar concentration of described acidic solution is preferably 0.5mol/L ~ 2.0mol/L, is more preferably 1.0mol/L ~ 1.5mol/L; The described standing time is preferably 24 hours ~ 36 hours, is more preferably 27 hours ~ 33 hours, most preferably is 30 hours.
Present invention also offers a kind of preparation method of carbon fiber, comprise the following steps:
Carbon fiber-ferriferrous oxide composite material preparation method described in technique scheme obtained mixes with acidic solution, leaves standstill postprecipitation and is separated, obtain carbon fiber.
The present invention, according to the technical scheme preparing carbon fiber-ferriferrous oxide composite material described in technique scheme, prepares carbon fiber-ferriferrous oxide composite material; Then mixed with acidic solution by the carbon fiber-ferriferrous oxide composite material obtained, Z 250 wherein and acidic solution react, and dissolve in the solution, by precipitate and separate after leaving standstill, obtain carbon fiber.The present invention is preferably extremely neutral by being separated the solid washed with de-ionized water obtained, and obtains carbon fiber.In the present invention, described acidic solution is preferably one or more in hydrochloric acid, nitric acid or sulfuric acid, is more preferably hydrochloric acid; The volumetric molar concentration of described acidic solution is preferably 0.5mol/L ~ 2.0mol/L, is more preferably 1.0mol/L ~ 1.5mol/L; The described standing time is preferably 24 hours ~ 36 hours, is more preferably 27 hours ~ 33 hours, most preferably is 30 hours.
The invention provides the preparation method of a kind of carbon material, carbon-ferriferrous oxide composite material.Chlorinated polyvinyl chloride for raw material with chlorinated polyvinyl chloride and iron cpd, directly mixes with iron cpd, obtains chlorinated polyvinyl chloride-iron complexes by method provided by the invention; Or chlorinated polyvinyl chloride and iron cpd are dissolved in organic solvent, then the mixing solutions obtained is carried out solvent spinning, obtain chlorinated polyvinyl chloride fibre-iron complexes; Then chlorinated polyvinyl chloride-the iron complexes obtained or chlorinated polyvinyl chloride fibre-iron complexes are carried out reacting by heating, complete to chlorinated polyvinyl chloride burning, obtain carbon ball-iron composite material or carbon fiber-iron composite material after cooling.Above-mentioned carbon ball-iron composite material of preparing or carbon fiber-iron composite material, in order to obtain carbon material, mix with acidic solution by the present invention, carry out precipitate and separate, obtain carbon ball or carbon fiber after leaving standstill.Method provided by the invention is using chlorinated polyvinyl chloride as the carbon source material synthesizing carbon material or carbon-iron cpd matrix material, under the quick catalysis of iron cpd, in combustion reactions process, chlorinated polyvinyl chloride carries out dehydrochlorination and crosslinked action, synthesis carbon-ferriferrous oxide composite material or carbon material.Method technique provided by the invention is simple, and productive rate is higher.Embodiment of the present invention result shows, method provided by the invention prepares the yield of carbon fiber-ferriferrous oxide composite material can up to 42.0%, and the yield preparing carbon ball can up to 32.8%.
In order to further illustrate the present invention, below in conjunction with embodiment, the preparation method to carbon material provided by the invention, carbon-ferriferrous oxide composite material is described in detail, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
By weight, by 99 parts, particle diameter is the chlorinated polyvinyl chloride of 75 nanometers and 1 part, particle diameter is 10 nanometers ferric oxide adds in ball mill simultaneously, carry out under under the speed of 50 revs/min being uniformly mixed 10 minutes, obtain chlorinated polyvinyl chloride-ferric oxide mixture;
Get above-mentioned chlorinated polyvinyl chloride-1 gram, ferric oxide mixture (comprising 0.99 gram of chlorinated polyvinyl chloride and 0.01 gram of ferric oxide) and be placed in 15 milliliters of crucibles, and add and be placed on crucible; Bottom gas burning lamp flame envelope heating crucible, after a few second, chlorinated polyvinyl chloride takes fire, and now in crucible, temperature is 700 DEG C; After no longer burning to chlorinated polyvinyl chloride, take off crucible, be put in shady and cool place and be cooled to room temperature; Obtain carbon-ferriferrous oxide composite material.
The quality that the present invention weighs the carbon-ferriferrous oxide composite material obtained is 0.32 gram, and calculating yield is 32.0%; Carbon-the ferriferrous oxide composite material obtained is carried out scanning electron microscope scanning analysis by the present invention, and result shows, carbon-ferriferrous oxide composite material that the present invention obtains is carbon ball-ferroferric oxide compound, and median size is 75 nanometer ~ 100 nanometers.
The present invention just volumetric molar concentration is that the aqueous hydrochloric acid of 1.0mol/L joins in carbon ball-Z 250 black mixture that technique scheme obtains, and placing 24 hours, precipitate and separate, is 7 by washed with de-ionized water to pH value.Now obtain the carbon material of purifying.
It is 0.29 gram that the present invention weighs the quality obtaining carbon material, and calculating yield is 29.3%; The carbon material obtained is carried out scanning electron microscope scanning analysis by the present invention, and result shows, the carbon material that the present invention obtains is carbon ball, and median size is 75 nanometer ~ 100 nanometers.
Embodiment 2
By weight, by 97.5 parts, particle diameter is the chlorinated polyvinyl chloride of 2 microns and 2.5 parts, particle diameter is that 20 nanometer ferric oxide add in ball mill simultaneously, carry out under under the speed of 50 revs/min being uniformly mixed 10 minutes, obtain mixture;
Get chlorinated polyvinyl chloride-1 gram, ferric oxide mixture (comprising 0.975 gram of chlorinated polyvinyl chloride and 0.025 gram of ferric oxide) that technique scheme obtains and be placed in 15 milliliters of crucibles, and add and be placed on crucible; Bottom gas burning lamp flame envelope heating crucible, after a few second, chlorinated polyvinyl chloride takes fire, and now in crucible, temperature is 700 DEG C; After no longer burning to chlorinated polyvinyl chloride, take off crucible, be put in shady and cool place and be cooled to room temperature, obtain carbon-ferriferrous oxide composite material.
The quality that the present invention weighs the carbon-ferriferrous oxide composite material obtained is 0.36 gram, and calculating yield is 36.0%; Carbon-the ferriferrous oxide composite material obtained is carried out scanning electron microscope scanning analysis by the present invention, and result shows, carbon-ferriferrous oxide composite material that the present invention obtains is carbon ball-ferroferric oxide compound, and median size is 2 microns ~ 2.5 microns.
The present invention just volumetric molar concentration is carbon ball-Z 250 black mixture that the aqueous hydrochloric acid of 1.0mol/L joins technique scheme and obtains, and places 24 hours, precipitate and separate, is 7, now obtains the carbon material of purifying by washed with de-ionized water to pH value.
The quality that the present invention weighs the carbon material obtained is 0.32 gram, and calculating yield is 32.8%; The carbon material obtained is carried out scanning electron microscope scanning analysis by the present invention, and result shows, the carbon material that the present invention obtains is carbon ball, and median size is 2 microns ~ 2.5 microns.
Embodiment 3
By weight, by 95 parts, particle diameter is the chlorinated polyvinyl chloride of 20 microns and 5 parts, particle diameter is 50 nanometers ferric oxide adds in ball mill simultaneously, carry out being uniformly mixed 10 minutes under the rotating speed of 50 revs/min, obtain chlorinated polyvinyl chloride-ferric oxide mixture;
Get chlorinated polyvinyl chloride-1 gram, ferric oxide mixture (comprising 0.95 gram of chlorinated polyvinyl chloride and 0.05 gram of ferric oxide) that technique scheme obtains and be placed in 15 milliliters of crucibles, and add and be placed on crucible; Bottom gas burning lamp flame envelope heating crucible, after a few second, chlorinated polyvinyl chloride takes fire, and now in crucible, temperature is 700 DEG C; After no longer burning to chlorinated polyvinyl chloride, take off crucible, be put in shady and cool place and be cooled to room temperature, obtain carbon-ferriferrous oxide composite material.
It is 0.41 gram that the present invention weighs the quality obtaining carbon-ferriferrous oxide composite material, and calculating yield is 41.0%; Carbon-the ferriferrous oxide composite material obtained is carried out scanning electron microscope scanning analysis by the present invention, and result shows, carbon-ferriferrous oxide composite material prepared by the present invention is carbon ball-ferroferric oxide compound, and median size is 20 microns ~ 25 microns.
Volumetric molar concentration is carbon ball-Z 250 black mixture that the aqueous hydrochloric acid of 1.0mol/L joins technique scheme and obtains by the present invention, places 24 hours, precipitate and separate, is 7, now obtains the carbon material of purifying by washed with de-ionized water to pH value;
The quality that the present invention weighs the carbon material obtained is 0.34 gram, and calculating yield is 35.8%; The carbon material obtained is carried out scanning electron microscope scanning analysis by the present invention, and result shows, the carbon material that the present invention obtains is carbon ball, and median size is 20 microns ~ 25 microns.
Embodiment 4
By weight, by 90 parts, particle diameter is the chlorinated polyvinyl chloride of 200 microns and 10 parts, particle diameter is 5 microns ironic hydroxide adds in ball mill simultaneously, carry out being uniformly mixed 10 minutes under the rotating speed of 50 revs/min, obtain chlorinated polyvinyl chloride-ironic hydroxide mixture;
Get chlorinated polyvinyl chloride-6 grams, ironic hydroxide mixture (comprising 5.4 grams of chlorinated polyvinyl chlorides and 0.6 gram of ironic hydroxide) that technique scheme obtains and be placed in 30 milliliters of crucibles, and add and be placed on crucible; Bottom gas burning lamp flame envelope heating crucible, after a few second, chlorinated polyvinyl chloride takes fire, and now in crucible, temperature is 500 DEG C; After no longer burning to chlorinated polyvinyl chloride, take off crucible, be put in shady and cool place and be cooled to room temperature, obtain carbon-ferriferrous oxide composite material.
It is 2.02 grams that the present invention weighs the quality obtaining carbon-ferriferrous oxide composite material, and calculating yield is 33.7%; Carbon-the ferriferrous oxide composite material obtained is carried out scanning electron microscope scanning analysis by the present invention, and result shows, carbon-ferriferrous oxide composite material provided by the invention is carbon ball-ferroferric oxide compound, and median size is 200 microns ~ 250 microns.
Be that the aqueous hydrochloric acid of 1.0mol/L joins above-mentioned carbon-Z 250 black matrix material by volumetric molar concentration, place 24 hours, precipitate and separate, be 7 by washed with de-ionized water to pH value, obtain the carbon material of purifying.
It is 1.90 grams that the present invention weighs the quality obtaining carbon material, and calculating yield is 35.2%; The carbon material obtained is carried out scanning electron microscope scanning analysis by the present invention, and result shows, carbon material prepared by the present invention is carbon ball, and median size is 200 microns ~ 250 microns.
Embodiment 5
By weight, by 95 parts, particle diameter is the chlorinated polyvinyl chloride of 100 microns and 5 parts, particle diameter is 10 nanometers ironic hydroxide joins tetrahydrofuran (THF)/N that volume ratio is 7:3, in dinethylformamide mixed solvent, after stirring and dissolving, by in the mixing solutions injected plastic syringe that obtains, again syringe is connected to the high-voltage power supply of 5KV, positive source connects spinning nozzle, negative pole connects copper sheet receptor, receptor ground connection simultaneously, fixing distance between spinning nozzle and receptor is 5 centimetres, carries out solvent spinning; Fiber spinning obtained peels from copper sheet, and be placed in the dry 24 little removal residual solvents of 80 DEG C of vacuum drying ovens, obtain chlorinated polyvinyl chloride fibre-ironic hydroxide mixture, the present invention detects the diameter obtaining fiber and is about 50 nanometers.
Get chlorinated polyvinyl chloride fibre-2 grams, ironic hydroxide mixture (comprising 1.9 grams of chlorinated polyvinyl chlorides and 0.1 gram of ironic hydroxide) that technique scheme obtains and be placed in 30 milliliters of crucibles, and add and be placed on crucible; Bottom gas burning lamp flame envelope heating crucible, after a few second, chlorinated polyvinyl chloride takes fire, and now in crucible, temperature is 500 DEG C; After no longer burning to chlorinated polyvinyl chloride, take off crucible, be put in shady and cool place and be cooled to room temperature, obtain carbon fiber-ferroferric oxide compound.
It is 0.80 gram that the present invention weighs the quality obtaining carbon fiber-ferroferric oxide compound, calculates yield 40.0%; It is 50 nanometer ~ 75 nanometers that the present invention detects the diameter obtaining carbon fiber-ferroferric oxide compound.
Volumetric molar concentration is that the aqueous hydrochloric acid of 1.0mo/L joins above-mentioned carbon fiber-Z 250 black mixture by the present invention, and placing 24 hours, precipitate and separate, is 7 by washed with de-ionized water to pH value.Now obtain the carbon fiber of purifying.
It is 0.65 gram that the present invention weighs the quality obtaining carbon fiber, and calculating yield is 34.2%; It is 50 nanometer ~ 75 nanometers that the present invention detects the diameter obtaining carbon fiber.
Embodiment 6
By weight, by 90 parts, particle diameter is the chlorinated polyvinyl chloride of 200 microns and 10 parts, particle diameter is the tetrahydrofuran (THF) and N that 20 nano ferriferrous oxides join that volume ratio is 7:3, in the mixed solvent of dinethylformamide, after stirring and dissolving, by in the mixing solutions injected plastic syringe that obtains, again syringe is connected to the high-voltage power supply of 40KV, positive source connects spinning nozzle, negative pole connects copper sheet receptor, receptor ground connection simultaneously, fixing distance between spinning nozzle and receptor is 30 centimetres, carries out solvent spinning; Fiber spinning obtained peels from copper sheet, and be placed in the dry 24 little removal residual solvents of 80 DEG C of vacuum drying ovens, obtain chlorinated polyvinyl chloride fibre-ironic hydroxide mixture, the present invention detects the diameter obtaining fiber and is about 0.2 micron.
Get chlorinated polyvinyl chloride fibre-6 grams, Z 250 mixture (comprising 5.4 grams of chlorinated polyvinyl chlorides and 0.6 gram of Z 250) that technique scheme obtains and be placed in 30 milliliters of crucibles, and add and be placed on crucible; Bottom gas burning lamp flame envelope heating crucible, after a few second, chlorinated polyvinyl chloride takes fire, and now in crucible, temperature is 700 DEG C; After no longer burning to chlorinated polyvinyl chloride, take off crucible, be put in shady and cool place and be cooled to room temperature, obtain carbon fiber-ferroferric oxide compound.
It is 2.52 grams that the present invention weighs the quality obtaining carbon fiber-ferroferric oxide compound, and calculating yield is 42.0%; It is 0.2 micron ~ 0.3 micron that the present invention detects the diameter obtaining carbon fiber-ferroferric oxide compound.
Volumetric molar concentration is that the aqueous hydrochloric acid of 1.0mol/L joins above-mentioned carbon fiber-Z 250 black mixture by the present invention, places 24 hours, precipitate and separate, is 7, obtains the carbon fiber of purifying by washed with de-ionized water to pH value.
The quality that the present invention weighs the carbon fiber obtained is 1.80 grams, and calculating yield is 33.3%; It is 0.2 micron ~ 0.3 micron that the present invention detects the diameter obtaining carbon fiber.
As seen from the above embodiment, the invention provides the preparation method of a kind of carbon material, carbon-ferriferrous oxide composite material.Chlorinated polyvinyl chloride for raw material with chlorinated polyvinyl chloride and iron cpd, directly mixes with iron cpd, obtains chlorinated polyvinyl chloride-iron complexes by method provided by the invention; Or chlorinated polyvinyl chloride and iron cpd are dissolved in organic solvent, then the mixing solutions obtained is carried out solvent spinning, obtain chlorinated polyvinyl chloride fibre-iron complexes; Then chlorinated polyvinyl chloride-the iron complexes obtained or chlorinated polyvinyl chloride fibre-iron complexes are carried out reacting by heating, complete to chlorinated polyvinyl chloride burning, obtain carbon ball-iron composite material or carbon fiber-iron composite material after cooling.Above-mentioned carbon ball-iron composite material of preparing or carbon fiber-iron composite material, in order to obtain carbon material, mix with acidic solution by the present invention, carry out precipitate and separate, obtain carbon ball or carbon fiber after leaving standstill.Method provided by the invention is using chlorinated polyvinyl chloride as the carbon source material synthesizing carbon material or carbon-iron cpd matrix material, under the quick catalysis of iron cpd, in combustion reactions process, chlorinated polyvinyl chloride carries out dehydrochlorination and crosslinked action, synthesis carbon-ferriferrous oxide composite material or carbon material.Method technique provided by the invention is simple, and productive rate is higher.Embodiment of the present invention result shows, method provided by the invention prepares the yield of carbon fiber-ferriferrous oxide composite material can up to 42.0%, and the yield preparing carbon ball can up to 32.8%.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (5)
1. a preparation method for carbon fiber-ferriferrous oxide composite material, is made up of following steps:
Chlorinated polyvinyl chloride and iron cpd are mixed in organic solvent, the mixing solutions obtained is carried out solvent spinning, obtains chlorinated polyvinyl chloride fibre-iron mixture; The voltage of described solvent spinning is 5KV ~ 40KV; Described iron cpd is one or more in iron protoxide, Z 250, ferrous hydroxide and ironic hydroxide;
In described solvent spinning, the distance of spinning nozzle and collector is 5 centimetres ~ 30 centimetres;
Described chlorinated polyvinyl chloride fibre-iron mixture is carried out reacting by heating, complete to chlorinated polyvinyl chloride burning, obtain carbon fiber-ferriferrous oxide composite material;
The temperature of described heating is 250 DEG C ~ 950 DEG C.
2. preparation method according to claim 1, is characterized in that, the mass ratio of described chlorinated polyvinyl chloride and iron cpd is (85 ~ 99.5): (0.5 ~ 15).
3. preparation method according to claim 1, is characterized in that, described organic solvent is tetrahydrofuran (THF), DMF, orthodichlorobenzene, one or more in dimethyl sulfoxide (DMSO) and acetone.
4. a preparation method for carbon fiber, comprises the following steps:
Carbon fiber-ferriferrous oxide composite material that preparation method described in claims 1 to 3 any one obtains is mixed with acidic solution, leaves standstill postprecipitation and be separated, obtain carbon fiber.
5. preparation method according to claim 4, is characterized in that, the volumetric molar concentration of described acidic solution is 0.5mol/L ~ 2.0mol/L.
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