CN108622893A - A kind of preparation method and porous carbon materials of porous carbon materials - Google Patents
A kind of preparation method and porous carbon materials of porous carbon materials Download PDFInfo
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- CN108622893A CN108622893A CN201810270504.3A CN201810270504A CN108622893A CN 108622893 A CN108622893 A CN 108622893A CN 201810270504 A CN201810270504 A CN 201810270504A CN 108622893 A CN108622893 A CN 108622893A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
Abstract
The present invention provides a kind of preparation methods of porous carbon materials, including：High molecular material is uniformly mixed with foaming agent to obtain mixture, high molecular foam material will be obtained after mixture machine-shaping, high molecular foam material is subjected to carbonization treatment, obtains porous carbon materials；The high molecular material includes by ethylene, propylene, methyl methacrylate, styrene, butadiene, vinyl chloride, chloropropene, 1, and at least one of 3 butadiene, dimethyl terephthalate (DMT), ethylene glycol, acrylonitrile, vinylacetate, methyl acrylate, caprolactam and its derivative are one or more in the polymer of monomer synthesis.This method prepares high molecular foam material using traditional processing forming method, and using it as carbon source, and high specific surface area porous carbon material is thermally treated resulting in through carbonization, the preparation method raw material sources are extensive, and at low cost, preparation process is simple, the volume production for realizing porous carbon materials, significantly reduces cost.The present invention also provides a kind of porous carbon materials.
Description
Technical field
The present invention relates to porous carbon preparing technical fields, preparation method more particularly to a kind of porous carbon materials and porous
Carbon material.
Background technology
Today's society, with the fast development of the surge and industry of population, people exceedingly develop and using non-renewable
The energy (such as coal, oil, natural gas fossil energy) so that energy shortage, meanwhile, also by a large amount of pollutant emissions to air,
It causes seriously to pollute.Problem of environmental pollution and energy crisis have become the significant challenge that human kind sustainable development faces.Therefore, it protects
Retaining ring border becomes the hot spot that scientist pays close attention to and studies with environmentally protective energy storage device is developed.
Carbon is present in nature in different forms, is the basis of all organic compounds.It is fast with material science
Speed development, carbon material are most popular one of the materials of current research due to its unique physicochemical properties.And porous carbon materials
The favor of researcher is just received once appearance, and is rapidly developed as one of research hotspot interdisciplinary.Factors make more
Hole carbon material is concerned.First, diversified presoma can be used to prepare porous carbon materials, and cost is relatively low.Secondly, porous
Carbon material also have big specific surface area, chemical stability is good, pore structure is abundant, high mechanical strength, electric conductivity well, density
More low many advantages.These comprehensive features, porous carbon materials be widely used in electrochemistry, catalysis, the energy, environment, absorption, every
The multiple fields such as heat.But the preparation method of existing porous carbon materials is of high cost, is difficult to industrialization.
Invention content
In consideration of it, first aspect present invention provides a kind of preparation method of porous carbon materials, which comes
Source is extensive, at low cost, and preparation-obtained porous carbon materials specific surface area is high, and structure easy-regulating is easy to industrialization.
Specifically, in a first aspect, the present invention provides a kind of preparation method of porous carbon materials, include the following steps：
High molecular material is uniformly mixed with foaming agent to obtain mixture, high score will be obtained after the mixture machine-shaping
The high molecular foam material is carried out carbonization treatment, obtains porous carbon materials by sub- expanded material；
The high molecular material includes by ethylene, propylene, methyl methacrylate, styrene, butadiene, vinyl chloride, chlorine
Propylene, 1,3 butadiene, dimethyl terephthalate (DMT), ethylene glycol, acrylonitrile, vinylacetate, methyl acrylate, caprolactam
And its it is one or more in the polymer that at least one of derivative is monomer synthesis.
Present invention selection is cheap, derives from a wealth of sources the high molecular material being easy to get, is processed using traditional diamond-making technique
At high molecular foam material, and using the high molecular foam material as carbon source, it is used for the preparation of porous carbon materials, is greatly reduced
Manufacturing cost, while realizing volume production.Wherein, the high molecular material specifically may include polyethylene (PE), polypropylene (PP), gather
Styrene (PS), polyethylene terephthalate (PET), polybutylene terephthalate (PBT) (PBT), poly-methyl methacrylate
Ester (PMMA), polyvinyl chloride (PVC), makrolon (PC), polytetrafluoroethylene (PTFE) (PTFE), polyamide (PA), phenoplasts (PF),
Amino resins (UF), thermoplastic polyurethane elastomer (TPU), acrylonitritrile-styrene resin (AS), acrylonitrile-butadiene-benzene
Ethylene-dien terpolymer (ABS), ethylene-vinyl acetate copolymer (EVA), styrene-butadiene copolymer (K glue), polyethers ether
Ketone (PEEK), polyolefin elastomer (POE), acetal resin (POM), polyphenylene oxide (PPO) and styrene series thermoplastic elastomer
(SBS) one or more in.
In the present invention, for different high molecular materials, the selection of the foaming agent is not particularly limited, using normal in field
Foaming agent, optionally, the foaming agent include azo-compound, sulfonyl hydrazines compound, nitroso compound, carbon
Hydrochlorate, waterglass, silicon carbide, carbon black, pentane, n-hexane, normal heptane, petroleum ether, Arcton 11, dicholorodifluoromethane,
It is one or more in dichlorotetra-fluoroethane, lauryl sodium sulfate, sodium sulfate of polyethenoxy ether of fatty alcohol and urea derivative.
The azo-compound includes but not limited to azodiisobutyronitrile (ABN), azodicarbonamide (ADC), diisopropanolamine (DIPA)
(DIPA)；The sulfonyl hydrazines compound can be but not limited to 4,4- disulfonyl hydrazide diphenyl ethers (OBSH), unifor
(TSH), three diazanyl s-triazine (THT)；The nitroso compound includes but not limited to dinitrosopentamethlyene tetramine (BN)；
The urea derivative includes but not limited to N- nitroguanidines.
Optionally, mass content of the foaming agent in the mixture is 0.5%-20%, can be further
1%-15%, 5%-10%.
In the present invention, the high molecular material is first dried before being mixed with the foaming agent, the temperature of the drying
Degree is 80-100 DEG C, and the time of the drying is 3-6 hours.
Optionally, the mode of the machine-shaping includes compression molding, extrusion molding, at fine or film forming.It is described to be processed into
The mode of type can be selected according to specific high molecular material type, select existing common molding mode.Wherein, institute
The molding temperature for stating compression molding is 60-500 DEG C, and soaking time is 2-600 minutes；Further molding temperature is 100-300
DEG C, 150-200 DEG C, soaking time be 5-100 minutes, 10-50 minutes.The extrusion temperature of the extrusion molding is 60-500 DEG C；
It is described at fine at 50-500 DEG C of fibrousness；Each temperature section heating temperature in the film forming procedure is 60-600 DEG C.The mould
Molded, extrusion molding, can be according to different high molecular material types and different holes at fine or film forming procedure processing temperature
Topology requirement etc. and set.
In the present invention, the carbonization treatment includes being carbonized for the first time, in the first time carbonisation, atmosphere be oxygen,
Air or inert gas, heating rate are 1-100 DEG C/min, and carburizing temperature is 150-1600 DEG C, and carbonization time is more than 3min.Into
One step, the heating rate is 3-50 DEG C/min, 10-20 DEG C/min, and the carburizing temperature is 300-700 DEG C, 400-600
DEG C, carbonization time is 1-5 hours, 2-4 hours.
In the present invention, optionally, when having requirements at the higher level to parameters such as the specific surface area of porous carbon materials and total pore volumes, institute
It states carbonization treatment and can further include second of carbonization, second of carbonization is completed laggard in first time carbonization
Row.In second of carbonisation, atmosphere is oxygen, air or inert gas, and heating rate is 1-100 DEG C/min, carbonization
Temperature is 150-1600 DEG C, and carbonization time is more than 3min.Further, the heating rate be 3-50 DEG C/min, 10-20 DEG C/
Min, the carburizing temperature are 800-1600 DEG C, 900-1200 DEG C, 1000-1500 DEG C, and carbonization time is 1-3 hours, 2-4 is small
When.In the present invention, activator is added in second of carbonisation, the activator includes LiOH, NaOH, KOH, H3PO4、
HNO3、H2SO4、LiCl、KCl、NaCl、ZnCl2、K2CO3、LiCO3、Na2CO3、NH3、CCl3H、CCl2H2、CClH3、CO2It is steamed with water
Gas it is one or more.When activator is gas, then corresponding gas is passed through during carbonization treatment.The activator can be with
Etching efficiency is improved, increasing specific surface area is conducive to the porous carbon materials for obtaining uniform pore diameter.Optionally, the first time carbon
The mass ratio for changing gained sample and the activator is 1:1-10 is further 1:3-8.
During the carbonization treatment, the high molecular foam material is placed in porcelain boat, then is transferred in tubular type retort
It is heat-treated, when activator is added in second of carbonisation, in order to which first time carbonization gained sample is then placed in by anticorrosion
In nickel boat, then it is transferred in tubular type retort and is heat-treated.Gas flow during the carbonization treatment is 30-500cc/
Min can be specifically 100-250cc/min, 120-200cc/min.
Optionally, before the first time carbonization treatment, first the high molecular foam material is dried, the drying
Temperature be 80-100 DEG C, time of the drying is 3-6 hours.Optionally, before second of carbonization treatment, first by institute
It states carbonization gained sample for the first time to be dried, the temperature of the drying is 80-100 DEG C, and the time of the drying is that 3-6 is small
When.
Since technique needs or in order to assign porous carbon materials other additional properties (such as flame retardant properties, antioxygenic property
Deng), it can also further comprise auxiliary agent in the mixture, optionally, the mass content of the auxiliary agent is 0.5%-20%, into one
Step ground can be 5%-10%.Optionally, the auxiliary agent include lubricant, it is heat stabilizer, light stabilizer, antioxidant, fire retardant, quiet
It is one or more in electric agent, coupling agent, compatilizer and nucleating agent.Wherein, the fire retardant includes chlorinated paraffin, chlorinated polyethylene
Alkene, tetrabromobisphenol A (such as FR-1525), deca-BDE, red phosphorus, ammonium polyphosphate, ammonium phosphate salt, phosphate, phosphate, phosphonitrile
Compound, organic hypophosphorous acid, melamine cyanurate, melamine phosphate, aluminium hydroxide, one kind in magnesium hydroxide or more
Kind.The lubricant includes higher aliphatic, aliphatic ester, higher fatty acids, fatty acid amide, paraffin, metal soap stearic acid
This, it is one or more in fatty acid soaps, fatty acid amide.The heat stabilizer includes that lead salt compound stabilizer, OBS organic groups are steady
Determine agent, organic tin stabilizer, liquid composite stabilizing agent, calcium-zinc composite stabilizing agent, barium zinc compound stabilizer, potassium zinc stable composition
It is one or more in agent.The light stabilizer includes salicylic acid lipid, benzophenone, benzotriazole, triazines, substitution
It is one or more in vinyl cyanide, Oxamides, organo-nickel compounds class, hindered amines.The antioxidant includes antioxidant
264, antioxidant 1076, antioxidant CA, antioxidant 330, MEB:2,2'- methylene bis (- 6 tert-butyl phenol of 4- ethyls), HBP:N,
Six methines of N'- double -3 (- 4 hydroxy phenyl of 3,5 di-t-butyl) propionamides, TBM:1,3,5- tri- (3,5 tertiary butyl-4-hydroxy benzyls
Base) trimethylbenzene, antioxidant 3114:1,3,5- tri- (3,5 di-tert-butyl-hydroxy phenyl) isocyanates, HLS:4- hydroxyls ten
Two alkanoic acid anilids, HSS:4- hydroxyoctadecanoic acids anilid, antioxidant 300:4,4'- thiobis (3- methyl-6-tert-butyls
Base phenol), MMB:2,2'- methylene bis (4- methyl-6-tert-butylphenols), DOD:4,4'- bis- t-octyl diphenylamines, EBP:1,6
Bis- (bis- tertiary J bases -4- hydroxy phenyls of the 3,5-) propionic esters of six methines, TNP:Three (nonyl is for phenyl) phosphite esters, TBP:Three (2,
4- di-tert-butyl-phenyls) phosphite ester, DPD:The double octadecyl ester pentaerythritol esters of diphosphorous acid and DLTDP:Thiodipropionic acid dilauryl
It is one or more in cinnamic acid ester.The electrostatic agent includes trihydroxyethyl methyl quaternary ammonium methyl sulfate, octadecyldimethyl
It is one or more in quaternary ammonium nitrate, alkylamide.The coupling agent include silane coupling agent (such as Z 6043, A1120,
AC-66E, KBM403 coupling agent), titanate coupling agent, aluminate coupling agent, bimetallic coupling agent, phosphate coupling agent, boric acid
Ester coupling agent, chromium complex and other higher fatty acids, alcohol, ester coupling agent in it is one or more.The compatilizer is ring
Shape acid anhydrides type (such as CMG9801, KT-915 compatilizer), carboxylic acid type, epoxy type, oxazoline type, imide-type, it is isocyanate-based in
It is one or more.The nucleating agent includes benzoic acid, adipic acid, diphenylacetic acid, sodium benzoate, odium stearate, stearic acid
Calcium, sodium acetate, p-phenolsulfonic acid's sodium, p-phenolsulfonic acid's calcium, sodium phenate, boron nitride, sodium carbonate, one kind in potassium carbonate or more
Kind.
Optionally, further include doped chemical (i.e. non-carbon in the mixture in order to promote other performances of porous carbon materials
Element), the doped chemical includes one or more in nitrogen, sulphur, boron, phosphorus, silicon, oxygen, hydrogen and metallic element, the doping member
The mass content of element is less than 35%.Still optionally further, the mass content of the doped chemical is 5%-20% or 10%-
15%.The doped chemical can be introduced by the auxiliary agent.
After the carbonization treatment, deionized water and ethyl alcohol wash products can be used to neutrality.Wherein, it is carbonized for second
Treated, and product can first use dilute hydrochloric acid to be cleaned by ultrasonic extra to remove when used activator is alkaline matter
Activator, then deionized water is respectively adopted and ethyl alcohol is cleaned to neutrality.A concentration of 0.1-5mol/L of the dilute hydrochloric acid, further
Ground is 1-2mol/L.
The preparation method for the porous carbon materials that first aspect present invention provides, high score is prepared using traditional processing forming method
Sub- expanded material, and using it as carbon source, high specific surface area porous carbon material is prepared through carbonization heat treatment, the preparation method is former
Material derives from a wealth of sources, at low cost, and preparation process is simple, realizes the volume production of porous carbon materials, significantly reduces cost；And due to hair
The unique foam structure of foam material itself, the porous structure for being conducive to obtain micropore and mesoporous quantity mostly and being evenly distributed, to
Greatly improve the surface area and total pore volume amount of porous carbon.
Second aspect, the present invention provides a kind of porous carbon materials, using the preparation method described in first aspect present invention
It is prepared.The specific surface area of the porous carbon materials is more than 200m2/ g, total pore volume amount are more than 2.5cm3/ g, lattice distance are
0.275nm-0.365nm.More specifically, specific surface area can be more than 1000m2/ g, such as 1888m2/ g, total pore volume amount is up to 2.5-
3.5cm3/g。
The porous carbon materials that second aspect of the present invention provides, large specific surface area, hole are distributed uniform, stable structure, can be wide
It is general to be applied to the fields such as electrochemistry, catalysis, the energy, environment, absorption, heat-insulated.For example, porous carbon materials of the present invention can be used for battery
Negative material.
Advantages of the present invention will be illustrated partly in the following description, and a part is apparent according to specification
, or can be through the embodiment of the present invention implementation and know.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of 11 preparation-obtained porous carbon materials of the embodiment of the present invention；
Fig. 2 is the nitrogen adsorption desorption curve of 11 preparation-obtained porous carbon materials of the embodiment of the present invention.
Specific implementation mode
As described below is the preferred embodiment of the embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, under the premise of not departing from principle of the embodiment of the present invention, several improvements and modifications can also be made, these improvement
The protection domain of the embodiment of the present invention is also considered as with retouching.
Embodiment 1
A kind of preparation method of porous carbon materials includes the following steps using polyethylene foamed as carbon source：
Polythene material is dried 4 hours first at 80 DEG C, then by the polyethylene dried (95wt%) and 4,4-
Disulfonyl hydrazide diphenyl ether (OBSH) foaming agent (5wt%) is uniformly mixed to get mixture, by the mixture in vulcanizing press
In carry out molding processing, processing temperature is 160 DEG C, and soaking time is 3 minutes, and resulting product is dried 2 hours at 60 DEG C.Then will
The product dried is transferred in porcelain boat, then is transferred in tubular type retort, (the nitrogen flow 120cc/ under flowing nitrogen atmosphere
Min), 3 hours are kept the temperature after being warming up to 400 DEG C with the rate of 3 DEG C/min and carries out carbonization treatment, waits for that temperature is cooled to room temperature, and are taken out
Sample obtains porous carbon materials.
Embodiment 2
A kind of preparation method of porous carbon materials includes the following steps using expanded polypropylene as carbon source：
Polypropylene material is dried 4 hours first at 80 DEG C, then sends out the polypropylene dried (93wt%) and ABN
Infusion (7wt%) is uniformly mixed to get mixture, and the mixture is carried out molding processing, processing temperature in vulcanizing press
It it is 230 DEG C, soaking time is 5 minutes, and resulting product is dried 2 hours at 60 DEG C.Then the product dried is transferred to porcelain boat
In, then be transferred in tubular type retort, under flowing nitrogen atmosphere (120cc/min), 500 DEG C are warming up to the rate of 3 DEG C/min
It keeps the temperature 4 hours afterwards and carries out carbonization treatment, wait for that temperature is cooled to room temperature, take out sample and obtain porous carbon materials.
Embodiment 3
A kind of preparation method of porous carbon materials includes the following steps using foamed polyvinyl chloride as carbon source：
Pvc material is dried 4 hours first at 80 DEG C, then by the polyvinyl chloride dried (94wt%), silicon
Alkane coupling agent Z6043 (3wt%) and DIPA foaming agents (3wt%) are uniformly mixed to get mixture, by the mixture in tablet
Molding processing is carried out in vulcanizer, processing temperature is 190 DEG C, and soaking time is 5 minutes, and resulting product is dried 2 hours at 60 DEG C.
Then the product dried is transferred in porcelain boat, then be transferred in tubular type retort, (the 120cc/ under flowing nitrogen atmosphere
Min), 3 hours are kept the temperature after being warming up to 500 DEG C with the rate of 3 DEG C/min and carries out carbonization treatment, waits for that temperature is cooled to room temperature, and are taken out
Sample obtains porous carbon materials.
Embodiment 4
A kind of preparation method of porous carbon materials includes the following steps using the polymethyl methacrylate that foams as carbon source：
Polymethyl methacrylate materials are dried 4 hours first at 80 DEG C, the polymethyl that then will have been dried
Sour methyl esters (92wt%), CMG9801 compatilizers (3wt%) and BN foaming agents (5wt%) are uniformly mixed to get mixture, will be described
Mixture carries out molding processing in vulcanizing press, and processing temperature is 240 DEG C, and soaking time is 5 minutes, and resulting product is 60
DEG C drying 2 hours.Then the product dried is transferred in porcelain boat, then be transferred in tubular type retort, in flowing nitrogen atmosphere
Under (120cc/min), kept the temperature after being warming up to 600 DEG C with the rate of 3 DEG C/min 4 hours carry out carbonization treatment, wait for that temperature is down to room
Wen Hou takes out sample and obtains porous carbon materials.
Embodiment 5
A kind of preparation method of porous carbon materials includes the following steps using foaming ABS as carbon source：
ABS material is dried 2 hours first at 80 DEG C, then by the ABS dried (94wt%), silane coupling agent
A1120 (3wt%) is uniformly mixed to get mixture with foaming agent TSH (3wt%), and the mixture is added in thin film extruding machine
Film forming, each temperature section heating temperature are 200 DEG C, speed of production 300m/min, and film thickness is 500 μm, and products obtained therefrom is at 80 DEG C
Drying 4 hours.Then it by the transferred product to porcelain boat dried, then is transferred in tubular type retort, under flowing nitrogen atmosphere
(120cc/min) keeps the temperature 4 hours and carries out carbonization treatment, wait for that temperature is down to room temperature after being warming up to 500 DEG C with the rate of 3 DEG C/min
Afterwards, it takes out sample and obtains porous carbon materials.
Embodiment 6
A kind of preparation method of porous carbon materials includes the following steps using foamed flame retardant PET as carbon source：
PET material is dried 2 hours first at 80 DEG C, then by the PET dried (91wt%), fire retardant FR-
1525 (3wt%) are uniformly mixed to get mixture with foaming agent N- nitroguanidines (6wt%), and film, which is added, in the mixture squeezes out
It forms a film in machine, each temperature section heating temperature is 250 DEG C, speed of production 300m/min, and film thickness is 500 μm, products obtained therefrom
It is dried 4 hours at 80 DEG C.Then it by the transferred product to porcelain boat dried, then is transferred in tubular type retort, in flowing nitrogen
4 hours are kept the temperature under atmosphere (120cc/min), after being warming up to 600 DEG C with the rate of 3 DEG C/min and carries out carbonization treatment, wait for that temperature drops
To room temperature, takes out sample and obtain porous carbon materials.
Embodiment 7
A kind of preparation method of porous carbon materials includes the following steps using foaming PET as carbon source：
PET material is dried 4 hours first at 80 DEG C, then by the PET dried (83wt%) and THT foaming agents
(7wt%) and AC-66E coupling agents (10wt%) are uniformly mixed to get mixture, and screw extruder is added in the mixture
The draw ratio of middle carry out blending extrusion, screw extruder is 20:1, screw diameter 25mm, each temperature range is respectively 165 DEG C,
245 DEG C, 250 DEG C, 250 DEG C, 250 DEG C, 250 DEG C, 255 DEG C, 265 DEG C, rotating speed 200rpm, gained particle is prepared in 80 DEG C of conditions
Lower drying 4 hours.Then the particle dried is transferred in porcelain boat, then be transferred in tubular type retort, in flowing nitrogen atmosphere
Under (120cc/min), kept the temperature after being warming up to 600 DEG C with the rate of 3 DEG C/min 4 hours carry out carbonization treatment, wait for that temperature is down to room
Wen Hou takes out sample and obtains porous carbon materials.
Embodiment 8
A kind of preparation method of porous carbon materials includes the following steps using foamed polyvinyl chloride as carbon source：
Pvc material is dried 4 hours first at 80 DEG C, then by polyvinyl chloride dry (85wt%) and
BN foaming agents (5wt%) and compatilizer KT-915 (10wt%) are uniformly mixed to get mixture, and spiral shell is added in the mixture
Blending extrusion is carried out in bar extruder, the draw ratio of screw extruder is 20:1, screw diameter 25mm, each temperature range difference
It is 105 DEG C, 185 DEG C, 190 DEG C, 190 DEG C, 190 DEG C, 190 DEG C, 195 DEG C, 205 DEG C, rotating speed 200rpm, prepares gained particle and exist
It is dried 4 hours under the conditions of 80 DEG C.Then the particle dried is transferred in porcelain boat, then be transferred in tubular type retort, flowed
4 hours are kept the temperature under nitrogen atmosphere (120cc/min), after being warming up to 600 DEG C with the rate of 3 DEG C/min carries out first time carbonization treatment
Obtain sample.Then first time carbonization treatment is obtained into sample with mass ratio 1:5 ratio is uniformly mixed with KOH, at 130 DEG C
Fully after drying, it is transferred in nickel boat, the nickel boat equipped with sample after mixing is transferred in tubular type retort, in flowing nitrogen atmosphere
Under (120cc/min), 1 hour kept the temperature after being warming up to 800 DEG C with the rate of 3 DEG C/min carry out second carbonization treatment and obtain sample
Product.It waits for that temperature is cooled to room temperature, sample is taken out, be used in combination excessive 2mol/L HCl to be cleaned by ultrasonic 1 hour, then spend respectively
It is neutrality that ionized water and ethyl alcohol, which clean 3 times to filter liquor, fully obtains porous carbon materials after drying.
Embodiment 9
A kind of preparation method of porous carbon materials includes the following steps using the polymethyl methacrylate that foams as carbon source：
Polymethyl methacrylate materials are dried 4 hours first at 80 DEG C, the polymethyl that then will have been dried
Sour methyl esters (91wt%) is uniformly mixed to get mixture with DIPA foaming agents (3wt%) and coupling agent KBM403 (6wt%), will
The mixture, which is added in screw extruder, carries out blending extrusion, and the draw ratio of screw extruder is 20:1, screw diameter is
25mm, each temperature range are respectively 155 DEG C, 235 DEG C, 240 DEG C, 240 DEG C, 240 DEG C, 240 DEG C, 245 DEG C, 255 DEG C, and rotating speed is
200rpm prepares gained particle and is dried 4 hours under the conditions of 80 DEG C.Then the particle dried is transferred in porcelain boat, then turned
Enter in tubular type retort, under flowing nitrogen atmosphere (120cc/min), 4 are kept the temperature after being warming up to 700 DEG C with the rate of 3 DEG C/min
Hour carries out carbonization treatment, waits for that temperature is cooled to room temperature, and takes out sample and obtains porous carbon materials.
Embodiment 10
A kind of preparation method of porous carbon materials includes the following steps using expanded polystyrene (EPS) as carbon source：
Polystyrene material is dried 4 hours first at 80 DEG C, then by polystyrene dry (85wt%) and
ADC foaming agents (5wt%) and antioxidant 1076 (10wt%) are uniformly mixed to get mixture, and screw rod is added in the mixture
Blending extrusion is carried out in extruder, the draw ratio of screw extruder is 20:1, screw diameter 25mm, each temperature range are respectively
105 DEG C, 185 DEG C, 190 DEG C, 190 DEG C, 190 DEG C, 190 DEG C, 195 DEG C, 205 DEG C, rotating speed 200rpm, gained particle is prepared 80
It is dried 4 hours under the conditions of DEG C.Then the particle dried is transferred in porcelain boat, then be transferred in tubular type retort, in flowing nitrogen
4 hours are kept the temperature under atmosphere is enclosed (120cc/min), after being warming up to 600 DEG C with the rate of 3 DEG C/min and carries out carbonization treatment, wait for temperature
It is cooled to room temperature, takes out sample and obtain porous carbon materials.
Embodiment 11
A kind of preparation method of porous carbon materials includes the following steps using foamed flame retardant polystyrene as carbon source：
Polystyrene material is dried 4 hours first at 80 DEG C, then by polystyrene dry (92wt%) and
ADC foaming agents (3wt%) and melamine flame retardants (5wt%) are uniformly mixed to get mixture, and the mixture is added
Blending extrusion is carried out in screw extruder, the draw ratio of screw extruder is 20:1, screw diameter 25mm, each temperature range point
Wei not be 105 DEG C, 185 DEG C, 190 DEG C, 190 DEG C, 190 DEG C, 190 DEG C, 195 DEG C, 205 DEG C, rotating speed 200rpm, prepare gained particle
It is dried 4 hours under the conditions of 80 DEG C.Then the particle dried is transferred in porcelain boat, then be transferred in tubular type retort, flowed
Under dynamic nitrogen atmosphere (120cc/min), 4 hours are kept the temperature after being warming up to 600 DEG C with the rate of 3 DEG C/min and is carried out at first time carbonization
Reason obtains sample.Then first time carbonization treatment is obtained into sample with mass ratio 1:5 ratio is uniformly mixed with KOH, at 130 DEG C
After lower fully drying, it is transferred in nickel boat, the nickel boat equipped with sample after mixing is transferred in tubular type retort, in flowing nitrogen atmosphere
1 hour is kept the temperature under enclosing (120cc/min), after being warming up to 900 DEG C with the rate of 3 DEG C/min carries out second of carbonization treatment acquisition sample
Product.It waits for that temperature is cooled to room temperature, sample is taken out, be used in combination excessive 2mol/L HCl to be cleaned by ultrasonic 1 hour, then spend respectively
It is neutrality that ionized water and ethyl alcohol, which clean 3 times to filter liquor, fully obtains porous carbon materials after drying.
Fig. 1 is the scanning electron microscope (SEM) photograph of 11 preparation-obtained porous carbon materials of the embodiment of the present invention, it can be seen from the figure that
Pore structure keeps good, and pore size distribution is uniform, and is interconnected between Kong Yukong.
Fig. 2 is the nitrogen adsorption desorption curve of 11 preparation-obtained porous carbon materials of the embodiment of the present invention.It can be seen that
Porous carbon materials have very high adsorbance to nitrogen, are computed and know, the specific surface of the obtained porous carbon materials of the present embodiment
Product is 1888m2/g。
Know after testing, its specific surface area of the preparation-obtained porous carbon materials of 1-11 of the embodiment of the present invention is all higher than
200m2/ g, wherein embodiment 3, embodiment 8,10 preparation-obtained porous carbon materials of embodiment specific surface area BET be respectively
251m2/ g, 1546m2/ g, 279m2/g.From the point of view of testing result, carries out second of carbonization treatment and the implementation of activator is added
Example, prepared by obtain porous carbon materials its specific surface areas and substantially promoted.
It should be noted that the announcement and elaboration of book, those skilled in the art in the invention may be used also according to the above description
To change and change to the above embodiment.Therefore, the invention is not limited in specific implementations disclosed and described above
Mode, some equivalent modifications and change to the present invention should also be as within the scope of the claims of the present invention.In addition,
Although having used some specific terms in this specification, these terms are merely for convenience of description, not to structure of the present invention
At any restrictions.
Claims (10)
1. a kind of preparation method of porous carbon materials, which is characterized in that include the following steps：
High molecular material is uniformly mixed with foaming agent to obtain mixture, macromolecule hair will be obtained after the mixture machine-shaping
The high molecular foam material is carried out carbonization treatment, obtains porous carbon materials by foam material；
The high molecular material include by ethylene, propylene, methyl methacrylate, styrene, butadiene, vinyl chloride, chloropropene,
1,3 butadiene, dimethyl terephthalate (DMT), ethylene glycol, acrylonitrile, vinylacetate, methyl acrylate, caprolactam and its spread out
At least one of biology is one or more in the polymer of monomer synthesis.
2. the preparation method of porous carbon materials as described in claim 1, which is characterized in that the high molecular material includes poly- second
Alkene, polypropylene, polystyrene, polyethylene terephthalate, polybutylene terephthalate (PBT), poly-methyl methacrylate
Ester, polyvinyl chloride, makrolon, polytetrafluoroethylene (PTFE), polyamide, phenoplasts, amino resins, thermoplastic polyurethane elastomer,
Acrylonitritrile-styrene resin, acrylonitrile-butadiene-styrene terpolymer, ethylene-vinyl acetate copolymer, benzene second
Alkene-butadiene copolymer, polyether-ether-ketone, polyolefin elastomer, acetal resin, polyphenylene oxide and styrene series thermoplastic elastomer
In it is one or more.
3. the preparation method of porous carbon materials as described in claim 1, which is characterized in that the foaming agent includes azo compounds
Object, sulfonyl hydrazines compound, nitroso compound, carbonate, waterglass, silicon carbide, carbon black, pentane, n-hexane, positive heptan
Alkane, petroleum ether, Arcton 11, dicholorodifluoromethane, dichlorotetra-fluoroethane, lauryl sodium sulfate, aliphatic alcohol polyethenoxy
It is one or more in ether sodium sulfate and urea derivative.
4. the preparation method of porous carbon materials as described in claim 1, which is characterized in that the mode of the machine-shaping includes
Compression molding, extrusion molding, at fine or film forming.
5. the preparation method of porous carbon materials as described in claim 1, which is characterized in that the carbonization treatment includes for the first time
It is carbonized, in the first time carbonisation, atmosphere is oxygen, air or inert gas, and heating rate is 1-100 DEG C/min, carbon
It is 150-1600 DEG C to change temperature, and carbonization time is more than 3min.
6. the preparation method of porous carbon materials as claimed in claim 5, which is characterized in that the carbonization treatment further includes second
Secondary carbonization, in second of carbonisation, atmosphere is oxygen, air or inert gas, and heating rate is 1-100 DEG C/min,
Carburizing temperature is 150-1600 DEG C, and carbonization time is more than 3min.
7. the preparation method of porous carbon materials as claimed in claim 6, which is characterized in that add in second of carbonisation
Enter activator, the activator includes LiOH, NaOH, KOH, H3PO4、HNO3、H2SO4、LiCl、KCl、NaCl、ZnCl2、K2CO3、
LiCO3、Na2CO3、NH3、CCl3H、CCl2H2、CClH3、CO2With it is one or more in vapor.
8. the preparation method of porous carbon materials as described in claim 1, which is characterized in that further include helping in the mixture
Agent, the auxiliary agent include lubricant, heat stabilizer, light stabilizer, antioxidant, fire retardant, electrostatic agent, coupling agent, compatilizer and
It is one or more in nucleating agent.
9. the preparation method of the porous carbon materials as described in claim 1 or 8, which is characterized in that the mixture includes mixing
Miscellaneous element, the doped chemical include one or more in nitrogen, sulphur, boron, phosphorus, silicon, oxygen, hydrogen and metallic element, the doping
The mass content of element is less than 35%.
10. a kind of porous carbon materials, which is characterized in that it is prepared using claim 1-9 any one of them preparation methods,
The specific surface area of the porous carbon materials is more than 200m2/g。
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| PCT/CN2018/116867 WO2019184401A1 (en) | 2018-03-29 | 2018-11-22 | Preparation method for porous carbon material and porous carbon material |
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| CN114715877B (en) * | 2022-04-20 | 2023-08-11 | 嘉应学院 | Porous carbon material with high specific surface area and preparation method thereof |
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