CN107032320A - A kind of preparation method based on polyaniline-modified phenolic resin base porous carbon - Google Patents
A kind of preparation method based on polyaniline-modified phenolic resin base porous carbon Download PDFInfo
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- CN107032320A CN107032320A CN201710297905.3A CN201710297905A CN107032320A CN 107032320 A CN107032320 A CN 107032320A CN 201710297905 A CN201710297905 A CN 201710297905A CN 107032320 A CN107032320 A CN 107032320A
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- phenolic resin
- polyaniline
- porous carbon
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- resin base
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Abstract
The invention discloses a kind of preparation method based on polyaniline-modified phenolic resin base porous carbon, its step is included in blending in phenolic resin and adds pore creating material, is crushed after 140~200 DEG C of solidifications, and 900 DEG C of charings are packed standby after ball mill grinding；5~8h will be stirred with 600~1000r/min speed at 40~60 DEG C in aniline monomer, organic active montmorillonite, the above-mentioned gained sample of protonic acid solution addition；Oxidant is dissolved in Bronsted acid at 0~20 DEG C, added in above-mentioned gained suspension system, 6~8h is reacted under nitrogen protection, through filtering, washing, be dried to obtain target product.It is produced by the present invention based in polyaniline-modified phenolic resin base porous carbon due to dispersing polyaniline preferably, specific surface area is larger, so as to compared with the simple composite of polyaniline in the prior art and phenolic resin, improve it as the specific capacitance of ultracapacitor.
Description
Technical field
The present invention relates to a kind of preparation method of porous carbon materials, and in particular to a kind of based on polyaniline-modified phenolic aldehyde tree
The preparation method of aliphatic radical porous carbon.
Background technology
Electrode material for super capacitor is divided into two classes, and a class is the super capacitor material with electric double layer energy storage property,
This kind of material includes the carbon materials such as activated carbon, carbon fiber, CNT and graphene film, and this kind of material has 10 to arrive 200F/g's
Specific capacitance, charge and discharge circulation life is long, and up to more than 10000 times, but all in all specific capacitance is not high；It is another kind of to be
Pseudocapacitors material with redox characteristic, both organic/inorganic substance, such as ruthenium-oxide, manganese oxide, tin oxide, iron oxide material
Material, there is a conducting polymer composite, such as polyaniline, polythiophene, polypyrrole again, this kind of material due to redox characteristic,
Capacitance is very big, and up to more than 500F/g specific capacitance, but the shortcoming of this kind of material is because redox reaction occurs
In material bodies, volume in material charge and discharge process is caused to occur acute variation, defect occurs in structure, influences following for electrode material
Ring life-span, cycle-index can only be at 3000 times or so.Therefore, many research and development work are concentrated on the electricity of layer mechanism
The electrode material of pole material and redox machinery is combined with each other, and being prepared into composite is used for ultracapacitor.
Publication No. CN 104743543B Chinese patent discloses a kind of preparation side of polyaniline/phenolic aldehyde base carbon material
Method, aniline, acid, oxidant are mixed in water and reacted, polyaniline is prepared, and then add resorcinol and formaldehyde continues the system of reacting
Standby phenolic resin, is transferred in water heating kettle and carries out hydro-thermal reaction, and washing heats carbonization after drying in nitrogen, obtain polyaniline/
Phenolic aldehyde base carbon material.But dispersing polyaniline is bad, easily assemble in resin matrix, pure phenolic resin active carbon material is deposited
The problems such as specific surface area is low, pore-size distribution is uneven, cause to be given full play to respectively by both compounded ultracapacitors
The chemical property of component, causes specific capacitance not high as expected.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of based on poly- for the deficiency that above-mentioned prior art is present
The preparation method of aniline modified phenolic resin base porous carbon, applied to ultracapacitor, improves the electrification of ultracapacitor
Learn performance.
The problem of to solve set forth above, the invention provides a kind of based on polyaniline-modified phenolic resin base porous carbon
Preparation method, comprise the following steps：
Step 1, phenolic resin and pore creating material are dissolved in absolute methanol respectively and are well mixed, and ultrasonic wave disperses 1h, then will
The two is mixed, and ultrasonic wave disperses 1h again, until solution clarification；
Step 2, step 1 gained mixed liquor is poured into culture dish, and be put into 50 DEG C of baking ovens, make solvent volatilization 45min, then
Chamber type electric resistance furnace is put into, room temperature is cooled to after the completion of isothermal curing 2h, solidification at 140~200 DEG C, is crushed；
Step 3, step 2 gained sample is placed in ceramic crucible, is put into after weighing in chamber type electric resistance furnace and is warming up to 900 DEG C, and
And insulation 1h carries out burying making charcoal, carbide is taken out and crushed after weighing with ball mill and powder loading packaging bag is standby；
Step 4, aniline monomer, organic active montmorillonite, protonic acid solution are added in step 3 gained sample, 40~60
5~8h is stirred with 600~1000r/min speed at DEG C；
Step 5, oxidant is dissolved in Bronsted acid at 0~20 DEG C, added in step 4 gained suspension system, protected in nitrogen
Shield 6~8h of lower reaction, through filtering, washing, be dried to obtain target product；
Wherein, the pore creating material in the step 1 is that one kind is connected variety classes segment by ester bond with active end group
Polymer, segment includes the different types of molecule segment of the different lengths such as polyester or polyethers, and active end group is hydroxyl or carboxylic
The active group of base.
Further, the pore creating material consumption in the step 1 is the 5~35% of phenolic resin weight fraction.
Wherein, aniline, Bronsted acid, the mol ratio of oxidant are 1 in the step 4 and 5：（0.05~0.1）：（0.5~
1）.
Wherein, the organic active montmorillonite in the step 4 is that the sodium base through the cation-intercalated modification of organic quaternary ammonium salt is covered
De- soil.
Wherein, the Bronsted acid in the step 4 is hydrochloric acid, sulfuric acid, sulfosalicylic acid, DBSA or adjacent benzene two
Formic acid.
Wherein, the oxidant in the step 5 is ammonium persulfate, potassium peroxydisulfate, ferric trichloride or ferric sulfate.
Compared with prior art, the invention has the advantages that：Polyaniline by with organic active montmorillonite-based nano
Yardstick is combined, and is improved dispersiveness of the polyaniline in phenolic resin, is efficiently solved what polyaniline was assembled in resin system
Problem, so that having given full play to polyaniline is improving the advantage of ultracapacitor chemical property；Add and make in phenolic resin
Hole agent, improves the specific surface area of porous carbon materials, improves porous carbon materials as the specific capacitance of ultracapacitor.
Embodiment
With reference to specific embodiment, the present invention is further illustrated.
Embodiment 1
Step 1,100 parts of phenolic resin and 5 parts of polyethylene glycol are dissolved in absolute methanol respectively and are well mixed, and ultrasonic wave is scattered
1h, then mixes the two, and ultrasonic wave disperses 1h again, until solution clarification；
Step 2, step 1 gained mixed liquor is poured into culture dish, and be put into 50 DEG C of baking ovens, make solvent volatilization 45min, then
Chamber type electric resistance furnace is put into, room temperature is cooled to after the completion of isothermal curing 2h, solidification at 140 DEG C, is crushed；
Step 3, step 2 gained sample is placed in ceramic crucible, is put into after weighing in chamber type electric resistance furnace and is warming up to 900 DEG C, and
And insulation 1h carries out burying making charcoal, carbide is taken out and crushed after weighing with ball mill and powder loading packaging bag is standby；
Step 4, aniline monomer, organic active montmorillonite, hydrochloric acid solution are added in step 3 gained sample, at 40 DEG C with
600r/min speed stirring 5h；
Step 5, oxidant is dissolved in Bronsted acid at 0 DEG C, added in step 4 gained suspension system, under nitrogen protection
6h is reacted, through filtering, washing, be dried to obtain target product.
Wherein aniline, hydrochloric acid, ammonium persulfate mol ratio are 1：0.05：0.5, organic active montmorillonite is through cetyl three
The sodium-based montmorillonite that methyl bromide ammonium is modified, consumption is the 3% of step 3 products therefrom consumption.
The present embodiment obtains modified polyaniline/phenolic resin porous carbon materials, and specific surface area is 722.3m2/ g, specific capacitance
For 178F/g.
Embodiment 2
Step 1,100 parts of phenolic resin and 35 parts of polyvinyl butyrals are dissolved in absolute methanol respectively and are well mixed, and ultrasound
Wavelength-division dissipates 1h, then mixes the two, and ultrasonic wave disperses 1h again, until solution clarification；
Step 2, step 1 gained mixed liquor is poured into culture dish, and be put into 50 DEG C of baking ovens, make solvent volatilization 45min, then
Chamber type electric resistance furnace is put into, room temperature is cooled to after the completion of isothermal curing 2h, solidification at 200 DEG C, is crushed；
Step 3, step 2 gained sample is placed in ceramic crucible, is put into after weighing in chamber type electric resistance furnace and is warming up to 900 DEG C, and
And insulation 1h carries out burying making charcoal, carbide is taken out and crushed after weighing with ball mill and powder loading packaging bag is standby；
Step 4, aniline monomer, organic active montmorillonite, sulfuric acid solution are added in step 3 gained sample, at 60 DEG C with
1000r/min speed stirring 8h；
Step 5, oxidant is dissolved in Bronsted acid at 20 DEG C, added in step 4 gained suspension system, under nitrogen protection
8h is reacted, through filtering, washing, be dried to obtain target product.
Wherein aniline, sulfuric acid, potassium peroxydisulfate mol ratio are 1：0.1：1, organic active montmorillonite is through cetyl front three
The sodium-based montmorillonite that base ammonium bromide is modified, consumption is the 3% of step 3 products therefrom consumption.
The present embodiment obtains modified polyaniline/phenolic resin porous carbon materials, and specific surface area is 797.7 m2/ g, specific capacitance
For 168 F/g.
Embodiment 3
Step 1,100 parts of phenolic resin and 5 parts of polyethylene glycol are dissolved in absolute methanol respectively and are well mixed, and ultrasonic wave is scattered
1h, then mixes the two, and ultrasonic wave disperses 1h again, until solution clarification；
Step 2, step 1 gained mixed liquor is poured into culture dish, and be put into 50 DEG C of baking ovens, make solvent volatilization 45min, then
Chamber type electric resistance furnace is put into, room temperature is cooled to after the completion of isothermal curing 2h, solidification at 160 DEG C, is crushed；
Step 3, step 2 gained sample is placed in ceramic crucible, is put into after weighing in chamber type electric resistance furnace and is warming up to 900 DEG C, and
And insulation 1h carries out burying making charcoal, carbide is taken out and crushed after weighing with ball mill and powder loading packaging bag is standby；
Step 4, aniline monomer, organic active montmorillonite, sulfosalisylic acid solution are added in step 3 gained sample, 40
7h is stirred with 800r/min speed at DEG C；
Step 5, oxidant is dissolved in Bronsted acid at 10 DEG C, added in step 4 gained suspension system, under nitrogen protection
7h is reacted, through filtering, washing, be dried to obtain target product.
Wherein aniline, sulfosalicylic acid, ferric trichloride mol ratio are 1：0.07：0.8, organic active montmorillonite is through 16
The sodium-based montmorillonite that alkyl trimethyl ammonium bromide is modified, consumption is the 3% of step 3 products therefrom consumption.
The present embodiment obtains modified polyaniline/phenolic resin porous carbon materials, and specific surface area is 709.0 m2/ g, specific capacitance
For 199 F/g.
Embodiment 4
Step 1, phenolic resin is dissolved in absolute methanol and be well mixed, and ultrasonic wave disperses 1h, until solution clarification；
Step 2, step 1 gained mixed liquor is poured into culture dish, and be put into 50 DEG C of baking ovens, make solvent volatilization 45min, then
Chamber type electric resistance furnace is put into, room temperature is cooled to after the completion of isothermal curing 2h, solidification at 160 DEG C, is crushed；
Step 3, step 2 gained sample is placed in ceramic crucible, is put into after weighing in chamber type electric resistance furnace and is warming up to 900 DEG C, and
And insulation 1h carries out burying making charcoal, carbide is taken out and crushed after weighing with ball mill and powder loading packaging bag is standby；
Step 4, aniline monomer, sulfosalisylic acid solution are added in step 3 gained sample, with 800r/min's at 40 DEG C
Speed stirs 7h；
Step 5, oxidant is dissolved in Bronsted acid at 0 DEG C, added in step 4 gained suspension system, under nitrogen protection
7h is reacted, through filtering, washing, be dried to obtain target product.
Wherein aniline, sulfosalicylic acid, ferric trichloride mol ratio are 1：0.07：0.8.
The polyaniline phenolic resin base porous carbon being modified without organic active montmorillonite and pore creating material that the present embodiment is obtained
Material, specific surface area is 509.0 m2/ g, specific capacitance is 169 F/g.
Embodiment 1~3 is the preferred embodiment for the present invention for example, gained is based on polyaniline-modified phenolic resin
The specific surface area and specific capacitance of base porous carbon are apparently higher than embodiment 4.
It is described above, be only presently preferred embodiments of the present invention, any formal limitation not done to the present invention, it is every according to
According to the present invention technical spirit above example is made any simple modification, equivalent variations, each fall within the present invention protection
Within the scope of.
Claims (7)
1. a kind of preparation method based on polyaniline-modified phenolic resin base porous carbon, it is characterised in that comprise the following steps：
Step 1, phenolic resin and pore creating material are dissolved in absolute methanol respectively and are well mixed, and ultrasonic wave disperses 1h, then will
The two is mixed, and ultrasonic wave disperses 1h again, until solution clarification；
Step 2, step 1 gained mixed liquor is poured into culture dish, and be put into 50 DEG C of baking ovens, make solvent volatilization 45min, then
Chamber type electric resistance furnace is put into, room temperature is cooled to after the completion of isothermal curing 2h, solidification at 140~200 DEG C, is crushed；
Step 3, step 2 gained sample is placed in ceramic crucible, is put into after weighing in chamber type electric resistance furnace and is warming up to 900 DEG C, and
And insulation 1h carries out burying making charcoal, carbide is taken out and crushed after weighing with ball mill and powder loading packaging bag is standby；
Step 4, aniline monomer, organic active montmorillonite, protonic acid solution are added in step 3 gained sample, 40~60
5~8h is stirred with 600~1000r/min speed at DEG C；
Step 5, oxidant is dissolved in Bronsted acid at 0~20 DEG C, added in step 4 gained suspension system, protected in nitrogen
Shield 6~8h of lower reaction, through filtering, washing, be dried to obtain target product.
2. a kind of preparation method based on polyaniline-modified phenolic resin base porous carbon according to claim 1, it is special
Levy and be, the pore creating material in the step 1 is a kind of to be connected variety classes segment by ester bond with active end group
Polymer, segment includes the different types of molecule segment of the different lengths such as polyester or polyethers, and active end group is hydroxyl or carboxyl
Active group.
3. a kind of preparation method based on polyaniline-modified phenolic resin base porous carbon according to claim 1, it is special
Levy and be, the pore creating material consumption in the step 1 is the 5~35% of phenolic resin weight fraction.
4. a kind of preparation method based on polyaniline-modified phenolic resin base porous carbon according to claim 1, it is special
Levy and be, aniline, Bronsted acid, the mol ratio of oxidant are 1 in the step 4 and 5：（0.05~0.1）：（0.5~1）.
5. a kind of preparation method based on polyaniline-modified phenolic resin base porous carbon according to claim 1, it is special
Levy and be, the organic active montmorillonite in the step 4 is the sodium-based montmorillonite through the cation-intercalated modification of organic quaternary ammonium salt.
6. a kind of preparation method based on polyaniline-modified phenolic resin base porous carbon according to claim 1, it is special
Levy and be, the Bronsted acid in the step 4 is hydrochloric acid, sulfuric acid, sulfosalicylic acid, DBSA or phthalic acid.
7. a kind of preparation method based on polyaniline-modified phenolic resin base porous carbon according to claim 1, it is special
Levy and be, the oxidant in the step 5 is ammonium persulfate, potassium peroxydisulfate, ferric trichloride or ferric sulfate.
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Cited By (3)
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| CN107297196A (en) * | 2017-08-29 | 2017-10-27 | 吉林师范大学 | A kind of fluorine-containing porous carbon materials and its preparation method and application |
| CN109289806A (en) * | 2018-10-24 | 2019-02-01 | 山西新华化工有限责任公司 | The preparation method of spherical formaldehyde adsorbent |
| CN110444411A (en) * | 2019-08-26 | 2019-11-12 | 河北省科学院能源研究所 | A kind of conductive organic polymer package phenolic resin base porous carbon composite material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107297196A (en) * | 2017-08-29 | 2017-10-27 | 吉林师范大学 | A kind of fluorine-containing porous carbon materials and its preparation method and application |
| CN109289806A (en) * | 2018-10-24 | 2019-02-01 | 山西新华化工有限责任公司 | The preparation method of spherical formaldehyde adsorbent |
| CN110444411A (en) * | 2019-08-26 | 2019-11-12 | 河北省科学院能源研究所 | A kind of conductive organic polymer package phenolic resin base porous carbon composite material |
| CN110444411B (en) * | 2019-08-26 | 2021-08-17 | 河北省科学院能源研究所 | Conductive organic polymer coated phenolic resin matrix porous carbon composite material |
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