CN107253708A - A kind of preparation method for the phenolic resin base porous carbon being modified based on graphene - Google Patents
A kind of preparation method for the phenolic resin base porous carbon being modified based on graphene Download PDFInfo
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- CN107253708A CN107253708A CN201710297894.9A CN201710297894A CN107253708A CN 107253708 A CN107253708 A CN 107253708A CN 201710297894 A CN201710297894 A CN 201710297894A CN 107253708 A CN107253708 A CN 107253708A
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- phenolic resin
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- 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
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Abstract
The invention discloses a kind of preparation method for the phenolic resin base porous carbon being modified based on graphene, its step mainly first uses soluble iron salt treatment graphene oxide, then mixed again with phenolic resin, ultrasonic disperse, the phenolic resin base porous carbon for obtaining being modified based on graphene finally by high temperature carbonization.It can be used for ultracapacitor by porous carbon materials produced by the present invention, because the graphene oxide after soluble iron salt treatment can significantly improve its dispersiveness in phenolic resin as matrix resin, so as to improve specific surface area and specific capacitance compared with prior art.
Description
Technical field
The present invention relates to a kind of preparation method of porous carbon materials, especially a kind of phenolic resin being modified based on graphene
The preparation method of base porous carbon.
Background technology
It is intensive available for the specific surface area and electric charge of storing up electricity that the charge storage ability of ultracapacitor depends primarily on electrode material
Degree.In theory, electrode surface area is bigger, and electric charge is more intensive, and its capacity is bigger.Because porous carbon has chemically stable
The features such as property, high-specific surface area, be the current most widely used material in ultracapacitor field.Phenolic resin base porous carbon is most
One of conventional electrode material for super capacitor, this kind of material has 10 specific capacitances for arriving 200F/g, charge and discharge circulation life
Long, up to more than 10000 times, but electrical conductivity is low, and all in all specific capacitance is not high, so chemical property and paying no attention to
Think.
Graphene is a kind of two-dimentional carbon nanomaterial, with high electrical conductivity and excellent mechanical performance and big theory
Specific surface area, is a kind of very potential ultracapacitor double layer electrodes material.Added in phenolic resin base porous carbon
Graphene, while graphene excellent properties are played, can further improve the specific surface area of porous carbon materials, so as to carry
High specific capacitance.But graphene, especially graphene oxide are very easy to reunite or accumulated so that effective ratio area reduces,
It is unfavorable for electrolyte ion to enter inside electrode material, causes actual capacitance to greatly reduce.
Graphene it has been related to add in the prior art in phenolic resin as matrix resin to improve porous carbon materials as super
The report of level capacitor chemical property, but do not propose to solve graphene poor dispersion in phenolic resin as matrix resin
Solution.
The content of the invention
The invention provides a kind of preparation method for the phenolic resin base porous carbon being modified based on graphene, graphite is solved
Alkene the problem of poor dispersion, so as to give full play to the advantage of graphene in the composite, is carried in phenolic resin as matrix resin
The surface area and specific capacitance of high porous carbon materials.
The invention discloses a kind of preparation method for the phenolic resin base porous carbon being modified based on graphene, including following step
Suddenly：
Step 1, phenolic resin is dissolved in absolute methanol and be well mixed, and ultrasonic wave disperses 1h, until solution clarification；
Step 2, graphene oxide, soluble ferric iron salt, concentrated ammonia liquor are mixed in water, stirred 1~3 hour；
Step 3, the liquid obtained by step 1 and step 2 is mixed, 5~8h of ultrasonic disperse at 40~60 DEG C；
Step 4, step 3 gained mixed liquor is poured into culture dish, is then placed in chamber type electric resistance furnace, the constant temperature at 160~200 DEG C
Solidify 2h, room temperature is cooled to after the completion of solidification, crush；
Step 5, step 4 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.
Soluble iron salt treatment is used graphite oxide, it is obtained compared to being directly combined with graphene oxide with phenolic resin
The specific surface area and specific capacitance of porous carbon materials increase.
Wherein, the phenolic resin in the step 1 is alkaline resol phenol-formaldehyde resin.
Wherein, the graphene oxide consumption in the step 2 is the 0.1~2% of phenolic resin quality.
Wherein, the soluble ferric iron salt in the step 2 is ferric trichloride.
Wherein, in the step 2 graphene oxide and the mol ratio of soluble ferric iron salt is 1：（1~10）.
Compared with prior art, the invention has the advantages that：Soluble iron salt treatment graphene oxide is first used, then
Compound with phenolic resin, with directly using graphene oxide and phenolic resin compound phase ratio, soluble ferric iron salt acts not only as oxygen
The intercalator of graphite alkene, improves dispersiveness of the graphene in resin matrix, solves the problem of graphene is easily reunited, may be used also
To form pseudocapacitors material-iron oxide with redox characteristic in carbonization process, so in general improving many
The specific surface area and specific capacitance of hole carbon material.The obtained specific surface area of phenolic resin base porous carbon that is modified based on graphene is
1950m2/ g, specific capacitance is 209F/g.
Embodiment
To further understand the present invention, the preferred embodiment of the invention is described with reference to embodiment, but should
Work as understanding, these descriptions are intended merely to further illustrate the features and advantages of the present invention, rather than to the limit of invention claim
System.
All raw materials of the present invention, originate to it and are not particularly limited, commercially buying or according to people in the art
Prepared by the conventional method known to member both may be used.
The invention discloses a kind of preparation method for the phenolic resin base porous carbon being modified based on graphene, including following step
Suddenly：
Step 1, phenolic resin is dissolved in absolute methanol and be well mixed, and ultrasonic wave disperses 1h, until solution clarification；
Step 2, graphene oxide, soluble ferric iron salt, concentrated ammonia liquor are mixed in water, stirred 1~3 hour；
Step 3, the liquid obtained by step 1 and step 2 is mixed, 5~8h of ultrasonic disperse at 40~60 DEG C；
Step 4, step 3 gained mixed liquor is poured into culture dish, is then placed in chamber type electric resistance furnace, the constant temperature at 160~200 DEG C
Solidify 2h, room temperature is cooled to after the completion of solidification, crush；
Step 5, step 4 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.
The resol is not particularly limited the present invention, can be prepared or commercially available purchase using well known method
Buy, resol of the present invention preferably presses preferred mass ratio 1 by phenol and formaldehyde：（1.3~1.5）It is made.
The graphene oxide is not particularly limited the present invention, can be prepared or commercially available purchase using well known method
, graphene oxide of the present invention be preferred to use improvement Hummers methods prepare or buy.
Embodiment 1：
Step 1,500g phenolic resin is dissolved in absolute methanol and be well mixed, and ultrasonic wave disperses 1h, until solution clarification；
Step 2,0.5g graphene oxides, ferric trichloride, concentrated ammonia liquor are mixed in water, stirred 3 hours；
Step 3, the liquid obtained by step 1 and step 2 is mixed, the ultrasonic disperse 5h at 50 DEG C；
Step 4, step 3 gained mixed liquor is poured into culture dish, is then placed in chamber type electric resistance furnace, the isothermal curing at 160 DEG C
Room temperature is cooled to after the completion of 2h, solidification, is crushed；
Step 5, step 4 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.
Wherein, the mol ratio of graphene oxide and ferric trichloride is 1:1.
Specific surface area, which is 1800m, to be detected to porous carbon prepared by embodiment 12/ g, specific capacitance is 188F/g, is compared
Directly it is combined with graphene oxide with phenolic resin, specific surface area and specific capacitance increase.
Embodiment 2：
Step 1,500g phenolic resin is dissolved in absolute methanol and be well mixed, and ultrasonic wave disperses 1h, until solution clarification；
Step 2,10g graphene oxides, ferric trichloride, concentrated ammonia liquor are mixed in water, stirred 3 hours；
Step 3, the liquid obtained by step 1 and step 2 is mixed, the ultrasonic disperse 8h at 50 DEG C；
Step 4, step 3 gained mixed liquor is poured into culture dish, is then placed in chamber type electric resistance furnace, the isothermal curing at 200 DEG C
Room temperature is cooled to after the completion of 2h, solidification, is crushed；
Step 5, step 4 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.
Wherein, the mol ratio of graphene oxide and ferric trichloride is 1:10.
Specific surface area, which is 1950m, to be detected to porous carbon prepared by embodiment 22/ g, specific capacitance is 178F/g, is compared
Directly it is combined with graphene oxide with phenolic resin, specific surface area and specific capacitance increase.
Embodiment 3：
Step 1,500g phenolic resin is dissolved in absolute methanol and be well mixed, and ultrasonic wave disperses 1h, until solution clarification；
Step 2,5g graphene oxides, ferric trichloride, concentrated ammonia liquor are mixed in water, stirred 3 hours；
Step 3, the liquid obtained by step 1 and step 2 is mixed, the ultrasonic disperse 8h at 50 DEG C；
Step 4, step 3 gained mixed liquor is poured into culture dish, is then placed in chamber type electric resistance furnace, the isothermal curing at 200 DEG C
Room temperature is cooled to after the completion of 2h, solidification, is crushed；
Step 5, step 4 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.
Wherein, the mol ratio of graphene oxide and ferric trichloride is 1:5.
Specific surface area, which is 1540m, to be detected to porous carbon prepared by embodiment 32/ g, specific capacitance is 209F/g, is compared
Directly it is combined with graphene oxide with phenolic resin, specific surface area and specific capacitance increase.
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 (5)
1. a kind of preparation method for the phenolic resin base porous carbon being modified based on graphene, it is characterised in that comprise the following steps：
Step 1, phenolic resin is dissolved in absolute methanol and be well mixed, and ultrasonic wave disperses 1h, until solution clarification；
Step 2, graphene oxide, soluble ferric iron salt, concentrated ammonia liquor are mixed in water, stirred 1~3 hour；
Step 3, the liquid obtained by step 1 and step 2 is mixed, 5~8h of ultrasonic disperse at 40~60 DEG C；
Step 4, step 3 gained mixed liquor is poured into culture dish, is then placed in chamber type electric resistance furnace, the constant temperature at 160~200 DEG C
Solidify 2h, room temperature is cooled to after the completion of solidification, crush；
Step 5, step 4 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.
2. a kind of preparation method of phenolic resin base porous carbon being modified based on graphene according to claim 1, it is special
Levy and be, the phenolic resin in the step 1 is alkaline resol phenol-formaldehyde resin.
3. a kind of preparation method of phenolic resin base porous carbon being modified based on graphene according to claim 1, it is special
Levy and be, the graphene oxide consumption in the step 2 is the 0.1~2% of phenolic resin quality.
4. a kind of preparation method of phenolic resin base porous carbon being modified based on graphene according to claim 1, it is special
Levy and be, the soluble ferric iron salt in the step 2 is ferric trichloride.
5. a kind of preparation method of phenolic resin base porous carbon being modified based on graphene according to claim 1, it is special
Levy and be, the mol ratio of graphene oxide and molysite in the step 2 is 1：（1~10）.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107902651A (en) * | 2017-10-18 | 2018-04-13 | 中国科学院山西煤炭化学研究所 | A kind of graphene-based capacitance carbon large-scale preparation method |
| CN108516546A (en) * | 2018-05-09 | 2018-09-11 | 中国铝业股份有限公司 | A kind of preparation method of activated carbon |
| CN112573502A (en) * | 2020-09-11 | 2021-03-30 | 四川大学 | Aromatic cyano/aromatic alkynyl porous carbon material and preparation method thereof |
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| CN112573502A (en) * | 2020-09-11 | 2021-03-30 | 四川大学 | Aromatic cyano/aromatic alkynyl porous carbon material and preparation method thereof |
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Application publication date: 20171017 |