CN108862233A - A kind of graphene composite porous charcoal and its preparation method and application - Google Patents
A kind of graphene composite porous charcoal and its preparation method and application Download PDFInfo
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- CN108862233A CN108862233A CN201710326871.6A CN201710326871A CN108862233A CN 108862233 A CN108862233 A CN 108862233A CN 201710326871 A CN201710326871 A CN 201710326871A CN 108862233 A CN108862233 A CN 108862233A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The present invention relates to electrode material fields, in particular to a kind of graphene composite porous charcoal and its preparation method and application.A kind of preparation method of graphene composite porous charcoal, includes the following steps：Phenolic resin, template and modified graphene are mixed, mixed liquor is made；Mixed liquor is cured, crush after, obtain carbon precursor；Carbon precursor is carbonized, and carbonized material is obtained；Carbonized material is mixed with alkaline matter and is activated, and obtained activation products are handled through acid, is then rinsed to neutrality, drying obtains the graphene composite porous charcoal.This method introduces activation method on the basis of template, and the two synergistic effect can prepare the porous carbon material being distributed with micropore-mesoporous multistage pore canal, and reaction process is mild；Graphene is introduced, the electric conductivity of material is greatly improved, promotes power characteristic of the porous carbon material as electrode material, which has very wide prospect for supercapacitor.
Description
Technical field
The present invention relates to electrode material fields, in particular to a kind of graphene composite porous charcoal and preparation method thereof
And application.
Background technique
Supercapacitor, also known as electrochemical capacitor are that a kind of collection high power density, charge/discharge speed be fast, cycle life
The novel energy storage apparatus of characteristics such as long.Core of the electrode material as supercapacitor, determines supercapacitor
Overall performance.Carbon Materials, metal oxide and conducting polymer are the most common electrode materials.Wherein, Carbon Materials are due to having
Controllable, the high conductivity of at low cost, large specific surface area, cellular structure, good physical and chemical stability and preparation process letter
The features such as single, is widely used as the electrode material of supercapacitor.In numerous Carbon Materials porous charcoal due to preparation process at
It is ripe, it is easy to industrialized production and be widely used.The traditional preparation methods of porous charcoal mainly have physical activation method and chemical activation
Two kinds of method.Using the simple process of physical activation method preparation porous charcoal, pollution is few, but reaction time consumption is long, and yield is low, is not suitable for big
Technical scale metaplasia produces.Chemical activation rule be using chemical reagent such as zinc chloride, phosphoric acid, potassium hydroxide as activator, with
The porous charcoal that priming reaction is then converted to hole prosperity occurs for rich carbon source materials.Specific surface can be prepared using chemical activation method
The biggish porous carbon material of product, but the porous carbon material of chemical activation method preparation is mainly based on micropore, and pore-size distribution is wider
It is not easy to control while higher using reagent costs such as potassium hydroxide and there are the corrosion of serious equipment and environmental pollutions.Therefore, it visits
The porous charcoal preparation process of Suo Xin has great importance.
One of an important factor for conductivity of porous carbon material is also influence supercapacitor charge-discharge performance.Due to porous
Charcoal hole is flourishing, and ratio shared by the carbon on hole wall is lower, and the contact area between porous charcoal particle is smaller, therefore, porous charcoal
The conductivity of material is not often high.Graphene has theoretically higher specific surface area and conductivity due to extensive by researcher because of it
Concern, but the characteristics of graphene is due to its structure, exclusive use there is a problem of larger.
Template charring is a kind of effective way of porous carbon material for obtaining controllable hole structure, but template preparation is more
Hole charcoal specific surface area is not often high.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of preparation method of graphene composite porous charcoal, for conventional activation method
The material specific surface area that the material pore-size distribution of preparation is wider, pore structure is complicated and prepared by uncontrollable and simple template method is not
The disadvantages of high, is prepared by template-activation synergistic effect with high-specific surface area and micropore-mesoporous classification fire wall porous charcoal
Material greatly reduces the dosage of alkaline matter, and reaction condition is mild, and greatly improves porous carbon material by introducing graphene
Electric conductivity.
The second object of the present invention is to provide graphene composite porous charcoal made from preparation method described in one kind, the material
Expect the advantage good with high specific capacitance and cycle performance.
The third object of the present invention is that providing the graphene composite porous charcoal is preparing the application in electrode material,
It has a extensive future.
In order to realize above-mentioned purpose of the invention, spy uses following technical scheme：
A kind of preparation method of graphene composite porous charcoal, includes the following steps：
(a), phenolic resin, template and modified graphene are mixed, mixed liquor is made, wherein the modified graphene
Graphene used is the graphene containing water soluble functional group；
(b), the mixed liquor it is cured, crush after, obtain carbon precursor；
(c), the carbon precursor is carbonized, and obtains carbonized material；
(d), the carbonized material is mixed with alkaline matter is activated, and activation products are obtained；
(e), the activation products are handled through acid, are then rinsed to neutrality, drying obtains the graphene composite porous charcoal.
The method that template can effectively control pore structure as one kind, the porous carbon material prepared compare with aperture
The features such as uniform, controllable, and the mesopore proportion in porous carbon material can be greatly improved.But it is simple using the more of template preparation
Hole charcoal often has that specific surface area is not high.The preparation method of graphene composite porous charcoal provided by the invention, in template
Activation method is introduced on the basis of method, further increases the specific surface area of porous charcoal, and the two synergistic effect can be prepared with micropore-
The porous carbon material of mesoporous multistage pore canal distribution；Also, this method gives full play to the advantage of the two, greatly reduces alkaline matter
Dosage, reaction process are milder；The present invention introduces graphene for the not high defect of porous carbon material electric conductivity simultaneously, can be big
The big electric conductivity for improving material further promotes power characteristic of the porous carbon material as electrode material.Graphene obtained is multiple
Closing porous carbon material has very wide prospect for supercapacitor.
In the present invention, selecting phenolic resin is that the carbon yield based on phenolic resin itself is relatively high, is relatively good carbon source；
Introducing template is to make entirely to react milder in addition it can reduce the dosage of alkaline matter for pore-creating；It selects water-soluble
Graphene make amalgamation between each ingredient good, the homogeneity being distributed in entire material conducive to graphene；Solidification process is
Phenolic resin is crosslinked the process of webbed three-dimensional-structure by linearity molecular structure；Activation is the chemical reaction that charcoal and alkali occur；
Sour processing intent is the impurity, including unreacted alkali, metal impurities etc. removed in porous charcoal.
Further, the template includes one of nitrate and triblock copolymer or a variety of.Nitrate is dissolved in
Ethyl alcohol, the Nitrates that selection is dissolved in ethyl alcohol are ethyl alcohol to be dissolved in based on phenolic resin, and subsequent removal is relatively convenient, and to ring
Border is more friendly.
Preferably, the nitrate includes one of magnesium nitrate, cobalt nitrate and nickel nitrate or a variety of.
Relative to magnesium nitrate, the effect of cobalt nitrate and nickel nitrate is more preferable, this is because cobalt and nickel also have made from catalysis
The effect of porous charcoal graphite alkylene, improves the electric conductivity of material；But the price of cobalt nitrate and nickel nitrate is higher.
Preferably, the triblock copolymer includes one of triblock copolymer F127 and triblock copolymer P123
Or two kinds.Triblock copolymer is introduced, has the function of increasing the mesopore proportion in porous charcoal obtained, increases conductivity.
In order to which the mesopore proportion in graphene composite porous charcoal obtained is appropriate, it is preferable that the template includes nitric acid
The mass ratio of salt and triblock copolymer, the triblock copolymer and the nitrate is 0.1-3：5, more preferably 0.8-
2.5：5, more preferably 0.8-1.0：5.If the mass ratio of triblock copolymer and nitrate can be 0.1：5,0.2：5,0.3：
5,0.5：5,0.6：5,0.7：5,0.8：5,1：5,1.3：5,1.5：5,2：5,2.5：5,3：5 etc..
Graphene has theoretically higher specific surface area and due to conductivity by researcher's extensive concern because of it, but graphene
The characteristics of due to its structure, exclusive use there is a problem of larger.Inventors have surprisingly discovered that graphene and porous carbon material into
Row is compound, can not only prevent the reunion of graphene but also the electric conductivity of porous charcoal can be improved, to prepare with high specific capacitance
With graphene/porous carbon composite material of cycle performance.
Further, the water soluble functional group includes any one of hydroxyl, carboxyl, amino, carbonyl, epoxy group or more
Kind.
Preferably, graphene used in the modified graphene is graphene oxide.
Further, step (a) is specially：
The template is dissolved in ethyl alcohol, the phenolic resin is added and mixes, obtains the first mixed liquor；
The modified graphene is added to as a solution in first mixed liquor, obtains the mixed liquor.
Preferably, it is stirred when the modified graphene is added to as a solution in first mixed liquor, institute
The speed for stating stirring is 500-2000r/min.Such as can for 500r/min, 800r/min, 1000r/min, 1500r/min,
1800r/min, 2000r/min etc..
Further, the modified graphene is to change graphene using one of PVA, PVP and PEG or a variety of
Property processing.
Preferably, the solution of the modified graphene is prepared by the following method：
By graphene ultrasonic disperse in distilled water, graphene solution is made；
Prepare modifying agent aqueous solution, the graphene solution be uniformly mixed with the aqueous solution of the modifying agent to get.
Further, in the graphene solution, the mass concentration of graphene is 0.3%-0.8%, more preferably
0.5%.
Further, in the aqueous solution of the modifying agent, the mass concentration of modifying agent is 8%-15%, more preferably
10%.
Preferably, the mass ratio of the graphene and the modifying agent is 1:10-50, preferably 1:15-30, more preferably
It is 1:20.
Further, in step (b), the cured temperature is 140-160 DEG C, time 4-6h；
Preferably, the granularity 180-250 mesh of the crushing.
Further, in step (c), the temperature of the charing is 500-600 DEG C, and the time of the charing is 100-
150min。
Preferably, the temperature of the charing is 550 DEG C.
Preferably, the time of the charing is 120min.
Preferably, the rate to heat up when the charing is 3-10 DEG C/min, more preferably 5 DEG C/min.
Further, in step (d), the temperature of the activation is 700-900 DEG C, and the time of the activation is 100-
150min。
Preferably, the temperature of the activation is 800 DEG C.
Preferably, the time of the activation is 120min.
Preferably, the rate to heat up when the activation is 3-10 DEG C/min, more preferably 5 DEG C/min；
Preferably, the mass ratio of the carbonized material and alkaline matter is 1:1-4；It such as can be 1：1,1：2,1：3,1：4 etc.
Deng.
Further, the alkaline matter includes strong base substance and strong base-weak acid salt, and the strong base substance is preferably hydrogen-oxygen
Change one or both of potassium and sodium hydroxide, the strong base-weak acid salt is preferably one of potassium carbonate and sodium carbonate or two
Kind.
Further, it is described acid processing be to be impregnated with acid solution, the pH of the acid solution between 1 and 2, the time of the dipping
For 8h or more, preferably 12-15h；
The acid solution is preferably aqueous hydrochloric acid solution.
Sour processing intent is the impurity, including unreacted alkali, metal impurities etc. removed in porous charcoal.Used in acid processing
Acid solution can be hydrochloric acid, nitric acid, sulfuric acid, acetic acid, formic acid etc., using aqueous hydrochloric acid solution high treating effect.
Further, the dosage of the graphene be the phenolic resin quality 0.2%-0.4%, the nitrate with
The mass ratio of the phenolic resin is (0.2-0.5)：1.
Mating reaction between each raw material, porous carbon comprehensive performance obtained are more superior.
The present invention also provides graphene composite porous charcoals made from above-mentioned preparation method.
Preferably, the specific surface area of graphene composite porous charcoal produced by the present invention is 1000-2500m2/ g, mesoporous are
20%-30%, conductivity 1500-2500S/m, specific capacitance 150-250F/g.
The present invention also provides the graphene composite porous charcoals to prepare the application in electrode material, and application prospect is wide
It is wealthy.
The present invention prepares porous carbon material using template and activation method synergistic effect, gives full play to the advantage of the two, mould
The regulation to pore structure may be implemented in the introducing of plate method；Graphene and porous carbon material progress are compound, can both prevent graphene
Reunion again the electric conductivity of porous charcoal can be improved, so that it is compound more to prepare the graphene with high specific capacitance and cycle performance
Hole charcoal, and further promote power characteristic of the porous carbon material as electrode material.
Compared with prior art, beneficial effects of the present invention are：
(1) present invention prepares porous carbon material using template and activation method synergistic effect, prepares with micropore-mesoporous
The porous carbon material of multistage pore canal distribution, while the present invention introduces graphene for the not high defect of porous carbon material electric conductivity,
It is greatly improved the electric conductivity of material, further promotes power characteristic of the porous carbon material as electrode material.
(2) present invention introduces triblock copolymers, and limit the ratio with nitrate, increase in porous charcoal obtained
Hole ratio increases conductivity.
(3) present invention also defines the type of parameter, each ingredient in each step and the ratios of each ingredient, so that being made
Product comprehensive performance it is more superior.
(4) graphene composite porous charcoal produced by the present invention is preparing having a extensive future in electrode material.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
Embodiment 1
Take 20g Mg (NO3)2It is dissolved in 100g dehydrated alcohol, 100g phenolic resin is then added and stirs evenly, obtains phenolic aldehyde
Resin uniform solution.
By graphene oxide (abbreviation GO) ultrasonic disperse in distilled water, 0.5wt% graphene oxide solution is made.It prepares
Concentration is the PVA aqueous solution of 10wt%, and a certain amount of graphene oxide solution is taken to mix with PVA solution, through high-speed stirred
Uniformly mixed GO/PVA mixed solution is obtained after (1000r/min), wherein the mass ratio of GO and PVA is 1:20.
GO/PVA solution is added in above-mentioned phenolic resin uniform solution simultaneously under high-speed stirred (1000r/min) state
It is uniformly mixed, so that GO accounts for the 0.25% of phenolic resin.
It is crushed after above-mentioned solution is solidified 6h at 150 DEG C, crushed material is placed in tube furnace and with the heating of 5 DEG C/min
Rate is warming up to 550 DEG C, and constant temperature 2h, obtains carbonized material.
By carbonized material and KOH according to mass ratio 1:1 ratio mixing, is placed in tube furnace with the heating rate of 3 DEG C/min
It is warming up to 800 DEG C, and constant temperature 2h.The dilute hydrochloric acid of product and 5wt% are mixed with dipping 12h, are then washed to neutrality using distillation,
Drying obtains porous carbon material at 120 DEG C.
Embodiment 2
Relative to embodiment 1, only change Mg (NO3)2Additive amount be 30g, remaining each condition is completely the same.
Embodiment 3
Relative to embodiment 1, only change Mg (NO3)2Additive amount be 40g, remaining each condition is completely the same.
Embodiment 4
Relative to embodiment 1, only change Mg (NO3)2Additive amount be 50g, remaining each condition is completely the same.
Embodiment 5
Take 50g Mg (NO3)2It is dissolved in 100g dehydrated alcohol jointly with 10g triblock copolymer F127,100g is then added
Phenolic resin stirs 2h, obtains uniform solution.Subsequent step is same as Example 1.
Embodiment 6
Take 50g Co (NO3)2It is dissolved in 100g dehydrated alcohol jointly with 10g triblock copolymer F127,100g is then added
Phenolic resin stirs 2h, obtains uniform solution.Subsequent step is same as Example 1.
Embodiment 7
Take 50g Ni (NO3)2It is dissolved in 100g dehydrated alcohol jointly with 10g triblock copolymer F127,100g is then added
Phenolic resin stirs 2h, obtains uniform solution.Subsequent step is same as Example 1.
Embodiment 8
50g Mg (NO will be taken3)2It is dissolved in 100g dehydrated alcohol with 1g triblock copolymer F127, is then added jointly
100g phenolic resin stirs 2h, obtains uniform solution.Subsequent step is same as Example 5.
Embodiment 9
50g Mg (NO will be taken3)2It is dissolved in 100g dehydrated alcohol with 2g triblock copolymer F127, is then added jointly
100g phenolic resin stirs 2h, obtains uniform solution.Subsequent step is same as Example 5.
Embodiment 10
50g Mg (NO will be taken3)2It is dissolved in 100g dehydrated alcohol with 4g triblock copolymer F127, is then added jointly
100g phenolic resin stirs 2h, obtains uniform solution.Subsequent step is same as Example 5.
Embodiment 11
50g Mg (NO will be taken3)2It is dissolved in 100g dehydrated alcohol with 6g triblock copolymer F127, is then added jointly
100g phenolic resin stirs 2h, obtains uniform solution.Subsequent step is same as Example 5.
Embodiment 12
50g Mg (NO will be taken3)2It is dissolved in 100g dehydrated alcohol with 8g triblock copolymer F127, is then added jointly
100g phenolic resin stirs 2h, obtains uniform solution.Subsequent step is same as Example 5.
Embodiment 13
50g Mg (NO will be taken3)2It is dissolved in 100g dehydrated alcohol with 10g triblock copolymer P123, is then added jointly
100g phenolic resin stirs 2h, obtains uniform solution.Subsequent step is same as Example 5.
Embodiment 14
50g Mg (NO will be taken3)2It is dissolved in 100g dehydrated alcohol with 12g triblock copolymer F127, is then added jointly
100g phenolic resin stirs 2h, obtains uniform solution.Subsequent step is same as Example 5.
Embodiment 15
50g Mg (NO will be taken3)2It is dissolved in 100g dehydrated alcohol with 15g triblock copolymer F127, is then added jointly
100g phenolic resin stirs 2h, obtains uniform solution.Subsequent step is same as Example 5.
Embodiment 16
50g Mg (NO will be taken3)2It is dissolved in 100g dehydrated alcohol with 20g triblock copolymer F127, is then added jointly
100g phenolic resin stirs 2h, obtains uniform solution.Subsequent step is same as Example 5.
Embodiment 17
50g Mg (NO will be taken3)2It is dissolved in 100g dehydrated alcohol with 25g triblock copolymer F127, is then added jointly
100g phenolic resin stirs 2h, obtains uniform solution.Subsequent step is same as Example 5.
Embodiment 18
50g Mg (NO will be taken3)2It is dissolved in 100g dehydrated alcohol with 30g triblock copolymer F127, is then added jointly
100g phenolic resin stirs 2h, obtains uniform solution.Subsequent step is same as Example 5.
Embodiment 19
Relative to embodiment 5, PVA is replaced with into PVP, remaining each condition is completely the same.
Embodiment 20
Relative to embodiment 5, PVA is replaced with into PEG, remaining each condition is completely the same.
Embodiment 21
Take 50g Ni (NO3)2It is dissolved in 100g dehydrated alcohol jointly with 10g triblock copolymer P123,100g is then added
Phenolic resin stirs 2h, obtains uniform solution.Subsequent step is same as Example 1.
Embodiment 22
Take 50g Co (NO3)2It is dissolved in 100g dehydrated alcohol jointly with 10g triblock copolymer P123,100g is then added
Phenolic resin stirs 2h, obtains uniform solution.Subsequent step is same as Example 1.
Embodiment 23
The dilute hydrochloric acid of 5wt% is changed into the acetic acid of 1M, subsequent step is same as Example 5.
Embodiment 24
Potassium hydroxide is changed to potassium carbonate, subsequent step is same as Example 5.
Embodiment 25
Carbonized material and KOH mass ratio 1:2, remaining step is same as Example 5.
Embodiment 26
Carbonized material and KOH mass ratio 1:4, remaining step is same as Example 5.
Embodiment 27
Take 50g Mg (NO3)2It is dissolved in 100g dehydrated alcohol jointly with 10g triblock copolymer F127,100g is then added
Phenolic resin stirs 2h, obtains uniform solution.
By graphene oxide (abbreviation GO) ultrasonic disperse in distilled water, 0.3wt% graphene oxide solution is made.It prepares
Concentration is the PVA aqueous solution of 8wt%, and a certain amount of graphene oxide solution is taken to mix with PVA solution, through high-speed stirred
Uniformly mixed GO/PVA mixed solution is obtained after (500r/min), wherein the mass ratio of GO and PVA is 1:20.
GO/PVA solution is added in above-mentioned phenolic resin uniform solution simultaneously under high-speed stirred (500r/min) state
It is uniformly mixed, so that GO accounts for the 0.2% of phenolic resin.
It is crushed after above-mentioned mixed solution is solidified 6h at 140 DEG C, the partial size of crushing is 200 mesh, and crushed material is placed in pipe
It is warming up to 550 DEG C, and constant temperature 2hmin in formula furnace and with the heating rate of 3 DEG C/min, obtains carbonized material.
By carbonized material and NaOH according to mass ratio 1:1 ratio mixing, is placed in tube furnace with the heating rate of 3 DEG C/min
It is warming up to 800 DEG C, and constant temperature 2h.The product dilute hydrochloric acid of 5wt% is impregnated into 12h, is then washed to neutrality using distillation,
Drying obtains porous carbon material at 120 DEG C.
Embodiment 28
Take 50g Mg (NO3)2It is dissolved in 100g dehydrated alcohol jointly with 10g triblock copolymer F127,100g is then added
Phenolic resin stirs 2h, obtains uniform solution.
By graphene oxide (abbreviation GO) ultrasonic disperse in distilled water, 0.8wt% graphene oxide solution is made.It prepares
Concentration is the PVA aqueous solution of 15wt%, and a certain amount of graphene oxide solution is taken to mix with PVA solution, through high-speed stirred
Uniformly mixed GO/PVA mixed solution is obtained after (2000r/min), wherein the mass ratio of GO and PVA is 1:20.
GO/PVA solution is added in above-mentioned phenolic resin uniform solution simultaneously under high-speed stirred (2000r/min) state
It is uniformly mixed, so that GO accounts for the 0.3% of phenolic resin.
It is crushed after above-mentioned mixed solution is solidified 5h at 150 DEG C, the partial size of crushing is 250 mesh, and crushed material is placed in pipe
It is warming up to 600 DEG C, and constant temperature 100min in formula furnace and with the heating rate of 10 DEG C/min, obtains carbonized material.
By carbonized material and NaOH according to mass ratio 1:1 ratio mixing is placed in the heating speed in tube furnace with 10 DEG C/min
Rate is warming up to 900 DEG C, and constant temperature 100min.The product dilute hydrochloric acid of 0.1M is impregnated into 8h, is then washed to neutrality using distillation,
Drying obtains porous carbon material at 120 DEG C.
Embodiment 29
Take 50g Mg (NO3)2It is dissolved in 100g dehydrated alcohol jointly with 10g triblock copolymer F127,100g is then added
Phenolic resin stirs 2h, obtains uniform solution.
By graphene oxide (abbreviation GO) ultrasonic disperse in distilled water, 0.5wt% graphene oxide solution is made.It prepares
Concentration is the PVP aqueous solution of 10wt%, and a certain amount of graphene oxide solution is taken to mix with PVP solution, through high-speed stirred
Uniformly mixed GO/PVP mixed solution is obtained after (1500r/min), wherein the mass ratio of GO and PVA is 1:20.
GO/PVP solution is added in above-mentioned phenolic resin uniform solution simultaneously under high-speed stirred (1500r/min) state
It is uniformly mixed, so that GO accounts for the 0.4% of phenolic resin.
It is crushed after above-mentioned mixed solution is solidified 4h at 160 DEG C, the granularity of crushing is 180 mesh, and crushed material is placed in pipe
It is warming up to 600 DEG C, and constant temperature 150min in formula furnace and with the heating rate of 8 DEG C/min, obtains carbonized material.
By carbonized material and KOH according to mass ratio 1:1 ratio mixing, is placed in tube furnace with the heating rate of 8 DEG C/min
It is warming up to 900 DEG C, and constant temperature 150min.The product dilute hydrochloric acid of 5wt% is impregnated into 15h, is then washed to neutrality using distillation,
Drying obtains porous carbon material at 120 DEG C.
Embodiment 30
Take 50g Mg (NO3)2It is dissolved in 100g dehydrated alcohol jointly with 10g triblock copolymer P123,100g is then added
Phenolic resin stirs 2h, obtains uniform solution.
By graphene oxide (abbreviation GO) ultrasonic disperse in distilled water, 0.5wt% graphene oxide solution is made.It prepares
Concentration is the PVA aqueous solution of 10wt%, and a certain amount of graphene oxide solution is taken to mix with PVA solution, through high-speed stirred
Uniformly mixed GO/PVA mixed solution is obtained after (1000r/min), wherein the mass ratio of GO and PVA is 1:15.
GO/PVA solution is added in above-mentioned phenolic resin uniform solution simultaneously under high-speed stirred (1000r/min) state
It is uniformly mixed, so that GO accounts for the 0.3% of phenolic resin.
It is crushed after above-mentioned mixed solution is solidified 4h at 150 DEG C, the partial size of crushing is 200 mesh, and crushed material is placed in pipe
It is warming up to 500 DEG C, and constant temperature 150min in formula furnace and with the heating rate of 5 DEG C/min, obtains carbonized material.
By carbonized material and KOH according to mass ratio 1:2 ratio mixing, is placed in tube furnace with the heating rate of 5 DEG C/min
It is warming up to 700 DEG C, and constant temperature 2h.The product dilute hydrochloric acid of 0.1M is impregnated into 12h, then neutrality is washed to using distillation, 120
Drying obtains porous carbon material at DEG C.
Embodiment 31
Take 50g Mg (NO3)2It is dissolved in 100g dehydrated alcohol jointly with 10g triblock copolymer P123,100g is then added
Phenolic resin stirs 2h, obtains uniform solution.
By graphene oxide (abbreviation GO) ultrasonic disperse in distilled water, 0.5wt% graphene oxide solution is made.It prepares
Concentration is the PEG aqueous solution of 10wt%, and a certain amount of graphene oxide solution is taken to mix with PEG solution, through high-speed stirred
Uniformly mixed GO/PEG mixed solution is obtained after (1000r/min), wherein the mass ratio of GO and PEG is 1:30.
GO/PEG solution is added in above-mentioned phenolic resin uniform solution simultaneously under high-speed stirred (1000r/min) state
It is uniformly mixed, so that GO accounts for the 0.3% of phenolic resin.
It is crushed after above-mentioned mixed solution is solidified 5h at 140 DEG C, the partial size of crushing is 200 mesh, and crushed material is placed in pipe
It is warming up to 550 DEG C, and constant temperature 2h in formula furnace and with the heating rate of 3 DEG C/min, obtains carbonized material.
By carbonized material and KOH according to mass ratio 1:1 ratio mixing, is placed in tube furnace with the heating rate of 3 DEG C/min
It is warming up to 750 DEG C, and constant temperature 2h.The product dilute hydrochloric acid of 5wt% is impregnated into 15h, is then washed to neutrality using distillation,
Drying obtains porous carbon material at 120 DEG C.
Embodiment 32
Take 50g Ni (NO3)2It is dissolved in 100g dehydrated alcohol jointly with 10g triblock copolymer P123,100g is then added
Phenolic resin stirs 2h, obtains uniform solution.
By graphene oxide (abbreviation GO) ultrasonic disperse in distilled water, 0.5wt% graphene oxide solution is made.It prepares
Concentration is the PVP aqueous solution of 10wt%, and a certain amount of graphene oxide solution is taken to mix with PVP solution, through high-speed stirred
Uniformly mixed GO/PVP mixed solution is obtained after (800r/min), wherein the mass ratio of GO and PVP is 1:50.
GO/PVP solution is added in above-mentioned phenolic resin uniform solution simultaneously under high-speed stirred (800r/min) state
It is uniformly mixed, so that GO accounts for the 0.3% of phenolic resin.
It is crushed after above-mentioned mixed solution is solidified 6h at 150 DEG C, the partial size of crushing is 200 mesh, and crushed material is placed in pipe
It is warming up to 550 DEG C, and constant temperature 2h in formula furnace and with the heating rate of 5 DEG C/min, obtains carbonized material.
By carbonized material and NaCO3According to mass ratio 1:3 ratio mixing is placed in the heating speed in tube furnace with 5 DEG C/min
Rate is warming up to 800 DEG C, and constant temperature 2h.The product dilute hydrochloric acid of 5wt% is impregnated into 15h, is then washed to neutrality using distillation,
Drying obtains porous carbon material at 120 DEG C.
Comparative example 1
Phenolic resin in embodiment 1 is changed to organic matter furfuryl alcohol, remaining step is identical.
Comparative example 2
Phenolic resin in embodiment 1 is changed to coal tar pitch, and by Mg (NO3)2It is changed to melamine, remaining step is identical.
Comparative example 3
According to application No. is the systems that a kind of high specific area disclosed in 201110353365.9 has hierarchical porous structure porous charcoal
The nano silicon oxide that partial size is 8nm is added dissolved in the ethanol solution of thermosetting phenolic resin resin Preparation Method, nano oxidized
Silicon and phenolic resin mass ratio are 1: 1, remove solvent, obtain powdered carbon, powdered carbon and KOH matter after charing, NaOH washing and drying
Amount for 1: 1 than mixing, and after 800 DEG C of activation 3h, HCl wash off extra KOH, can prepare high-specific surface area with hierarchical porous structure
Porous charcoal.
Comparative example 4
Take 20g Mg (NO3)2It is dissolved in 100g dehydrated alcohol, 100g phenolic resin is then added and stirs evenly, obtains phenolic aldehyde
Resin uniform solution.
It is crushed after above-mentioned solution is solidified 6h at 150 DEG C, crushed material is placed in tube furnace and with the heating of 5 DEG C/min
Rate is warming up to 550 DEG C, and constant temperature 2h, obtains carbonized material.
By carbonized material and KOH according to mass ratio 1:1 ratio mixing, is placed in tube furnace with the heating rate of 3 DEG C/min
It is warming up to 800 DEG C, and constant temperature 2h.The dilute hydrochloric acid of product and 5wt% are mixed with dipping 12h, are then washed to neutrality using distillation,
Drying obtains porous carbon material at 120 DEG C.
By porous carbon material, conductive black and binder made from embodiment 1-32 and comparative example 1-4 according to 85:
10:5 mass ratio mixing, then exceed the speed limit under the speed of 2000-20000rpm shear-mixed again, then by hanging down at 80MPa
It directly rolls and level rolls to form the uniform film of thickness, and film is placed at 100 DEG C and is placed for 24 hours.By dried film
It is cut into 1*1cm electrode slice, weighing is placed between two panels nickel foam, and is drawn with nickel sheet, it is compacted at 8MPa using tablet press machine,
Obtain electrode to be measured.Electrode to be measured is placed in the KOH solution of 6M after impregnating for 24 hours, electrochemical workstation is accessed, using three electrodes
System is tested, and the results are shown in Table 1.
1 test result of table
It is found from the test of embodiment 1-4, as nitrate additive amount increases, mesoporous is gradually increased, and specific surface area increases
Adding, conductivity decline, specific capacitance increases, still, mesoporous or relatively low；On this basis, inventors have found that addition three block
After copolymer, mesoporous is substantially improved, and different nitrate cooperates from the triblock copolymer of certain content with different
Effect, wherein more preferable with cobalt nitrate and nickel nitrate overall effect, this is because cobalt and nickel also have catalysis porous charcoal obtained
The effect of graphite alkylene improves the electric conductivity of material, also, best with cobalt nitrate effect, still, both nitrate prices
It is higher；In addition, embodiment 8-18 is shown in the influence for being investigated the amount centering porosity of the triblock copolymer of addition, it is found that with
The increase of triblock copolymer, mesoporous gradually increase, and specific surface area is reduced, and conductivity decline, specific capacitance increases to certain journey
It reduces, comprehensively considers after degree, the ratio of triblock copolymer and nitrate is preferably 0.8-2.5：5, more preferably 0.8-1.0：
5。
Embodiment 19-20 and embodiment 5 are the modifications for graphene oxide, it is found that PVA, PVP and PEG group sheet
Difference is little；Embodiment 13,21-22 and embodiment 5-7 are the ratios carried out about F127 the and P123 type of triblock copolymer
Compared with, it is found that both copolymer difference are substantially little；Embodiment 23 and embodiment 5 constitute the difference of pickling, and acid solution used is not
Together, it is seen then that pickling uses hydrochloric acid solution better effect；Embodiment 24 and embodiment 5 are different for the alkaline agent of priming reaction, alkaline agent
Select strong alkaline substance better effect；It is more to can be seen that activation alkaline matter used from embodiment 5, embodiment 25-26,
Then mesoporous is higher, and specific surface area rises, and specific capacitance increases, but conductivity reduces, accordingly, it is considered to the safety of operation, charcoal
The mass ratio of material and alkaline matter is preferably 1:1, reaction is as mild as a dove.
Test discovery, the graphene content of addition is too high, the poor compatibility with other materials, and porous carbon performance obtained is steady
Qualitative difference, and content is too low, then conductivity is low, cannot play corresponding effect；The dosage of graphene is phenolic resin quality
0.2%-0.4% is preferred.
From comparative example as can be seen that the specific selection phenolic resin of the present invention introduces on the basis of template as carbon source
Activation method, while modified graphene is introduced, it is common to act synergistically, it prepares porous with micropore-mesoporous multistage pore canal distribution
Carbon Materials, also, greatly reduce the dosage of alkaline matter, reaction process is milder, improves the electric conductivity of material, improves
Power characteristic of the porous carbon material as electrode material, the high comprehensive performance of porous carbon materials obtained.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from of the invention
Many other change and modification can be made in the case where spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. a kind of preparation method of graphene composite porous charcoal, which is characterized in that include the following steps：
(a), phenolic resin, template and modified graphene are mixed, mixed liquor is made, wherein used in the modified graphene
Graphene be the graphene containing water soluble functional group；
(b), the mixed liquor it is cured, crush after, obtain carbon precursor；
(c), the carbon precursor is carbonized, and obtains carbonized material；
(d), the carbonized material is mixed with alkaline matter is activated, and activation products are obtained；
(e), the activation products are handled through acid, are then rinsed to neutrality, drying obtains the graphene composite porous charcoal.
2. preparation method according to claim 1, which is characterized in that the template includes nitrate and triblock copolymer
One of object is a variety of；
Preferably, the nitrate includes one of magnesium nitrate, cobalt nitrate and nickel nitrate or a variety of；
Preferably, the triblock copolymer includes one of triblock copolymer F127 and triblock copolymer P123 or two
Kind；
Preferably, the template includes nitrate and triblock copolymer, the triblock copolymer and the nitrate
Mass ratio is 0.1-3：5；Preferably 0.8-2.5：5, more preferably 0.8-1.0：5.
3. preparation method according to claim 1, which is characterized in that the water soluble functional group includes hydroxyl, carboxyl, ammonia
Base, carbonyl, epoxy group are any one or more of；
Graphene used in the modified graphene is preferably graphene oxide；
Further, step (a) is specially：
The template is dissolved in ethyl alcohol, the phenolic resin is added and mixes, obtains the first mixed liquor；
The modified graphene is added to as a solution in first mixed liquor, obtains the mixed liquor；
Preferably, it is stirred when the modified graphene is added to as a solution in first mixed liquor, it is described to stir
The speed mixed is 500-2000r/min；
Preferably, the modified graphene is that graphene is modified place using one of PVA, PVP and PEG or a variety of
Reason；
Preferably, the solution of the modified graphene is prepared by the following method：
By graphene ultrasonic disperse in distilled water, graphene solution is made；
Prepare modifying agent aqueous solution, the graphene solution be uniformly mixed with the aqueous solution of the modifying agent to get；
Further, in the graphene solution, the mass concentration of graphene is 0.3%-0.8%, preferably 0.5%；
Further, in the aqueous solution of the modifying agent, the mass concentration of modifying agent is 8%-15%, preferably 10%；
Preferably, the mass ratio of the graphene and the modifying agent is 1:10-50, preferably 1:15-30, more preferably 1:
20。
4. preparation method according to claim 1, which is characterized in that in step (b), the cured temperature is 140-
160 DEG C, time 4-6h；
Preferably, the granularity 180-250 mesh of the crushing.
5. preparation method according to claim 1, which is characterized in that in step (c), the temperature of the charing is 500-
600 DEG C, the time of the charing is 100-150min；
The temperature of the charing is preferably 550 DEG C, and the time of the charing is preferably 120min；
Preferably, the rate to heat up when the charing is 3-10 DEG C/min, more preferably 5 DEG C/min.
6. preparation method according to claim 1, which is characterized in that in step (d), the temperature of the activation is 700-
900 DEG C, the time of the activation is 100-150min；
The temperature of the activation is preferably 800 DEG C, and the time of the activation is preferably 120min；
Preferably, the rate to heat up when the activation is 3-10 DEG C/min, more preferably 5 DEG C/min；
Preferably, the mass ratio of the carbonized material and alkaline matter is 1:1-4；
Further, the alkaline matter includes strong base substance and strong base-weak acid salt, and the strong base substance is preferably potassium hydroxide
One or both of with sodium hydroxide, the strong base-weak acid salt is preferably one or both of potassium carbonate and sodium carbonate.
7. preparation method according to claim 1, which is characterized in that the acid processing is impregnated with acid solution, the acid solution
PH between 1 and 2, time of the dipping is 8h or more, preferably 12-15h；
The acid solution is preferably aqueous hydrochloric acid solution.
8. preparation method according to claim 1-7, which is characterized in that the dosage of the graphene is the phenol
The mass ratio of the 0.2%-0.4% of urea formaldehyde quality, the nitrate and the phenolic resin is (0.2-0.5)：1.
9. graphene composite porous charcoal, which is characterized in that the specific surface area of the graphene composite porous charcoal is 1000-2500m2/
G, mesoporous 20%-30%, conductivity 1500-2500S/m, specific capacitance 150-250F/g.
10. graphene composite porous charcoal as claimed in claim 9 is preparing the application in electrode material.
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