CN110028067A - A kind of super capacitor active carbon and preparation method thereof - Google Patents
A kind of super capacitor active carbon and preparation method thereof Download PDFInfo
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- CN110028067A CN110028067A CN201910326385.3A CN201910326385A CN110028067A CN 110028067 A CN110028067 A CN 110028067A CN 201910326385 A CN201910326385 A CN 201910326385A CN 110028067 A CN110028067 A CN 110028067A
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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
- C01B32/33—Preparation characterised by the starting materials from distillation residues of coal or petroleum; from petroleum acid sludge
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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
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
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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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 invention belongs to active carbon preparation technical fields, and in particular to a kind of super capacitor active carbon and preparation method thereof.This method through charing, obtains super capacitor active carbon after priming reaction for after lignite thermally dissolving and catalytic heavy component and pre-oxidation agent hybrid reaction, the large specific surface area of the active carbon, total pore volume and mesoporous is higher, good conductivity.In addition, the content of ash content and heavy metal in the raw material of super capacitor active carbon is lower, the impurity content of super capacitor active carbon is thereby reduced, and can preferably control the number of super capacitor active carbon surface functional group, help to improve the conductivity of active carbon.
Description
Technical field
The invention belongs to active carbon preparation technical fields, and in particular to a kind of super capacitor active carbon and preparation method thereof.
Background technique
Active carbon has biggish specific surface area, pore structure abundant, high temperature high voltage resistant, stable chemical property, energy
The advantages such as enough regeneration is reused, price is low, can be widely applied to purification gas, sewage treatment, catalyst carrier, medicine, army
The technical fields such as work, new energy.
In recent years, new-energy automobile is widelyd popularize in global range, also conventional fuel oil automobile is sold in pause in succession for various regions
Timetable, to the performance of electric car, more stringent requirements are proposed.Currently, the commercially available electric vehicle generally existing charging time it is long,
The disadvantages of course continuation mileage is short, service life is short, mostly with high power density, big specific capacitance, the supercapacitor of high circulation substitution
Conventional batteries solve disadvantages mentioned above.According to energy storage mechnism difference, supercapacitor can be divided into double layer capacitor, pseudocapacitors
With the two mixed type.Because its electrode material uses transition metal, a series of redox reactions can occur pseudocapacitors for when energy storage,
There are stable cycle performances it is poor, the charging time is long the disadvantages of；The electrode material of double layer capacitor is Carbon Materials, with active carbon
Based on, active carbon has biggish specific surface area, pore structure abundant, high temperature high voltage resistant, stable chemical property, Neng Gouzai
The advantages such as raw reuse, cheap, therefore the cyclical stability of double layer capacitor is preferable, practicability is stronger, easily realizes and produces
Industry.
With greatly developing for new-energy automobile, the requirement to active carbon is higher and higher, generally, the specific surface area of active carbon
For 1000~1500m2·g-1, but it has been difficult to meet the needs of current, development and production specific surface area is more than 1500m2·g-1, inhale
Attached capacity is big, impurity is few, the reasonable super-activated carbon of pore-size distribution is extremely urgent.The raw material of active carbon can be any one
Substance based on kind is carbon containing, such as plant shell, pitch heavy component；But plant shell is limited to season interference, active carbon produces
Rate is low, production scale is limited；The heavy components such as pitch are the by-products of Coal dressing process, from a wealth of sources, resourceful, price
It is cheap, it is mainly used in the industries such as smelting, building and novel charcoal material at present, how to improve the high added value of pitch, widen
Application surface has become current hot spot.Chinese patent literature CN108584952A discloses a kind of preparation method of spherical porous charcoal,
This method includes being heated coal liquefaction pitch to obtain pitch, and spray-dried processing, charing, is lived at pre-oxidation
Change obtains spherical porous charcoal, but the spherical porous charcoal that there are micropores is flourishing, mesoporous is low, pore-size distribution is unreasonable and surface
The excessive feature of functional group, so that it is difficult to be suitable in supercapacitor.
Summary of the invention
Therefore, the technical problem to be solved in the present invention is that overcoming the active carbon of preparation in the prior art, there are micropore hairs
It reaches, the defects of mesoporous is low, pore-size distribution is unreasonable, to provide a kind of super capacitor active carbon and preparation method thereof.
For this purpose, the present invention provides following technical schemes:
The present invention provides a kind of preparation methods of super capacitor active carbon, including, by lignite thermally dissolving and catalytic heavy component
It mixes and reacts with pre-oxidation agent, obtain non-fusible intermediate product；
Be uniformly mixed the non-fusible intermediate product to obtain mixed material with activator, carbonized, activate after obtain institute
State super capacitor active carbon.
It further, further include that wetting agent is added to be mixed when the non-fusible intermediate product being mixed with activator
The step of material, wherein the mass ratio of the non-fusible intermediate product, the activator and the wetting agent is 1:(1-5):
(0.0001-0.0005)。
It further, further include that activator is first dissolved in water before the non-fusible intermediate product is mixed with activator
Middle step.
The activator is KOH, NaOH and NaHCO3Deng at least one；
The wetting agent is at least one of acetone, methanol and ethyl alcohol.
The lignite thermally dissolving and catalytic heavy component and the mass ratio of pre-oxidation agent are not less than 2:1.
After the lignite thermally dissolving and catalytic heavy component is mixed with pre-oxidation agent, with the heating rate liter of 0.5-1.5 DEG C/min
Temperature keeps the temperature 1-20h to 250-350 DEG C, and reaction obtains the non-fusible intermediate product.
Further, under oxygen-free environment, the mixed material is warming up to 400-600 with the heating rate of 2-10 DEG C/min
After DEG C, 0.5-3h is kept the temperature, the carbonization reaction is carried out.
After the charing, oxygen-free environment is kept, 600-1000 DEG C is warming up to the heating rate of 3-20 DEG C/min, protects
Temperature is not more than 6h, completes the priming reaction.
The method also includes washing the product after activation, the step of pickling and drying；Preferably, to activation
Product afterwards washed, pickling to neutrality, is then dried again；
The temperature of the drying is 100-180 DEG C, drying time 3-8h.
The pre-oxidation agent is H2O2、KNO3, dense H2SO4With dense HNO3At least one of Deng；
The non-fusible reaction is carried out in air atmosphere, and the flow velocity of the air is 10-50mLmin-1g-1；
In the carbonization reaction and priming reaction, need to be passed through nitrogen as protective gas, the flow velocity of nitrogen is 10-
100mL·min-1g1。
The lignite thermally dissolving and catalytic heavy component mix with pre-oxidation agent again after broken, milling, sieve processing
Even, sieve mesh number is not less than 80 mesh in the sieve.
It by the boiling point that thermally dissolving and catalytic technological reaction generates is 450-510 that the lignite thermally dissolving and catalytic heavy component, which is lignite,
DEG C product.
The present invention also provides a kind of super capacitor active carbons that the above method is prepared.
Technical solution of the present invention has the advantages that
1. the preparation method of super capacitor active carbon provided by the invention, this method includes will be made from lignite thermally dissolving and catalytic
Heavy component is mixed and is reacted with pre-oxidation agent, obtains non-fusible intermediate product；By the non-fusible intermediate product and activator
Be uniformly mixed obtain mixed material, carbonized, activate after obtain the super capacitor active carbon.Super capacitor made from this method
The large specific surface area of active carbon, total pore volume and mesoporous is higher, good conductivity, wherein the multiple spot BET ratio of super capacitor active carbon
Surface area is not less than 2500m2·g-1, total pore volume is not less than 1.5cm3·g-1, pore-size distribution is reasonable, mesoporous between 40%~
50%, it is suitably applied supercapacitor field.
In addition, the content of ash content and heavy metal in the raw material is lower, thereby reduce miscellaneous in super capacitor active carbon
Matter content, and the number of super capacitor active carbon surface functional group can be preferably controlled, help to improve super capacitor activity
The conductivity of charcoal.
Lignite thermally dissolving and catalytic heavy component 2. the preparation method of super capacitor active carbon provided by the invention, in this method
Ash content and content of beary metal it is lower, and activator level is less, can preferably control super capacitor active carbon surface function
The number of group, helps to improve the conductivity of sample；The patent is by screening, the excellent wetting agent for having selected better effects, significantly
The contact area for improving non-fusible intermediate product and activator improves activation efficiency, shortens activation time；It is simultaneously existing
Wetting agent dosage is hundreds times of dosage of the present invention in technology, and compared with prior art, the dosage of wetting agent of the present invention obviously drops
It is low.
In addition, activator and wetting agent also belong to one of the composition of impurity in active carbon, dosage is few to be namely equivalent to drop
The content of impurity in low active carbon.
3. the preparation method of super capacitor active carbon provided by the invention can by adjusting the heating rate of preparation method
To control total pore volume, mesoporous and the electric conductivity of super capacitor active carbon；
Active carbon is washed after priming reaction, pickling can neutralize the pH value of activated material, reduce in activated material
Ash content.
Specific embodiment
There is provided following embodiments is to preferably further understand the present invention, it is not limited to the best embodiment party
Formula is not construed as limiting the contents of the present invention and protection scope, anyone under the inspiration of the present invention or by the present invention and its
The feature of his prior art is combined and any and identical or similar product of the present invention for obtaining, all falls within of the invention
Within protection scope.
Specific experiment step or condition person are not specified in embodiment, according to the literature in the art described routine experiment
The operation of step or condition can carry out.Reagents or instruments used without specified manufacturer, being can be by commercially available acquisition
Conventional reagent product.
In the following Examples and Comparative Examples, coal thermally dissolving and catalytic heavy component the preparation method is as follows:
30~50wt% brown coal powder, 50~70wt%1- methyl naphthalene and 0.01~5wt% halide are thoroughly mixed
At coal slurry, the reaction of coal slurry thermally dissolving and catalytic generates thermosol liquefaction products, hydrogenation temperature is 400~500 DEG C, pressure be 6~13MPa,
Hydrogen to oil volume ratio is 400~600, and air speed is 0.2~1.2h-1, thermosol liquefaction products are separated into lightweight hot-melt object and lignite heat
Molten catalysis heavy component, wherein separation method includes normal pressure separation or decompression separation, and lightweight hot-melt object is that boiling point is lower than 170 DEG C
Front-end volatiles, lignite thermally dissolving and catalytic heavy component is the tails that boiling point is 450~510 DEG C, and the ash content of tails is lower than
0.1%, C content > 95%, molecular weight are 700~2800.
Embodiment 1
The preparation method for present embodiments providing a kind of super capacitor active carbon, specifically includes,
35wt% brown coal powder, 64.95wt%1- methyl naphthalene and 0.05wt% iodate zinc catalyst are thoroughly mixed into
Coal slurry, the reaction of coal slurry thermally dissolving and catalytic generate thermosol liquefaction products, and hydrogenation temperature is 420 DEG C, pressure 6MPa, hydrogen to oil volume ratio are
500, air speed 1h-1, obtained thermosol liquefaction products are separated into the lignite thermally dissolving and catalytic weight that lightweight thermosol object and boiling point are 500 DEG C
Matter component；
Lignite thermally dissolving and catalytic heavy component is broken, milling, after the screening of 100 mesh screens, screenings and KNO3According to matter
Amount is uniformly mixed than 1:0.1 and is placed in reaction kettle, is passed through air, flow velocity 20mLmin-1·g-1, then, with 0.5 DEG C
min-1280 DEG C are warming up to, carries out non-fusible reaction at such a temperature, reaction time 12h obtains non-fusible intermediate product；
Non-fusible intermediate product, KOH aqueous solution and methanol are uniformly mixed, wherein non-fusible intermediate product, KOH and methanol
Mass ratio be 1:2:0.0001, be put into high-temperature reactor, be passed through nitrogen, gas flow rate is controlled in 50mLmin-1·g-1, so
Afterwards with 5 DEG C of min-1It is warming up to 600 DEG C of progress carbonization reactions, reaction time 1h, then with 5 DEG C of min-1It is warming up to 900 DEG C of progress
Priming reaction obtains activated material after reacting 1h；It takes out activated material to impregnate, rinse into the water, adds 2wt% dilute hydrochloric acid and be washed till
Aqueous solution is in neutrality, and drying in air dry oven is put into after filtering, obtains super capacitor active carbon after constant temperature 6h at 115 DEG C.
Embodiment 2
The preparation method for present embodiments providing a kind of super capacitor active carbon, specifically includes,
33wt% brown coal powder, 64.5wt%1- methyl naphthalene and 2.5wt% iodate zinc catalyst are thoroughly mixed coal-forming
Slurry, the reaction of coal slurry thermally dissolving and catalytic generate thermosol liquefaction products, and hydrogenation temperature is 435 DEG C, pressure 8MPa, hydrogen to oil volume ratio are
450, air speed 1.2h-1, obtained thermosol liquefaction products are separated into the lignite thermally dissolving and catalytic of lightweight thermosol object and boiling point > 500 DEG C
Heavy component；
Lignite thermally dissolving and catalytic heavy component is broken, milling, after the screening of 150 mesh screens, screenings and HNO3According to matter
Amount is uniformly mixed than 1:0.5 and is placed in reaction kettle, is passed through air, flow velocity 35mLmin-1·g-1, then, with 1 DEG C
min-1300 DEG C are warming up to, carries out non-fusible reaction at such a temperature, reaction time 8h obtains non-fusible intermediate product；
Non-fusible intermediate product, NaOH aqueous solution and ethyl alcohol are uniformly mixed, wherein non-fusible intermediate product, NaOH and second
The mass ratio of alcohol is 1:1.8:0.0002, is put into high-temperature reactor, is passed through nitrogen, and gas flow rate is controlled in 70mLmin-1·g-1, then with 3 DEG C of min-1It is warming up to 550 DEG C of progress carbonization reactions, reaction time 1.5h, then with 3 DEG C of min-1It is warming up to 850
DEG C carry out priming reaction, react 2h after obtain activated material；It takes out activated material to impregnate, rinse into the water, adds the dilute salt of 3wt%
Pickling to aqueous solution is in neutrality, and drying in air dry oven is put into after filtering, obtains super capacitor activity at 130 DEG C after constant temperature 4h
Charcoal.
Embodiment 3
The preparation method for present embodiments providing a kind of super capacitor active carbon, specifically includes,
33wt% brown coal powder, 64.5wt%1- methyl naphthalene and 2.5wt% iodate zinc catalyst are thoroughly mixed coal-forming
Slurry, the reaction of coal slurry thermally dissolving and catalytic generate thermosol liquefaction products, and hydrogenation temperature is 435 DEG C, pressure 8MPa, hydrogen to oil volume ratio are
450, air speed 1.2h-1, obtained thermosol liquefaction products are separated into the lignite thermally dissolving and catalytic of lightweight thermosol object and boiling point > 500 DEG C
Heavy component；
Lignite thermally dissolving and catalytic heavy component is broken, milling, after the screening of 300 mesh screens, screenings and KNO3According to matter
Amount is uniformly mixed than 1:0.15 and is placed in reaction kettle, is passed through air, flow velocity 25mLmin-1·g-1, then, with 1.5
℃·min-1320 DEG C are warming up to, carries out non-fusible reaction at such a temperature, reaction time 5h obtains non-fusible intermediate product；
By non-fusible intermediate product, NaHCO3Aqueous solution and propyl alcohol are uniformly mixed, wherein non-fusible intermediate product, NaHCO3
Mass ratio with propyl alcohol is 1:2.5:0.0001, is put into high-temperature reactor, is passed through nitrogen, and gas flow rate is controlled in 65mLmin-1·g-1, then with 5 DEG C of min-1It is warming up to 500 DEG C of progress carbonization reactions, reaction time 3h, then with 5 DEG C of min-1It is warming up to
850 DEG C of progress priming reactions obtain activated material after reacting 3h；It takes out activated material to impregnate, rinse into the water, adds 5wt%
Dilute hydrochloric acid is washed till aqueous solution and is in neutrality, and drying in air dry oven is put into after filtering, obtains super capacitor after constant temperature 3h at 120 DEG C
Active carbon.
Embodiment 4
The preparation method for present embodiments providing a kind of super capacitor active carbon, specifically includes,
33wt% brown coal powder, 64.5wt%1- methyl naphthalene and 2.5wt% iodate zinc catalyst are thoroughly mixed coal-forming
Slurry, the reaction of coal slurry thermally dissolving and catalytic generate thermosol liquefaction products, and hydrogenation temperature is 435 DEG C, pressure 8MPa, hydrogen to oil volume ratio are
450, air speed 1.2h-1, obtained thermosol liquefaction products are separated into the lignite thermally dissolving and catalytic of lightweight thermosol object and boiling point > 500 DEG C
Heavy component；
Lignite thermally dissolving and catalytic heavy component is broken, milling, after the screening of 300 mesh screens, screenings and KNO3According to matter
Amount is uniformly mixed than 1:0.01 and is placed in reaction kettle, is passed through air, flow velocity 50mLmin-1·g-1, then, with 1.2
℃·min-1250 DEG C are warming up to, carries out non-fusible reaction at such a temperature, reaction time 20h obtains non-fusible intermediate production
Object；
By non-fusible intermediate product, NaHCO3Aqueous solution and wetting agent (mixture of propyl alcohol and ethyl alcohol mass ratio 1:1) are mixed
It closes uniformly, wherein non-fusible intermediate product, NaHCO3Mass ratio with wetting agent is 1:2.5:0.0001, is put into pyroreaction
Device, is passed through nitrogen, and gas flow rate is controlled in 10mLmin-1·g-1, then with 2 DEG C of min-1400 DEG C are warming up to be carbonized
Reaction, reaction time 2h, then with 20 DEG C of min-1600 DEG C of progress priming reactions are warming up to, obtain activated material after reacting 6h；It takes out
Activated material is impregnated into the water, is rinsed, and is added 5wt% dilute hydrochloric acid and is washed till aqueous solution and is in neutrality, and forced air drying is put into after filtering
It is dry in case, super capacitor active carbon is obtained after constant temperature 8h at 150 DEG C.
Embodiment 5
The preparation method for present embodiments providing a kind of super capacitor active carbon, specifically includes,
33wt% brown coal powder, 64.5wt%1- methyl naphthalene and 2.5wt% iodate zinc catalyst are thoroughly mixed coal-forming
Slurry, the reaction of coal slurry thermally dissolving and catalytic generate thermosol liquefaction products, and hydrogenation temperature is 435 DEG C, pressure 8MPa, hydrogen to oil volume ratio are
450, air speed 1.2h-1, obtained thermosol liquefaction products are separated into the lignite thermally dissolving and catalytic of lightweight thermosol object and boiling point > 500 DEG C
Heavy component；
Lignite thermally dissolving and catalytic heavy component is broken, milling, after the screening of 300 mesh screens, screenings and KNO3According to matter
Amount is uniformly mixed than 1:0.35 and is placed in reaction kettle, is passed through air, flow velocity 10mLmin-1·g-1, then, with 0.8
℃·min-1350 DEG C are warming up to, carries out non-fusible reaction at such a temperature, reaction time 1h obtains non-fusible intermediate product；
By non-fusible intermediate product, NaHCO3Aqueous solution and propyl alcohol are uniformly mixed, wherein non-fusible intermediate product, NaHCO3
Mass ratio with propyl alcohol is 1:2.5:0.0001, is put into high-temperature reactor, is passed through nitrogen, and gas flow rate is controlled in 90mLmin-1·g-1, then with 10 DEG C of min-1It is warming up to 600 DEG C of progress carbonization reactions, reaction time 0.5h, then with 12 DEG C of min-1It rises
Temperature obtains activated material after reacting 0.5h to 1000 DEG C of progress priming reactions；Activated material is taken out to impregnate, rinse into the water, then plus
Enter 5wt% dilute hydrochloric acid and be washed till aqueous solution to be in neutrality, be put into air dry oven dry after filtering, is obtained after constant temperature 4h at 180 DEG C
Super capacitor active carbon.
Comparative example 1
This comparative example provides a kind of preparation method of active carbon, the difference from embodiment 1 is that, with lignite thermally dissolving and catalytic
Heavy component is raw material, and active carbon is made using conventional method, specifically includes,
35wt% brown coal powder, 64.95wt%1- methyl naphthalene and 0.05wt% iodate zinc catalyst are thoroughly mixed into
Coal slurry, the reaction of coal slurry thermally dissolving and catalytic generate thermosol liquefaction products, and hydrogenation temperature is 420 DEG C, pressure 6MPa, hydrogen to oil volume ratio are
500, obtained thermosol liquefaction products are separated into the lignite thermally dissolving and catalytic that lightweight thermosol object and boiling point are 500 DEG C by air speed 1h-1
Heavy component；
Lignite thermally dissolving and catalytic heavy component is broken, milling, after the screening of 100 mesh screens, screenings according to 1:4 quality
Than non-fusible intermediate product to be uniformly mixed with KOH aqueous solution, it is put into high-temperature reactor, is passed through nitrogen, gas flow rate control exists
Then 50mLmin-1g-1 is warming up to 600 DEG C of progress carbonization reactions with 5 DEG C of min-1, reaction time 1h, then with 5 DEG C
Min-1 is warming up to 900 DEG C of progress priming reactions, obtains activated material after reacting 1h；Activated material is taken out to impregnate, rinse into the water,
It adds 2% hydrochloric acid and is washed till aqueous solution and be in neutrality, be put into air dry oven dry after filtering, obtained after constant temperature 6h at 115 DEG C
Active carbon.
Test example
This test example provides performance test methods and as a result, the test of active carbon made from embodiment 1-5 and comparative example 1
It the results are shown in Table 1, test method is as follows；
The test method of specific surface area: use volumetric method at 77K with high-purity N2It is 10 in relative pressure for adsorbate-7-
It carries out inhaling/being desorbed in the range of 1.0, measures its Adsorption and desorption isotherms.By BET method in relative pressure P/P0=0.01-0.05 model
Enclose the specific surface area for calculating sample；
The test method of total pore volume: use volumetric method at 77K with high-purity N2It is 10 in relative pressure for adsorbate-7-
It carries out inhaling/being desorbed in the range of 1.0, measures its Adsorption and desorption isotherms.Suction when total pore volume is by relative pressure P/P0=0.996
Attached amount is calculated；
The test method of Micropore volume: national standard GB/T 21650.3-2011 " mercury injection method and gas determination of adsorption method solid are pressed
Material pore-size distribution and porosity " third portion " gas adsorption method analysis micropore " measurement；
The test method of mesopore volume: national standard GB/T 21650.2-2008 " mercury injection method and gas determination of adsorption method solid are pressed
Material pore-size distribution and porosity " part 2 " gas adsorption method analyze mesoporous and macropore " measurement；
The test method of mesoporous: the percentage of mesopore volume and total pore volume；
The test method of conductivity: the conductivity of material can be from resistance rate conversion, and resistivity measurement method presses GB/
T24525-2009 " carbon material determination of resistivity method " measurement；
The test method of specific capacitance: weighing active carbon and polytetrafluoroethylene (PTFE) (lotion of 60wt%) by the mass ratio of 95:5,
Ethanol in proper amount is added, mixture, which is carried out adequately grinding, in the agate mortar makes binder be uniformly dispersed in active carbon；So
Hydraulic press is used afterwards, and at 10MPa, it is 0.5mm that sample, which is pressed into thickness, and diameter is the disk of 13.3mm, respectively by carbon plate pressure
Electrode slice is made in foamed nickel current collector, tantalum foil collector and aluminum foil current collector in system；It is carried out using electrochemical workstation super
The Cyclic voltamogram of capacitor is tested, by the specific capacitance of cyclic voltammetry curve integral calculation active carbon.
The test method of surface functional group content: Boehm titration is used.
The performance test results of active carbon made from 1 embodiment 1-5 of table and comparative example
From table 1, it can be seen that the specific surface area and mesoporous of super capacitor active carbon made from embodiment 1 are obvious
Higher than active carbon made from comparative example 1, illustrate provided by the invention using lignite thermally dissolving and catalytic heavy component as the preparation side of raw material
The better performances of super capacitor active carbon made from method.The large specific surface area of super capacitor active carbon produced by the present invention, total hole
Hold and mesoporous is higher, good conductivity, wherein the multiple spot BET specific surface area of super capacitor active carbon is not less than 2500m2·g-1,
Total pore volume is not less than 1.5cm3·g-1, pore-size distribution is reasonable, and mesoporous is between 40%~50%, and mesoporous is higher helps to mention
The service life of high super capacitor active carbon.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And thus amplify out it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of preparation method of super capacitor active carbon, which is characterized in that including by lignite thermally dissolving and catalytic heavy component and in advance
Oxidant is mixed and is reacted, and obtains non-fusible intermediate product；
Be uniformly mixed the non-fusible intermediate product to obtain mixed material with activator, carbonized, activate after obtain it is described super
Grade capacitor active carbon.
2. preparation method according to claim 1, which is characterized in that mix the non-fusible intermediate product with activator
When, further include the steps that wetting agent, which is added, obtains mixed material, wherein the non-fusible intermediate product, the activator and institute
The mass ratio for stating wetting agent is 1:(1-5): (0.0001-0.0005).
3. preparation method according to claim 2, which is characterized in that the activator is KOH, NaOH and NaHCO3In
It is at least one；
The wetting agent is at least one of acetone, methanol and ethyl alcohol.
4. preparation method according to claim 1-3, which is characterized in that the lignite thermally dissolving and catalytic heavy component
It is not less than 2:1 with the mass ratio of pre-oxidation agent.
5. preparation method according to claim 1-4, which is characterized in that the lignite thermally dissolving and catalytic heavy component
After being mixed with pre-oxidation agent, it is warming up to 250-350 DEG C with the heating rate of 0.5-1.5 DEG C/min, keeps the temperature 1-20h, reaction obtains
The non-fusible intermediate product.
6. preparation method according to claim 1-5, which is characterized in that under oxygen-free environment, the mixture
After material is warming up to 400-600 DEG C with the heating rate of 2-10 DEG C/min, 0.5-3h is kept the temperature, the carbonization reaction is carried out.
7. preparation method according to claim 1-6, which is characterized in that after the charing, keep anaerobic
Environment is warming up to 600-1000 DEG C with the heating rate of 3-20 DEG C/min, and heat preservation is not more than 6h, completes the priming reaction.
8. preparation method according to claim 1-7, which is characterized in that further include, to the product after activation into
The step of row washing, pickling and drying.
9. preparation method according to claim 1-8, which is characterized in that the lignite thermally dissolving and catalytic heavy component
The product for being 450-510 DEG C by the boiling point that thermally dissolving and catalytic technological reaction generates for lignite.
10. a kind of super capacitor active carbon that the described in any item methods of claim 1-9 are prepared.
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