CN104512891B - Activated carbon microsphere with high specific surface area, manufacturing method thereof, electrode plate and capacitor - Google Patents
Activated carbon microsphere with high specific surface area, manufacturing method thereof, electrode plate and capacitor Download PDFInfo
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- CN104512891B CN104512891B CN201310535952.9A CN201310535952A CN104512891B CN 104512891 B CN104512891 B CN 104512891B CN 201310535952 A CN201310535952 A CN 201310535952A CN 104512891 B CN104512891 B CN 104512891B
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- activated carbon
- specific surface
- surface area
- carbon microballon
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 209
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 47
- 239000004005 microsphere Substances 0.000 title claims abstract description 21
- 239000003990 capacitor Substances 0.000 title abstract description 9
- 239000002931 mesocarbon microbead Substances 0.000 claims abstract description 63
- 239000011347 resin Substances 0.000 claims abstract description 37
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 230000004913 activation Effects 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 49
- 239000012190 activator Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000012805 post-processing Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910001868 water Inorganic materials 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical group [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 3
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 229910000160 potassium phosphate Inorganic materials 0.000 claims 1
- 235000011009 potassium phosphates Nutrition 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 3
- 230000003213 activating effect Effects 0.000 abstract description 2
- 239000011325 microbead Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 7
- 238000003763 carbonization Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- -1 hydrogen Potassium oxide Chemical class 0.000 description 3
- 239000011806 microball Substances 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011302 mesophase pitch Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910019785 NBF4 Inorganic materials 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical group C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- QNEFNFIKZWUAEQ-UHFFFAOYSA-N carbonic acid;potassium Chemical compound [K].OC(O)=O QNEFNFIKZWUAEQ-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention provides an activated carbon microsphere with high specific surface area, a manufacturing method thereof, an electrode plate and a capacitor. The manufacturing method comprises the following steps: providing a mesocarbon microbead, wherein the mesocarbon microbead comprises gamma-resin; a drying step is carried out, and the mesocarbon microbeads are heated for 8 to 12 hours at the temperature of between 410 and 550 ℃; and performing an activation step on the intermediate phase carbon microspheres subjected to the drying step to form activated carbon microspheres, wherein the content of the gamma-resin in the intermediate phase carbon microspheres is less than 0.5 weight percent. The activated carbon microsphere with high specific surface area is prepared by the preparation method. The electrode plate comprises the activated carbon microspheres with high specific surface area. The capacitor comprises the electrode plate. The manufacturing method removes the gamma-resin of the mesocarbon microbeads through the drying step, reduces the using amount of the activating agent, and the prepared activated carbon microbeads have high specific surface area and high specific capacitance value and can be applied to electrode plates and capacitors.
Description
Technical field
The invention relates to a kind of activated carbon microballon and manufacture method thereof, and in particular to a kind of high-specific surface area
Activated carbon microballon and manufacture method thereof and comprise the electrode slice of activated carbon microballon and the electric capacity of this high-specific surface area, belong to
In technical field of active carbon.
Background technology
Double-layer capacitor (Electric Double Layer Capacitors；EDLC) it is a kind of electric with common between battery
Energy storage equipment between appearance, is generally of the biggest capacitance, and being primarily due to double-layer capacitor is to be divided by electric charge
The mode left stores energy.The area of storage electric charge is the biggest or the segregate distance of electric charge is the least, and capacitance will
The biggest.Therefore, double-layer capacitor electric automobile, fuel combination automobile, exceptional load automobile, electric power, railway,
The various fields such as communication, national defence, consumption electronic products have huge using value and market potential.
The double-layer capacitor of present stage generally utilizes porous charcoal system electrode material to obtain big storage electric charge area.Example
As, activated carbon is the material with high-specific surface area and electric conductivity, therefore can be as porous charcoal system electrode material.Its
In, the surface area (specific surface area in Unit Weight；Unit is m2/ g) can be relevant with storable capacitance, when than table
When area is the biggest, storable capacitance can be the biggest.
But, currently with the activated carbon obtained by general technology, generally cannot be simultaneously with high specific capacitance and high ratio
The feature of surface area, or need the cost paying costliness that activated carbon just can be made to reach high specific capacitance and high-specific surface area
Feature.
In view of this, activated carbon microballon and the manufacture method thereof that a kind of high-specific surface area is provided is needed badly, to overcome known work
The variety of problems that skill faces.
Summary of the invention
For solving above-mentioned technical problem, an object of the present invention is to provide the activated carbon microballon of a kind of high-specific surface area
Manufacture method.This manufacture method is before carrying out activation step, first will dry containing the MCMB of γ-resin
Dry step, so that the content of γ-resin is less than 0.5 percentage by weight, is consequently formed the activated carbon microballon of high-specific surface area.
It is a further object of the present invention to provide the activated carbon microballon of a kind of high-specific surface area.The activated carbon of this high-specific surface area
Microsphere utilizes obtained by above-mentioned manufacture method.The activated carbon microballon of this high-specific surface area has the specific surface area of excellence
And compare capacitance.
It is a further object of the present invention to provide a kind of electrode slice.This electrode slice comprises the activated carbon of above-mentioned high-specific surface area
Microsphere.
Another object of the present invention is to provide a kind of electric capacity.This electric capacity comprises above-mentioned electrode slice.
For reaching above-mentioned purpose, the present invention provides the manufacture method of the activated carbon microballon of a kind of high-specific surface area, comprises following
Step:
A MCMB, described MCMB is provided to comprise γ-resin；
Carry out a baking step, with the temperature more than 410 DEG C to 550 DEG C, described MCMB is heated 8 to 12
Hour；And
MCMB through described baking step is carried out an activation step, with the activated carbon microballon described in formation,
Wherein, described γ-resin content in described MCMB is less than 0.5 percentage by weight.
In the manufacture method of the activated carbon microballon of above-mentioned high-specific surface area, it is preferable that described γ-resin is in described centre
Content in phase carbon microspheres is 0.05 to 0.4 percentage by weight.
In the manufacture method of the activated carbon microballon of above-mentioned high-specific surface area, it is preferable that described γ-resin is in described centre
Content in phase carbon microspheres is 0.05 to 0.3 percentage by weight.
In the manufacture method of the activated carbon microballon of above-mentioned high-specific surface area, it is preferable that described baking step is with 420
DEG C to 500 DEG C temperature to described MCMB heat 8 to 10 hours.
In the manufacture method of the activated carbon microballon of above-mentioned high-specific surface area, it is preferable that described baking step is with 420
DEG C to 450 DEG C temperature to described MCMB heat 8 hours.
In the manufacture method of the activated carbon microballon of above-mentioned high-specific surface area, it is preferable that described activation step comprises:
Carry out a blend step, mix an activator and the MCMB through described baking step, mixed to form one
Compound；And
Described mixture is carried out a heating steps, its be under nitrogen atmosphere, from 10-40 DEG C with 1 DEG C/minute to 5 DEG C/
The heating rate divided is warming up to 520 DEG C and keeps temperature 1.5 hours, then is warming up to 900 DEG C with this heating rate and protects
Hold temperature 4 hours, with the activated carbon microballon described in formation.
In the manufacture method of the activated carbon microballon of above-mentioned high-specific surface area, it is preferable that described activator be alkali metal or
The hydroxide of alkaline-earth metal.
In the manufacture method of the activated carbon microballon of above-mentioned high-specific surface area, it is preferable that described activator is Lithium hydrate
(LiOH), sodium carbonate (Na2CO3), zinc chloride (ZnCl2), phosphorus pentoxide (P2O5), potassium carbonate (K2CO3), hydrogen-oxygen
Change calcium (Ca (OH)2), potassium phosphate (K3PO4), steam (H2O), carbon dioxide (CO2), potassium hydroxide (KOH),
Sodium hydroxide (NaOH) or ferrous sulfate (FeSO4)。
In the manufacture method of the activated carbon microballon of above-mentioned high-specific surface area, it is preferable that described MCMB and institute
The weight ratio stating activator is 1:3.
In the manufacture method of the activated carbon microballon of above-mentioned high-specific surface area, it is preferable that after described activation step,
Further including at least described activated carbon microballon being carried out an activation post-processing step.
In the manufacture method of the activated carbon microballon of above-mentioned high-specific surface area, it is preferable that described activation post-processing step bag
Contain: utilize activated carbon microballon described in steam treatment；Carry out an acid pickling step again；And carry out a hot water cleaning step.
In the manufacture method of the activated carbon microballon of above-mentioned high-specific surface area, it is preferable that through described activation post-processing step
The specific surface area of activated carbon microballon be at least 2800m2/ g, and it is at least 180F/g than capacitance.
In the manufacture method of the activated carbon microballon of above-mentioned high-specific surface area, it is preferable that through described activation post-processing step
The specific surface area of activated carbon microballon be at least 2837m2/ g, and it is at least 185F/g than capacitance.
The present invention also provides for the activated carbon microballon of a kind of high-specific surface area, and it is by the activated carbon of above-mentioned high-specific surface area
Obtained by the manufacture method of microsphere.
The present invention also provides for a kind of electrode slice, and it comprises the activated carbon microballon of above-mentioned high-specific surface area.
The present invention also provides for a kind of electric capacity, and it comprises above-mentioned electrode slice.
The manufacture method of the activated carbon microballon of the high-specific surface area of the present invention includes carrying out MCMB drying step
Suddenly, to reduce γ-resin content in MCMB, the activated carbon formed after thus making activated step is micro-
Ball has high-specific surface area and high specific capacitance, it is adaptable to electrode slice and electric capacity, and the technique overcoming processes well known to face is held high
Your problem.
Accompanying drawing explanation
Fig. 1 is the part manufacture method flow chart of the activated carbon microballon of the high-specific surface area of one embodiment of the invention.
Primary clustering symbol description:
100 methods
110 steps that MCMB is provided
120 baking steps
130 activation steps
Detailed description of the invention
Described in brought forward, the present invention provides the manufacture method of the activated carbon microballon of a kind of high-specific surface area, and it is in mesophase
Before carbon microspheres carries out activation step, with the temperature more than 410 DEG C to 550 DEG C, MCMB is heated 8 to 12
Hour, so that the content of γ-resin that MCMB contains is for less than 0.5 percentage by weight, thus it is greatly improved
The specific surface area of the activated carbon microballon formed and compare capacitance.
Referring to Fig. 1, it is the part manufacture method of activated carbon microballon of high-specific surface area of one embodiment of the invention
Flow chart.Profess it, in an embodiment of the inventive method 100, first, as provided the step of MCMB
Shown in rapid 110, it is provided that MCMB (GMP:Green Mesophase Powder), this MCMB
Comprise γ-resin.In one embodiment, above-mentioned applicable carbon microspheres can the most commercially available Mesophase Pitch-based Carbon micro-
Ball, wherein this mesophase pitch carbon microspheres to process, to have the mesophase stratiform of at least 60% (v/v) without any carbonization
Structure and quinoline non-soluble composition (quinoline insoluble, hereinafter referred to as QI) are preferred more than 95% (w/w).Its
Secondary, in one embodiment, γ-resin is defined as the resin that volatilization temperature is at 200 DEG C to 400 DEG C.
After the step 110 providing MCMB, carrying out baking step 120, it is with more than 410 DEG C to 550
DEG C temperature to MCMB heat 8 to 12 hours.It is noted that usual MCMB γ-tree
Fat can react with activator, and the usage amount of activator is increased.Therefore when carrying out baking step 120, if
Temperature is less than or equal to 410 DEG C, will be unable to the γ-resin effectively volatilizing in MCMB, and makes making of activator
Consumption increases；If temperature is more than 600 DEG C, will result in the easy carbonization of MCMB so that MCMB
Crystallinity own improves and the activation effect of unfavorable follow-up activation step 130.In one embodiment, baking step
MCMB can be heated 8 to 10 hours by 120 with the temperature of 420 DEG C to 500 DEG C.In one embodiment, dry
Dry step 120 can be that MCMB is heated 8 hours by the temperature with 420 DEG C to 450 DEG C.
Afterwards, the MCMB of drying step 120 is carried out activation step 130, to form activated carbon microballon,
Wherein γ-resin content in MCMB is less than 0.5 percentage by weight.γ-resin is in MCMB
If content in is higher than 0.5 percentage by weight, then γ-resin will consume more activator, and causes activator
Use cost rises.In one embodiment, γ-resin content in MCMB can be 0.05 to 0.4 weight
Percentage ratio.In one embodiment, γ-resin content in MCMB can be 0.05 to 0.3 percentage by weight.
In one embodiment, activation step 130 can comprise and carries out blend step and heating steps.Blend step is mixing
Activator and the MCMB of drying step 120.Then described mixture is carried out heating steps, its be in
Under nitrogen atmosphere, it is warming up to 520 DEG C with the heating rate of 1 DEG C/minute to 5 DEG C/minute from 10-40 DEG C and keeps temperature 1.5
Hour, then be warming up to 900 DEG C with this heating rate and keep temperature 4 hours, to form activated carbon microballon.Real one
Executing in example, activator can be the hydroxide of alkali metal or alkaline-earth metal.In one embodiment, activator can comprise but
It is not limited to Lithium hydrate (LiOH), sodium carbonate (Na2CO3), zinc chloride (ZnCl2), phosphorus pentoxide (P2O5), carbonic acid
Potassium (K2CO3), calcium hydroxide (Ca (OH)2), potassium phosphate (K3PO4), steam (H2O), carbon dioxide (CO2), hydrogen
Potassium oxide (KOH), sodium hydroxide (NaOH) or ferrous sulfate (FeSO4).In another embodiment, intermediate-phase carbon is micro-
Ball can be 1:3 with the weight ratio of activator.
According to one embodiment of the invention, after above-mentioned activation step 130, more it is selectively included the work to gained
Property carbon microspheres carry out activate post-processing step.In one embodiment, the activation post-processing step being suitable for can comprise but not limit
After the step utilizing steam treatment activated carbon microballon, then carry out acid pickling step and hot water cleaning step.Described water
Steam treated, pickling and hot water clean available known manner to be carried out.
In one embodiment, the specific surface area of the activated carbon microballon of activated post-processing step can be at least 2800m2/ g,
And can be at least 180F/g than capacitance.In one embodiment, the ratio table of the activated carbon microballon of activated post-processing step
Area can be at least 2837m2/ g, and can be at least 185F/g than capacitance.
It is noted that generally MCMB γ-resin can react with activator, and make the use of activator
Amount increases.And the present invention is that MCMB first carries out baking step 120, so that it is micro-originally to there is intermediate-phase carbon
The γ of ball-resin volatilization, the most just carries out activation step 130 to form activated carbon microballon.Therefore, in activated carbon microballon
γ-resin can reduce, therefore also reduce the usage amount of activator, therefore manufacturing cost can be reduced, and can make follow-up
The activated carbon microballon formed has high-specific surface area and high specific capacitance value.
Secondly as the easy carbonization more than 600 DEG C of the material of MCMB, and make MCMB originally
Body crystallinity improves and is difficult to be activated, so being with the temperature more than 410 DEG C to 550 DEG C in baking step 120
MCMB is heated, to avoid the situation of carbonization to produce.It is noted that the most so-called being difficult to is activated
Refer to, because it is to make MCMB produce loose structure that MCMB carries out activation step, so that
MCMB has high-specific surface area.And if MCMB produces carbonization reaction, then carrying out activation step
Time, activator can be difficult to be reacted to form loose structure with the MCMB of carbonization, therefore cannot make intermediate-phase carbon
Microsphere forms the loose structure with high-specific surface area further.
Following with several embodiments so that technical scheme to be described, what so it was not limited to the present invention can be real
Executing scope, art those skilled in the art of the present invention are without departing from the spirit and scope of the present invention, various when making
Change and retouching.
Embodiment 1
First, by MCMB G (green mesophase powder, GMP；GP-24；fix carbon>90%；
Fugitive constituent 8 ± 2%；QI is 95%, mean diameter (D50) it is 25 μm；China Steel Chemical Co., Ltd.,
TaiWan, China) it is placed at a temperature of 420 DEG C and heats 12 hours, to remove γ-resin contained therein, in the middle of being formed
Phase carbon microspheres DG.
Then, by MCMB DG and potassium hydroxide (KOH；Purity 95%；TaiWan, China paper industry is limited
Company, TaiWan, China) ratio with weight ratio as 1:3 forms mixture, and again mixture carried out heating steps,
It is under nitrogen atmosphere, utilizes the mode of two benches linear heat, from 10-40 DEG C with the liter of 1 DEG C/minute to 5 DEG C/minute
Temperature ramp to 520 DEG C and keeps temperature 1.5 hours, then is warming up to 900 DEG C with this heating rate and keeps temperature 4
Hour, to obtain activated carbon microballon.
Then, carry out activating post-processing step, its be steam is reacted with activated carbon microballon after, carry out filtering, sour
Wash, the step such as hot water cleaning to be to obtain activated carbon microballon.
Comparative example 1
With the preparation method of embodiment 1, at difference, it is that comparative example 1 is to provide MCMB BG (middle steel carbon
The chemical limited company of element, TaiWan, China), it is that MCMB G is added part low softening point mesophase
Carbon microspheres is formed, and MCMB BG does not carry out baking step.
Comparative example 2
With the preparation method of embodiment 1, it is that comparative example 2 is to provide MCMB G at difference, and does not carries out
Baking step.
Assessment mode
Embodiment 1 carries out multinomial performance test with the activated carbon microballon of comparative example 1 to 2.Test event is as follows:
1, assessment γ-resin and the content of β-resin
Utilize commercially available thermogravimetric analyzer (Perkin Elmer SII, Pyris Diamond TG/DTA) with per minute about 20
DEG C heating rate measure γ-resin and the content of β-resin in MCMB, wherein the definition of β-resin is for waving
Send out temperature at the resin more than 400 DEG C to 600 DEG C, the result of gained is as shown in table 1.
Table 1
2, assessment specific surface area, total hole volume and average pore size
Commercially available Porosimetry (Micromeritics, model ASAP2020) is utilized to measure the ratio table of activated carbon microballon
Area (BET；m2/ g), average pore size (nm), total hole volume (cm3), the result of gained is as shown in table 1.
3, capacitance is compared in assessment
First, with the activated carbon microballon of 3.2g, the N-methyl 2-pyrrolidone N-of 13.4g, the Kynoar of 0.6g, 0.2g
Then the accelerator of conductive black and 0.004g is modulated into viscosity and is about the activated carbon slurry of 3500cps, and utilizes commercially available
Viscosimeter (Brookfiled LVDV viscosimeter), with test parameter as 10rpm, No. 64 rotors, shear rates be
2.1/ second, obtain viscosity test result.
Then, the activated carbon slurry of above-mentioned gained is coated on the aluminium foil of 30 μ m-thick, through temperature 150 DEG C and 10
Forming activated carbon electrodes sheet after minute baking, and it is respectively 1.327 squares of public affairs that activated carbon electrodes sheet cuts into two areas
Point circular test piece, by two circular test pieces collocation polypropylene (PP) isolating membrane and electrolyte (electrolysis that concentration is 1M
Matter is tetraethylammonium tetrafluoroborate (Et4NBF4)；Solvent is Allyl carbonate (PC)), to be formed and international standards
The test electric capacity that the battery specifications of CR2032 is identical.
Then measure with electrochemical apparatus, carry out the Electrochemical Scanning of electric current/volt with the sweep speed of 10mV/s, and
Obtaining the ratio capacitance of each test electric capacity after integrated, the result of gained is as shown in table 1.
As shown in Table 1, the activated carbon microballon of embodiment 1 has at least 2800m2The specific surface area of/g and
The high specific capacitance value of at least 180F/g, reaches the purpose of the present invention really, and wherein the activated carbon microballon of embodiment 1 is more
There is at least 2837m2The specific surface area of/g and the high specific capacitance value of at least 185F/g.But, comparative example 1 with than
The specific surface area of the relatively carbon microspheres of example 2 and be smaller than the respective value of embodiment 1 than capacitance.
Need to supplement, though the present invention makees with specific material, technique, reaction condition, analysis method or particular instrument
For illustrating, illustrate the present invention for electrode slice and the activated carbon microballon of the high-specific surface area of electric capacity and manufacture method thereof,
But the technical field of the invention those skilled in the art understand, and the present invention is not limited to this, in the essence without departing from the present invention
In god and scope, the present invention for electrode slice and the activated carbon microballon of the high-specific surface area of electric capacity and manufacture method thereof also
Other material, technique, reaction condition, analysis method or instrument can be used to carry out.
From embodiments of the invention described above, the activated carbon microballon of the high-specific surface area of the present invention and manufacture method thereof with
And comprise electrode slice and the electric capacity of this activated carbon microballon, have an advantage in that and utilize baking step to remove containing of γ-resin
Amount, in addition to the consumption being effectively reduced activator, also can increase specific surface area and the ratio capacitance of activated carbon microballon,
And then apply in electrode slice and electric capacity.
Although the present invention is disclosed above with several embodiments, so it is not limited to the present invention, skill belonging to the present invention
Art skilled person, without departing from the spirit and scope of the present invention, when making various change and retouching, because of
This protection scope of the present invention is when being as the criterion with claims.
Claims (16)
1. a manufacture method for the activated carbon microballon of high-specific surface area, comprises the steps of
There is provided a MCMB, described MCMB to comprise γ-resin, and described γ-resin is defined as volatilization
Temperature is at the resin of 200 DEG C to 400 DEG C；
Carry out a baking step, with the temperature more than 410 DEG C to 550 DEG C, described MCMB is heated 8 to 12
Hour；And
MCMB through described baking step is carried out an activation step, with the activated carbon microballon described in formation,
Wherein, described γ-resin content in described MCMB is less than 0.5 percentage by weight.
The manufacture method of the activated carbon microballon of high-specific surface area the most according to claim 1, wherein, described γ-
Resin content in described MCMB is 0.05 to 0.4 percentage by weight.
The manufacture method of the activated carbon microballon of high-specific surface area the most according to claim 1, wherein, described γ-
Resin content in described MCMB is 0.05 to 0.3 percentage by weight.
The manufacture method of the activated carbon microballon of high-specific surface area the most according to claim 1, wherein, described baking
Dry step is that described MCMB is heated 8 to 10 hours by the temperature with 420 DEG C to 500 DEG C.
The manufacture method of the activated carbon microballon of high-specific surface area the most according to claim 1, wherein, described baking
Dry step is that described MCMB is heated 8 hours by the temperature with 420 DEG C to 450 DEG C.
The manufacture method of the activated carbon microballon of high-specific surface area the most according to claim 1, wherein, described work
Change step to comprise:
Carry out a blend step, mix an activator and the MCMB through described baking step, mixed to form one
Compound；And
Described mixture is carried out a heating steps, its be under nitrogen atmosphere, from 10-40 DEG C with 1 DEG C/minute to 5 DEG C/
The heating rate divided is warming up to 520 DEG C and keeps temperature 1.5 hours, then is warming up to 900 DEG C with this heating rate and protects
Hold temperature 4 hours, with the activated carbon microballon described in formation.
The manufacture method of the activated carbon microballon of high-specific surface area the most according to claim 6, wherein, described work
Agent is the hydroxide of alkali metal or alkaline-earth metal.
The manufacture method of the activated carbon microballon of high-specific surface area the most according to claim 6, wherein, described work
Agent is Lithium hydrate, sodium carbonate, zinc chloride, phosphorus pentoxide, potassium carbonate, calcium hydroxide, potassium phosphate, water steaming
Gas, carbon dioxide, potassium hydroxide, sodium hydroxide or ferrous sulfate.
The manufacture method of the activated carbon microballon of high-specific surface area the most according to claim 6, wherein, described in
Between the weight ratio of phase carbon microspheres and described activator be 1:3.
The manufacture method of the activated carbon microballon of high-specific surface area the most according to claim 1, in described activation step
After Zhou, further including at least described activated carbon microballon being carried out an activation post-processing step.
The manufacture method of the activated carbon microballon of 11. high-specific surface areas according to claim 10, wherein, described
Activation post-processing step comprises:
Utilize activated carbon microballon described in steam treatment；
Carry out an acid pickling step again；And
Carry out a hot water cleaning step.
The manufacture method of the activated carbon microballon of 12. high-specific surface areas according to claim 11, wherein, through institute
The specific surface area of the activated carbon microballon stating activation post-processing step is at least 2800m2/ g, and be at least than capacitance
180F/g。
The manufacture method of the activated carbon microballon of 13. high-specific surface areas according to claim 11, wherein, through institute
The specific surface area of the activated carbon microballon stating activation post-processing step is at least 2837m2/ g, and be at least than capacitance
185F/g。
The activated carbon microballon of 14. 1 kinds of high-specific surface areas, it is to utilize the Gao Bibiao described in any one of claim 1-13
Obtained by the manufacture method of the activated carbon microballon of area, the ratio table of the activated carbon microballon of wherein said high-specific surface area
Area is at least 2800m2/ g, and it is at least 180F/g than capacitance.
15. 1 kinds of electrode slices, it is characterised in that this electrode slice comprises the high-specific surface area described in claim 14
Activated carbon microballon, the specific surface area of the activated carbon microballon of wherein said high-specific surface area is at least 2800m2/ g, and
It is at least 180F/g than capacitance.
16. 1 kinds of electric capacity, it is characterised in that this electric capacity comprises the electrode slice described in claim 15.
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| CN115893409B (en) * | 2022-10-26 | 2024-06-28 | 中国石油大学(华东) | Method for preparing mesoporous-microporous biomass super-activated carbon based on carbon dioxide-phosphoric anhydride-copper complex combined activation |
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| US5143889A (en) * | 1987-11-20 | 1992-09-01 | Osaka Gas Company Limited | Active carbon and processes for preparation of same |
| CN101143720A (en) * | 2006-09-29 | 2008-03-19 | 北京化工大学 | Active carbon micro-sphere absorption material and preparation method thereof |
| CN101717085A (en) * | 2009-12-07 | 2010-06-02 | 北京化工大学 | Activated carbon microspheres and preparation method thereof |
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| TWI525038B (en) * | 2011-07-19 | 2016-03-11 | China Steel Chemical Corp | High specific surface area active toner manufacturing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5143889A (en) * | 1987-11-20 | 1992-09-01 | Osaka Gas Company Limited | Active carbon and processes for preparation of same |
| CN101143720A (en) * | 2006-09-29 | 2008-03-19 | 北京化工大学 | Active carbon micro-sphere absorption material and preparation method thereof |
| CN101717085A (en) * | 2009-12-07 | 2010-06-02 | 北京化工大学 | Activated carbon microspheres and preparation method thereof |
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