CN104512891A - 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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- CN104512891A CN104512891A CN201310535952.9A CN201310535952A CN104512891A CN 104512891 A CN104512891 A CN 104512891A CN 201310535952 A CN201310535952 A CN 201310535952A CN 104512891 A CN104512891 A CN 104512891A
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- activated carbon
- specific surface
- surface area
- carbon microballon
- mcmb
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 186
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 47
- 239000004005 microsphere Substances 0.000 title abstract description 11
- 239000003990 capacitor Substances 0.000 title abstract description 9
- 239000002931 mesocarbon microbead Substances 0.000 claims abstract description 72
- 239000011347 resin Substances 0.000 claims abstract description 36
- 229920005989 resin Polymers 0.000 claims abstract description 36
- 230000004913 activation Effects 0.000 claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 50
- 239000012190 activator Substances 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 11
- 239000000203 mixture Substances 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
- 238000010792 warming Methods 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000005554 pickling Methods 0.000 claims description 5
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 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
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 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
- 229910052728 basic metal Inorganic materials 0.000 claims description 3
- 150000003818 basic metals Chemical class 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 235000011089 carbon dioxide Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims 1
- 235000011116 calcium hydroxide Nutrition 0.000 claims 1
- 229940093916 potassium phosphate Drugs 0.000 claims 1
- 229910000160 potassium phosphate Inorganic materials 0.000 claims 1
- 235000011009 potassium phosphates Nutrition 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 3
- 230000003213 activating effect Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000011325 microbead Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 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
- 230000008569 process Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000003860 storage Methods 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
- 230000008859 change Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000007772 electrode material Substances 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
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical group CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- -1 tetraethylammonium tetrafluoroborate Chemical compound 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 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
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002904 solvent 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 relate to a kind of activated carbon microballon of high-specific surface area and manufacture method thereof especially and comprise the electrode slice of activated carbon microballon and the electric capacity of this high-specific surface area, belong to technical field of active carbon.
Background technology
Double-layer capacitor (Electric Double Layer Capacitors; EDLC) be a kind of energy storage equipment between battery and conventional capacitive, there is very large electrical capacity usually, mainly because double-layer capacitor is the mode storage power charge separation to be come.The area of storage electric charge is larger or the segregate distance of electric charge is less, and electrical capacity will be larger.Therefore, double-layer capacitor has huge using value and market potential in various fields such as electromobile, propellant combination automobile, exceptional load automobile, electric power, railway, communication, national defence, consumption electronic products.
The double-layer capacitor of present stage utilizes porous charcoal system electrode materials to obtain large storage electric charge area usually.Such as, gac is the material with high-specific surface area and electroconductibility, therefore can be used as porous charcoal system electrode materials.Wherein, the surface-area (specific surface area in unit weight; Unit is m
2/ g) can be relevant with storable electrical capacity, when specific surface area is larger, storable electrical capacity can be larger.
But, utilize the gac obtained by general technology at present, usually cannot simultaneously with the feature of high specific capacitance and high-specific surface area, or needing to pay expensive cost just can make gac reach the feature of high specific capacitance and high-specific surface area.
In view of this, need activated carbon microballon and manufacture method thereof that a kind of high-specific surface area is provided badly, to overcome the variety of problems that processes well known faces.
Summary of the invention
For solving the problems of the technologies described above, an object of the present invention is to provide a kind of manufacture method of activated carbon microballon of high-specific surface area.This manufacture method is before carrying out activation step, first the MCMB containing γ-resin is carried out baking step, to make the content of γ-resin lower than 0.5 weight percent, forms the activated carbon microballon of high-specific surface area thus.
Another object of the present invention is to provide a kind of activated carbon microballon of high-specific surface area.The activated carbon microballon of this high-specific surface area utilizes obtained by above-mentioned manufacture method.The activated carbon microballon of this high-specific surface area has excellent specific surface area and ratio capacitance value.
Another object of the present invention is to provide a kind of electrode slice.This electrode slice comprises the activated carbon microballon of above-mentioned high-specific surface area.
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 invention provides a kind of manufacture method of activated carbon microballon of high-specific surface area, comprising following steps:
There is provided a MCMB, described MCMB comprises γ-resin;
Carry out a baking step, to be greater than the temperature of 410 DEG C to 550 DEG C to described MCMB heating 8 to 12 hours; And
Carry out an activation step to the MCMB through described baking step, to form described activated carbon microballon, wherein, the content of described γ-resin in described MCMB is lower than 0.5 weight percent.
In the manufacture method of the activated carbon microballon of above-mentioned high-specific surface area, preferably, the content of described γ-resin in described MCMB is 0.05 to 0.4 weight percent.
In the manufacture method of the activated carbon microballon of above-mentioned high-specific surface area, preferably, the content of described γ-resin in described MCMB is 0.05 to 0.3 weight percent.
In the manufacture method of the activated carbon microballon of above-mentioned high-specific surface area, preferably, described baking step is to described MCMB heating 8 to 10 hours with the temperature of 420 DEG C to 500 DEG C.
In the manufacture method of the activated carbon microballon of above-mentioned high-specific surface area, preferably, described baking step heats 8 hours with the temperature of 420 DEG C to 450 DEG C to described MCMB.
In the manufacture method of the activated carbon microballon of above-mentioned high-specific surface area, preferably, described activation step comprises:
Carry out a mixing step, mix an activator and the MCMB through described baking step, to form a mixture; And
One heating steps is carried out to described mixture, it is warming up to 520 DEG C with the temperature rise rate of 1 DEG C/minute to 5 DEG C/minute and keeps temperature 1.5 hours under nitrogen atmosphere, from 10-40 DEG C, be warming up to 900 DEG C with this temperature rise rate again and keep temperature 4 hours, to form described activated carbon microballon.
In the manufacture method of the activated carbon microballon of above-mentioned high-specific surface area, preferably, described activator is the oxyhydroxide of basic metal or alkaline-earth metal.
In the manufacture method of the activated carbon microballon of above-mentioned high-specific surface area, preferably, described activator is lithium hydroxide (LiOH), sodium carbonate (Na
2cO
3), zinc chloride (ZnCl
2), Vanadium Pentoxide in FLAKES (P
2o
5), salt of wormwood (K
2cO
3), calcium hydroxide (Ca (OH)
2), potassiumphosphate (K
3pO
4), water vapour (H
2o), carbonic acid gas (CO
2), potassium hydroxide (KOH), sodium hydroxide (NaOH) or ferrous sulfate (FeSO
4).
In the manufacture method of the activated carbon microballon of above-mentioned high-specific surface area, preferably, the weight ratio of described MCMB and described activator is 1:3.
In the manufacture method of the activated carbon microballon of above-mentioned high-specific surface area, preferably, after described activation step, at least comprise further and an activation post-processing step is carried out to described activated carbon microballon.
In the manufacture method of the activated carbon microballon of above-mentioned high-specific surface area, preferably, 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.
In the manufacture method of the activated carbon microballon of above-mentioned high-specific surface area, preferably, the specific surface area through the activated carbon microballon of described activation post-processing step is at least 2800m
2/ g, and ratio capacitance value is at least 180F/g.
In the manufacture method of the activated carbon microballon of above-mentioned high-specific surface area, preferably, the specific surface area through the activated carbon microballon of described activation post-processing step is at least 2837m
2/ g, and ratio capacitance value is at least 185F/g.
The present invention also provides a kind of activated carbon microballon of high-specific surface area, and it is obtained by the manufacture method of the activated carbon microballon of above-mentioned high-specific surface area.
The present invention also provides a kind of electrode slice, and it comprises the activated carbon microballon of above-mentioned high-specific surface area.
The present invention also provides a kind of electric capacity, and it comprises above-mentioned electrode slice.
The manufacture method of the activated carbon microballon of high-specific surface area of the present invention comprises carries out baking step to MCMB, to reduce the content of γ-resin in MCMB, the activated carbon microballon formed after making activated step thus has high-specific surface area and high specific capacitance, be applicable to electrode slice and electric capacity, and overcome the expensive process problem that processes well known faces.
Accompanying drawing explanation
Fig. 1 is the part manufacture method schema of the activated carbon microballon of the high-specific surface area of one embodiment of the invention.
Primary clustering nomenclature:
100 methods
110 steps that MCMB is provided
120 baking steps
130 activation steps
Embodiment
Described in brought forward, the invention provides a kind of manufacture method of activated carbon microballon of high-specific surface area, it is before MCMB carries out activation step, to be greater than the temperature of 410 DEG C to 550 DEG C to MCMB heating 8 to 12 hours, the content of the γ-resin contained to make MCMB is lower than 0.5 weight percent, significantly improves specific surface area and the ratio capacitance value of the activated carbon microballon formed thus.
Refer to Fig. 1, it is the part manufacture method schema of the activated carbon microballon of the high-specific surface area of one embodiment of the invention.Profess it, in an embodiment of the inventive method 100, first, as MCMB is provided step 110 shown in, provide MCMB (GMP:Green Mesophase Powder), this MCMB comprises γ-resin.In one embodiment, above-mentioned applicable carbon microspheres can be such as commercially available mesophase pitch carbon microspheres, wherein this mesophase pitch carbon microspheres is with without any charing process, the mesophase spherule laminate structure with at least 60% (v/v) and quinoline non-soluble composition (quinoline insoluble, hereinafter referred to as QI) is greater than 95% (w/w) is preferred.Secondly, in one embodiment, γ-resin is defined as volatilization temperature at the resin of 200 DEG C to 400 DEG C.
After the step 110 that MCMB is provided, carry out baking step 120, its be greater than 410 DEG C to 550 DEG C temperature to MCMB heating 8 to 12 hours.It is worth mentioning that, usual MCMB γ-resin can react with activator, and the usage quantity of activator is increased.Therefore when carrying out baking step 120, if temperature is less than or equal to 410 DEG C, the γ-resin that cannot effectively volatilize in MCMB, and the usage quantity of activator is increased; If temperature is greater than 600 DEG C, MCMB will be caused easily to carbonize, the crystallinity of MCMB own is improved and the activation effect of unfavorable follow-up activation step 130.In one embodiment, baking step 120 can 420 DEG C to 500 DEG C temperature to MCMB heating 8 to 10 hours.In one embodiment, baking step 120 can be and heats 8 hours with the temperature of 420 DEG C to 450 DEG C to MCMB.
Afterwards, carry out activation step 130 to the MCMB of drying step 120, to form activated carbon microballon, wherein the content of γ-resin in MCMB is lower than 0.5 weight percent.If the content of γ-resin in MCMB is higher than 0.5 weight percent, then γ-resin will consume more activator, and causes the use cost of activator to rise.In one embodiment, the content of γ-resin in MCMB can be 0.05 to 0.4 weight percent.In one embodiment, the content of γ-resin in MCMB can be 0.05 to 0.3 weight percent.
In one embodiment, activation step 130 can comprise and carries out mixing step and heating steps.Mixing step is the MCMB of hybrid activator and drying step 120.Then heating steps is carried out to described mixture, it is warming up to 520 DEG C with the temperature rise rate of 1 DEG C/minute to 5 DEG C/minute and keeps temperature 1.5 hours under nitrogen atmosphere, from 10-40 DEG C, be warming up to 900 DEG C with this temperature rise rate again and keep temperature 4 hours, to form activated carbon microballon.In one embodiment, activator can be the oxyhydroxide of basic metal or alkaline-earth metal.In one embodiment, activator can including but not limited to lithium hydroxide (LiOH), sodium carbonate (Na
2cO
3), zinc chloride (ZnCl
2), Vanadium Pentoxide in FLAKES (P
2o
5), salt of wormwood (K
2cO
3), calcium hydroxide (Ca (OH)
2), potassiumphosphate (K
3pO
4), water vapour (H
2o), carbonic acid gas (CO
2), potassium hydroxide (KOH), sodium hydroxide (NaOH) or ferrous sulfate (FeSO
4).In another embodiment, the weight ratio of MCMB and activator can be 1:3.
According to one embodiment of the invention, after above-mentioned activation step 130, more optionally comprise and activation post-processing step is carried out to the activated carbon microballon of gained.In one embodiment, the activation post-processing step be applicable to including but not limited to after the step utilizing steam treatment activated carbon microballon, then can carry out acid pickling step and hot water cleaning step.Described steam treatment, pickling and hot water cleaning can utilize known manner to carry out.
In one embodiment, the specific surface area of the activated carbon microballon of activated post-processing step at least can be 2800m
2/ g, and ratio capacitance value at least can be 180F/g.In one embodiment, the specific surface area of the activated carbon microballon of activated post-processing step at least can be 2837m
2/ g, and ratio capacitance value at least can be 185F/g.
It is worth mentioning that, usual MCMB γ-resin can react with activator, and the usage quantity of activator is increased.And MCMB is first carried out baking step 120 by the present invention, to make the γ-resin volatilization that originally there is MCMB, just carry out activation step 130 afterwards to form activated carbon microballon.Therefore, the γ-resin in activated carbon microballon can reduce, and therefore also reduces the usage quantity of activator, therefore can reduce manufacturing cost, and follow-up formed activated carbon microballon can be made to have high-specific surface area and high specific capacitance value.
Secondly, due to material easily charing more than 600 DEG C of MCMB, and make the crystallinity of MCMB own improve and not easily be activated, so be that the temperature being greater than 410 DEG C to 550 DEG C heats MCMB in baking step 120, produce to avoid situation about carbonizing.Be noted that so-called not easily being referred to by activation, because carrying out activation step to MCMB is to make MCMB produce vesicular structure, having high-specific surface area to make MCMB herein.And if MCMB produces carbonization reaction, then when carrying out activation step, activator can be difficult to react to form vesicular structure with the MCMB carbonized, therefore MCMB cannot be made to form the vesicular structure with high-specific surface area further.
Below utilize several embodiment so that technical scheme of the present invention to be described, so itself and be not used to limit of the present invention can practical range, skilled person belonging to the present invention without departing from the spirit and scope of the present invention, when doing various change and retouching.
Embodiment 1
First, by MCMB G (green mesophase powder, GMP; GP-24; Fix carbon>90%; Fugitive constituent 8 ± 2%; QI Wei≤95%, median size (D
50) be 25 μm; China Steel Chemical Co., Ltd., TaiWan, China) to be placed at the temperature of 420 DEG C heating 12 hours, to remove wherein contained γ-resin, to form MCMB DG.
Then, by MCMB DG and potassium hydroxide (KOH; Purity 95%; TaiWan, China Paper Co., Ltd, TaiWan, China) be that the ratio of 1:3 forms mixture with weight ratio, and again heating steps is carried out to mixture, it is under nitrogen atmosphere, utilize the mode of two benches linear heat, be warming up to 520 DEG C with the temperature rise rate of 1 DEG C/minute to 5 DEG C/minute from 10-40 DEG C and keep temperature 1.5 hours, then be warming up to 900 DEG C with this temperature rise rate and keep temperature 4 hours, to obtain activated carbon microballon.
Then, carry out activation post-processing step, it is after water vapour and activated carbon microballon being reacted, and carries out filtering, pickling, the step such as hot water cleaning to be to obtain activated carbon microballon.
Comparative example 1
With the preparation method of embodiment 1, difference is in and is to provide MCMB BG (China Steel Chemical Co., Ltd. in comparative example 1, TaiWan, China), it formed MCMB G adding portion low softening point MCMB, and MCMB BG does not carry out baking step.
Comparative example 2
With the preparation method of embodiment 1, difference is in and is to provide MCMB G in comparative example 2, and does not carry 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, the content of γ-resin and β-resin is assessed
Utilize commercially available thermogravimetric analyzer (Perkin Elmer SII, Pyris Diamond TG/DTA) with the content of γ-resin and β-resin in the temperature rise rate of per minute about 20 DEG C measurement MCMB, wherein β-resin is defined as volatilization temperature at the resin being greater than 400 DEG C to 600 DEG C, and the result of gained is as shown in table 1.
Table 1
2, specific surface area, total hole volume and mean pore size is assessed
Commercially available Porosimetry (Micromeritics, model ASAP2020) is utilized to measure the specific surface area (BET of activated carbon microballon; m
2/ g), mean pore size (nm), total hole volume (cm
3), the result of gained is as shown in table 1.
3, ratio capacitance value is assessed
First, the gac slurry that viscosity is about 3500cps is modulated into the then promotor of the graphitized carbon black of the polyvinylidene difluoride (PVDF) of the N-methyl 2-pyrrolidone N-of the activated carbon microballon of 3.2g, 13.4g, 0.6g, 0.2g and 0.004g, and utilize commercially available viscosmeter (Brookfiled LVDV viscosmeter), take test parameter as 10rpm, No. 64 rotors, shearing rates are 2.1/ second, obtain viscosity test result.
Then, the gac slurry of above-mentioned gained is coated on 30 μm of thick aluminium foils, activated carbon electrodes sheet is formed after temperature 150 DEG C and baking in 10 minutes, and activated carbon electrodes sheet is cut into the circular test piece that two areas are respectively 1.327 square centimeters, be that (ionogen is tetraethylammonium tetrafluoroborate (Et for the electrolytic solution of 1M by two circular test pieces collocation polypropylene (PP) barrier films and concentration
4nBF
4); Solvent is propylene carbonate (PC)), to form the test electric capacity identical with the battery specifications of international standards CR2032.
Then measure with electrochemical apparatus, carry out the Electrochemical Scanning of electric current/volt with the scanning speed of 10mV/s, and after integration, obtain the ratio capacitance value of each test electric capacity, 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 2800m
2the high specific capacitance value of the specific surface area of/g and at least 180F/g, really reach object of the present invention, wherein the activated carbon microballon of embodiment 1 has more at least 2837m
2the high specific capacitance value of the specific surface area of/g and at least 185F/g.But the specific surface area of the carbon microspheres of comparative example 1 and comparative example 2 and ratio capacitance value are all less than the respective value of embodiment 1.
What need supplement is, though the present invention with specific material, technique, reaction conditions, analytical procedure or particular instrument illustratively, activated carbon microballon and the manufacture method thereof of the high-specific surface area for electrode slice and electric capacity of the present invention are described, but the technical field of the invention those skilled in the art are known, the present invention is not limited to this, without departing from the spirit and scope of the present invention, the activated carbon microballon of the high-specific surface area for electrode slice and electric capacity of the present invention and manufacture method thereof also can use other material, technique, reaction conditions, analytical procedure or instrument to carry out.
From the embodiment of the invention described above, the activated carbon microballon of high-specific surface area of the present invention and manufacture method thereof and comprise electrode slice and the electric capacity of this activated carbon microballon, its advantage is to utilize baking step to remove the content of γ-resin, except can effectively reduce except the consumption of activator, also can increase specific surface area and the ratio capacitance value of activated carbon microballon, and then be applied in electrode slice and electric capacity.
Although the present invention discloses as above with several embodiment; so itself and be not used to limit the present invention, the technical field of the invention those skilled in the art, without departing from the spirit and scope of the present invention; when doing various change and retouching, therefore 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 following steps:
There is provided a MCMB, described MCMB comprises γ-resin;
Carry out a baking step, to be greater than the temperature of 410 DEG C to 550 DEG C to described MCMB heating 8 to 12 hours; And
Carry out an activation step to the MCMB through described baking step, to form described activated carbon microballon, wherein, the content of described γ-resin in described MCMB is lower than 0.5 weight percent.
2. the manufacture method of the activated carbon microballon of high-specific surface area according to claim 1, wherein, the content of described γ-resin in described MCMB is 0.05 to 0.4 weight percent.
3. the manufacture method of the activated carbon microballon of high-specific surface area according to claim 1, wherein, the content of described γ-resin in described MCMB is 0.05 to 0.3 weight percent.
4. the manufacture method of the activated carbon microballon of high-specific surface area according to claim 1, wherein, described baking step is to described MCMB heating 8 to 10 hours with the temperature of 420 DEG C to 500 DEG C.
5. the manufacture method of the activated carbon microballon of high-specific surface area according to claim 1, wherein, described baking step heats 8 hours with the temperature of 420 DEG C to 450 DEG C to described MCMB.
6. the manufacture method of the activated carbon microballon of high-specific surface area according to claim 1, wherein, described activation step comprises:
Carry out a mixing step, mix an activator and the MCMB through described baking step, to form a mixture; And
One heating steps is carried out to described mixture, it is warming up to 520 DEG C with the temperature rise rate of 1 DEG C/minute to 5 DEG C/minute and keeps temperature 1.5 hours under nitrogen atmosphere, from 10-40 DEG C, be warming up to 900 DEG C with this temperature rise rate again and keep temperature 4 hours, to form described activated carbon microballon.
7. the manufacture method of the activated carbon microballon of high-specific surface area according to claim 6, wherein, described activator is the oxyhydroxide of basic metal or alkaline-earth metal.
8. the manufacture method of the activated carbon microballon of high-specific surface area according to claim 6, wherein, described activator is lithium hydroxide, sodium carbonate, zinc chloride, Vanadium Pentoxide in FLAKES, salt of wormwood, calcium hydroxide, potassiumphosphate, water vapour, carbonic acid gas, potassium hydroxide, sodium hydroxide or ferrous sulfate.
9. the manufacture method of the activated carbon microballon of high-specific surface area according to claim 6, wherein, the weight ratio of described MCMB and described activator is 1:3.
10. the manufacture method of the activated carbon microballon of high-specific surface area according to claim 1, after described activation step, at least comprises further and carries out an activation post-processing step to described activated carbon microballon.
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, the specific surface area through the activated carbon microballon of described activation post-processing step is at least 2800m
2/ g, and ratio capacitance value is at least 180F/g.
The manufacture method of the activated carbon microballon of 13. high-specific surface areas according to claim 11, wherein, the specific surface area through the activated carbon microballon of described activation post-processing step is at least 2837m
2/ g, and ratio capacitance value is at least 185F/g.
The activated carbon microballon of 14. 1 kinds of high-specific surface areas, its be the activated carbon microballon of the high-specific surface area utilized described in any one of claim 1-13 manufacture method obtained by.
15. 1 kinds of electrode slices, is characterized in that, this electrode slice comprises the activated carbon microballon of high-specific surface area according to claim 14.
16. 1 kinds of electric capacity, is characterized in that, this electric capacity comprises electrode slice according to claim 15.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108529585A (en) * | 2017-12-26 | 2018-09-14 | 天津大学 | A kind of sodium-ion battery preparation method for being modified mesocarbon microspheres as negative material |
| CN115315539A (en) * | 2022-06-24 | 2022-11-08 | 上海杉杉科技有限公司 | Spherical silicon-based lithium storage material and preparation method thereof |
| CN115893409A (en) * | 2022-10-26 | 2023-04-04 | 中国石油大学(华东) | Method for preparing meso-microporous biomass super-activated carbon based on combined activation of carbon dioxide-phosphoric anhydride-copper complex |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| TW396650B (en) * | 1997-08-05 | 2000-07-01 | Sony Corp | Carbonaceous precursor, carbonaceous anode material, and nonaqueous rechargeable battery |
| TWI525038B (en) * | 2011-07-19 | 2016-03-11 | China Steel Chemical Corp | High specific surface area active toner manufacturing method |
-
2013
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108529585A (en) * | 2017-12-26 | 2018-09-14 | 天津大学 | A kind of sodium-ion battery preparation method for being modified mesocarbon microspheres as negative material |
| CN115315539A (en) * | 2022-06-24 | 2022-11-08 | 上海杉杉科技有限公司 | Spherical silicon-based lithium storage material and preparation method thereof |
| CN115315539B (en) * | 2022-06-24 | 2024-05-03 | 上海杉杉科技有限公司 | Spherical silicon-based lithium storage material and preparation method thereof |
| CN115893409A (en) * | 2022-10-26 | 2023-04-04 | 中国石油大学(华东) | Method for preparing meso-microporous biomass super-activated carbon based on combined activation of carbon dioxide-phosphoric anhydride-copper complex |
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| TW201512090A (en) | 2015-04-01 |
| CN104512891B (en) | 2016-11-09 |
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