CN105236404A - Petroleum coke based activated carbon for electrode material of supercapacitor, preparation method therefor and use thereof - Google Patents
Petroleum coke based activated carbon for electrode material of supercapacitor, preparation method therefor and use thereof Download PDFInfo
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- CN105236404A CN105236404A CN201510515399.1A CN201510515399A CN105236404A CN 105236404 A CN105236404 A CN 105236404A CN 201510515399 A CN201510515399 A CN 201510515399A CN 105236404 A CN105236404 A CN 105236404A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/13—Energy storage using capacitors
Abstract
The invention provides petroleum coke based activated carbon, a preparation method therefor and use thereof. The petroleum coke based activated carbon has the following characteristics that the specific surface area calculated by the BET method is 1,700-2,500m<2>/g, the ratio of mesopores with the pore size of 2-50nm accounts for 20-40% of whole pores, the average particle diameter is 5-20 microns, the total content of surface oxygen-containing functional groups tested by the Boehm titration method is lower than 0.1mmol/g, the content of contained total heavy-metal impurities is lower than 100ppm, and the content of anions is lower than 50ppm. The petroleum coke based activated carbon has a high specific surface area, reasonable pore size distribution, low impurity content and high specific capacity and can be applied to supercapacitors.
Description
Technical field
The invention belongs to electrode materials technical field, relate to a kind of gac for ultracapacitor, preparation method and its usage, be specifically related to a kind of with refinery coke be raw material prepare gac method and for the application in ultracapacitor.
Background technology
Ultracapacitor is a kind of green novel energy-storing element between ordinary capacitor and battery, have that power density is large, charge velocities be fast, have extended cycle life, the advantage such as environmentally safe, be widely used in the standby power supply of various electronic product and the accessory power supply of hybrid vehicle.
The development core of supercapacitor technologies is electrode materials.Absorbent charcoal material is cheap with it, specific surface area is high, aperture is controlled, chemical property is superior and eco-friendly feature obtains applying the most widely in ultracapacitor field.The raw material of current production super capacitor active carbon mainly comprises plant (Exocarpium cocois (Cocos nucifera L), apricot shell etc.), high score subclass (resol etc.) and fossil oil class (refinery coke, coke etc.).Refinery coke presoma is with its wide material sources, cheap, and the high and ash content of carbon content is low etc., and advantage becomes the Activated Carbon Production raw material with industrial applications prospect.Adopt the refinery coke with class graphite microcrystalline structure as raw material, the outstanding key utilizing it lower and active function groups can obtain higher operating voltage and energy density in organic electrolyte.But compared with itself having the vegetable raw material of short texture, the fossil oil class presoma degree of graphitization height compact structures such as refinery coke, there is some problems in activation relative difficulty in preparation process and in Properties of Activated Carbon lifting.
At present, preparing active carbon with high specific surface area take mainly potassium hydroxide as activator, is obtained by chemical activation raw material.If Chinese patent CN102838115A is raw material with refinery coke, through charing and H
2o
2be activator with potassium hydroxide after preoxidation, the burnt weight ratio of alkali is 3:1, and when activation temperature is 850 DEG C, obtained BET specific surface area is up to 3097m
2the gac of/g.But owing to easily introducing various oxygen-containing functional group at activated carbon surface in alkali reactivation process, and excessive oxygen-containing functional group easily decomposes in charge and discharge process thus affect the cycle performance of material.Japan specially JP2007-112704, to be crushed to the refinery coke of 75 μm for raw material, take potassium hydroxide as activator, and the burnt weight ratio of alkali is 2:1, and 600 DEG C is 1377m through the obtained BET specific surface area of activation in 2 hours
2the gac of/g.This invention, owing to not carrying out suitable pre-treatment to refinery coke raw material, causes activation effect not good enough, and gained gac specific surface area is lower.Japan specially JP2011-207722 uses the method to refinery coke raw material carries out pre-oxidation treatment improve the interaction of refinery coke raw material and basic metal activator and effectively improve the specific surface area that activation effect improves refinery coke gac, but the excessive oxygen-containing functional group introduced in preoxidation process removing not yet in effect.The special JP2004-015366 of Japan is to be crushed to the refinery coke of 75 μm for raw material, take potassium hydroxide as activator, the burnt weight ratio of alkali is 2:1,600 DEG C is the gac of 1377m2/g through the obtained BET specific surface area of activation in 2 hours, gained gac is through removing surface oxygen functional group lower than under the heating condition of activation temperature, metallic impurity are removed to circulate and gas generation property from improving it again through pickling purifying, but other oxygen-containing functional groups again introduced in purifying acid cleaning process removing not yet in effect, limited to the performance boost of absorbent charcoal material.It take refinery coke as the method that super-activated carbon prepared by raw material that CN101028923A discloses a kind of.Front refinery coke will be forged and be crushed to 10 ~ 200 orders, first under oxygenous atmosphere, certain temperature is warming up to the speed of 5 ~ 25 DEG C/min, carry out pre-oxidation treatment, volatile substances is oxidized and burns mistake, form the preoxidation with certain porosity burnt simultaneously, then preoxidation Jiao is mixed by certain mass ratio with alkali metal hydroxide, rise to certain temperature under an inert atmosphere and activate, after cooling, obtain super-activated carbon product through washing, drying.But, other oxygen-containing functional groups that this prior art is again introduced in purifying acid cleaning process removing not yet in effect, limited to the performance boost of absorbent charcoal material.In addition, this invention uses burn tinctuer as the evaluation of preoxidation effect, truly cannot reflect the degree of oxidation of pre-oxidizing conditions part of the body cavity below the umbilicus, housing the bladder, kidneys and bowels class raw material, cannot provide controlled processing parameter for preparation of industrialization preoxidation presoma.Simultaneously, this invention is for preparing active carbon with high specific surface area and its rational pore size distribution range of control not yet in effect, easily cause the micropore that in higher specific surface area, major part is less than 2nm by aperture to provide, the consumption for the gac as electrode material for super capacitor promotes limited.
Meanwhile, also ubiquity is not enough as follows in preparation process for above-mentioned patented method: the alkali carbon ratio that (1) adopts is higher, and activation yield is lower, and raw material consumption amount is large, and soak time is long, easily causes production cost higher and seriously polluted; (2) use KOH excessive as activator gained activated carbon capillary proportion, capacity is lower and pore size distribution is unreasonable; (3) presoma particle diameter comparatively large (tens of to hundreds of μm) cause granule interior activation in reactivation process insufficient different from activating agent degree cause activating uneven; (4) harshness is required to raw material refinery coke sulphur content, increase the preparation cost etc. of refinery coke gac.In addition, when preparing bigger serface activated carbon for super capacitors by alkali activation method, often need higher alkali carbon ratio and higher activation temperature, a large amount of alkali activators used considerably increase the manufacturing cost of gac; Sulfur in petroleum coke content is higher to be caused consuming partial activation agents thus reduces activation efficiency, and can generate various by product affect gac cycle performance in reactivation process; Meanwhile, when high-carbon raw material and alkali activator mix, often because high-carbon raw material hydrophobicity causes with water miscible alkali activating agent insufficient, cause activating insufficient and lower specific surface area.Therefore, study a kind of easily to the pretreatment process that refinery coke raw material carries out to a certain degree, strengthen the exposure level with alkali activator, thus be conducive to using comparatively gentle activation condition, prepare while controlling cost and there is high specific surface area and heavy body, have concurrently pore size distribution rationally and the preparation method of the refinery coke class gac of low impurity content activated carbon for super capacitors material be current problem demanding prompt solution.
Summary of the invention
For the problem of prior art, an object of the present invention is to provide a kind of refinery coke matrix activated carbon, and it has high specific surface area and heavy body, have concurrently pore size distribution rationally, low impurity content and low oxygen-containing functional group content, shown in specific as follows:
A kind of refinery coke matrix activated carbon, is characterized in that, it is 1700 ~ 2500m that BET method calculates gained specific surface area
2/ g, the ratio of aperture all well shared by the mesopore of 2 ~ 50nm is 20 ~ 40% (such as 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36% or 38%), median size is 5 ~ 20 μm (such as 6 μm, 8 μm, 10 μm, 12 μm, 14 μm, 16 μm or 18 μm), Boehm volumetry test surfaces oxygen-containing functional group total content <0.1mmol/g, contained total heavy metal foreign matter content is lower than 100ppm, and anion-content is lower than 50ppm.
The inorganic system specific storage of described refinery coke matrix activated carbon is greater than 240F/g, and organic system specific storage is greater than 140F/g.
Two of object of the present invention is the preparation method providing a kind of refinery coke matrix activated carbon, described method is prepared under can be implemented in the condition of low cost has high specific surface area and heavy body, has pore size distribution concurrently rationally and the refinery coke class gac of low impurity content activated carbon for super capacitors material.
To achieve these goals, present invention employs following technical scheme:
A preparation method for refinery coke matrix activated carbon, comprises the following steps:
(1) the refinery coke powder being 1 ~ 50 μm by median size (D50) is placed in closed furnace chamber, passes into oxidizing gas, and preoxidation is carried out in heating, obtains preoxidation presoma;
(2) step (1) gained preoxidation presoma and activator mix is even, and activate under protective atmosphere;
(3) by the washing of step (2) gained activation products and pickling, then pH is adjusted to for neutral rear dry;
(4) step (3) products therefrom is heat-treated under protective atmosphere, obtain refinery coke matrix activated carbon.
The present invention obtains preoxidation presoma-preoxidation refinery coke by carrying out pre-oxidation treatment to the refinery coke powder being crushed to certain particle size (median size (D50) is 1 ~ 50 μm).In this preoxidation process, sulfide-oxidation makes sulphur content reduce, and forms pore in irregular shape or crack, thus strengthens with the exposure level of activator and contribute to the formation of reactivation process central hole structure.Meanwhile, pre-oxidation treatment also can remove volatile matter remaining in refinery coke, reduces volatile matter to the consumption of activator, improves activation efficiency.
The present invention is by adjusting the granularity of raw material and carry out pre-treatment to raw material, thus strengthen the exposure level with activator, improve the uniformity of activation, reduce activation condition complexity, and prepare while controlling cost there is high specific surface area and heavy body, have the rational activated carbon for super capacitors material of pore size distribution concurrently.Meanwhile, the present invention uses rational purifying and thermal treatment process, can control in lower level by activated carbon surface oxygen-containing functional group while introduce metallic impurity in deactivation process, promote the cycle performance of gac further.
Preferably, by refinery coke raw material pulverizing to median size (D50) be the refinery coke powder of 1 ~ 50 μm.
Preferably, described pulverize use in ball milling, comminution by gas stream or Mechanical Crushing any one, be preferably comminution by gas stream.
Preferably, the ball-grinding machine of described ball milling is any one in ball mill by wet process, planetary ball mill, horizontal ball mill, drum-type grinding mill, vibration mill or sand mill.
Preferably, the abrading-ball of described ball milling is the mixing of any one or at least two kinds in Stainless Steel Ball, agate ball, Ceramic Balls or zirconia ball.
Preferably, described refinery coke is the carbides etc. such as needle coke, shot coke, sponge coke or pitch coke, and what preferably degree of graphitization was lower forges front refinery coke.
Preferably, the median size (D50) of described refinery coke powder is 5 ~ 10 μm, such as 6 μm, 7 μm, 8 μm or 9 μm.The present invention preferably adopts and refinery coke raw material is adjusted to particle diameter needed for finished product before activation, after activation, gained gac median size is 5 ~ 15 μm, ensure that the homogeneity of preoxidation, it also avoid the yield occurred after finished product refinery coke matrix activated carbon ball milling to decline, also be conducive to fully contacting of refinery coke and activator, ensure that the homogeneity of activation.
Preferably, the described closed furnace chamber of step (1) be box-type furnace, revolution oxidized still or tunnel pusher furnace in any one, preferably turn round oxidized still.
Preferably, described preoxidation time is preferably 1 ~ 4h, such as 1.2h, 1.4h, 1.6h, 1.8h, 2.0h, 2.2h, 2.4h, 2.6h, 2.8h, 3.0h, 3.2h, 3.4h, 3.6h or 3.8h, Pre oxidation is preferably 250 ~ 450 DEG C, such as 270 DEG C, 290 DEG C, 310 DEG C, 330 DEG C, 350 DEG C, 370 DEG C, 390 DEG C, 410 DEG C or 430 DEG C.Pre oxidation is insufficient lower than 250 DEG C of preoxidation, higher than 450 DEG C of then preoxidation decreased effectiveness.Described Pre oxidation is preferably 300 DEG C, and preoxidation time is preferably 1-2h.Adopt this preferably pre-oxidizing conditions, more excellent activation effect can be ensured, the specific storage of the refinery coke matrix activated carbon product that raising obtains and specific surface area etc.
Preferably, step (1) is warming up to Pre oxidation with the temperature rise rate of 5 ~ 100 DEG C/min, and described temperature rise rate is such as 10 DEG C/min, 20 DEG C/min, 30 DEG C/min, 40 DEG C/min, 50 DEG C/min, 60 DEG C/min, 70 DEG C/min, 80 DEG C/min or 90 DEG C/min.
Preferably, step (1) described oxidizing gas is the combination of any one or at least two kinds in air, oxygen, ozone, nitrogen protoxide or chlorine, is preferably air.
Preferably, the flow of step (1) oxidizing gas is 200L/h.
Preferably, after step (1) preoxidation terminates, under oxidizing gas atmosphere, be quickly cooled to room temperature, obtain preoxidation presoma.
Preferably, step (1) described preoxidation presoma specific surface area is>=50m
2/ g, organic volatile matter≤20%, preferred specific surface area is 50 ~ 200m
2/ g, organic volatile matter 10 ~ 17%.The volatile matter comparatively refinery coke powder raw material reduction of preoxidation presoma, specific surface area increases, known, in this preoxidation process, define pore in irregular shape or crack, thus strengthen with the exposure level of activator and contribute to the formation of reactivation process central hole structure.Meanwhile, pre-oxidation treatment eliminates volatile matter remaining in refinery coke, reduces volatile matter to the consumption of activator, improves activation efficiency.The present invention, by being optimized the specific surface area of preoxidation presoma and volatile matter, further improves the activation effect of refinery coke matrix activated carbon.
Preferably, the mass ratio of the described preoxidation presoma of step (2) and activator (in solid) is 1:3 ~ 1:5, such as 1:3,1:3.5,1:4,1:4.5 or 1:4.5.
Preferably; step (2) described activator is alkali metal hydroxide; the mixing of any one or at least two kinds in preferred potassium hydroxide, sodium hydroxide, cesium hydroxide or calcium hydroxide, is preferably sodium hydroxide, more preferably sodium hydrate solid powder, particle or tablet.
Preferably, above-mentioned steps (2) described soak time is 1 ~ 5h, such as 1.5h, 2h, 2.5h, 3h, 3.5h, 4h or 4.5h, is preferably 1 ~ 2h; Activation temperature is 550 ~ 850 DEG C, such as 570 DEG C, 590 DEG C, 600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C or 800 DEG C, be preferably 700 ~ 850 DEG C, activation temperature then activates insufficient lower than 550 DEG C, higher than 850 DEG C then activation effect weaken.
Preferably, step (2) is warming up to activation temperature with the temperature rise rate of 5 ~ 100 DEG C/min, and described temperature rise rate is such as 10 DEG C/min, 20 DEG C/min, 30 DEG C/min, 40 DEG C/min, 50 DEG C/min, 60 DEG C/min, 70 DEG C/min, 80 DEG C/min or 90 DEG C/min.
Preferably, step (2) described protective atmosphere is the combination of any one or at least two kinds in nitrogen, argon gas, helium or neon, is preferably nitrogen.
Preferably, the described pickling of step (3) uses in one in hydrochloric acid, sulfuric acid or nitre aqueous acid or the combination of at least two kinds.
Preferably, the concentration of step (3) described spent pickling acid is 1wt% ~ 60wt%, such as 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt% or 60wt%, be preferably 1wt% ~ 20wt%.
Removal of impurities is carried out in the acid that the present invention adopts concentration lower, and by sample clean to close to neutral, removal of impurities can be made more complete, reduce negatively charged ion remaining in gac simultaneously, contribute to the inflatable problem of inhibit activities charcoal super capacitor, the cycle life of ultracapacitor can be extended.
Preferably, step (3) described drying temperature is 100 ~ 150 DEG C, and time of drying is 2 ~ 24h.
Preferably, step (4) the heat treated time is 1 ~ 5h, such as 1.5h, 2h, 2.5h, 3h, 3.5h, 4h or 4.5h, be preferably 1 ~ 2h, thermal treatment temp is 450 ~ 850 DEG C, such as 500 DEG C, 550 DEG C, 600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C or 800 DEG C, be preferably 750 ~ 850 DEG C.
Preferably, a kind of preparation method of refinery coke matrix activated carbon, comprises the following steps:
A refinery coke raw material pulverizing to median size is the refinery coke powder of 1 ~ 50 μm by ();
B step (a) gained refinery coke powder is placed in closed furnace chamber by (), pass into oxidizing gas atmosphere, be warming up to Pre oxidation with 5 ~ 100 DEG C/min, carry out preoxidation, then in oxidizing atmosphere, be quickly cooled to room temperature, obtain preoxidation presoma;
C step (b) gained preoxidation presoma mixes by 1:3 ~ 1:5 mass ratio with activator by ();
D mixture that step (c) obtains by () under protective atmosphere under with 5 ~ 100 DEG C/min be warming up to 550 ~ 850 DEG C activation 1 ~ 5h, then under protective atmosphere, be quickly cooled to room temperature, obtain activation products;
E activation products that step (d) obtains by () carry out washing and pickling, then to be adjusted to pH be after neutrality, dry 2 ~ 24h between 100 ~ 150 DEG C;
F product that step (e) obtains by () is heat-treated, and heat treatment time is 1 ~ 5h, and be preferably 1 ~ 2h, thermal treatment temp is 450 ~ 850 DEG C, is preferably 750 ~ 850 DEG C, through cooling, obtains refinery coke matrix activated carbon.
Three of object of the present invention is to provide a kind of refinery coke matrix activated carbon as above as the application of double electric layers supercapacitor and lithium ion super capacitor electrode materials.
Be applied to electrode material for super capacitor about refinery coke matrix activated carbon of the present invention below and make following explanation;
This electrode plates forms active substance by the mixing of refinery coke matrix activated carbon, binding agent and conductive additive and current collector forms;
The binding agent that the present invention uses comprises the polyvinyl alcohol be widely used at present, sodium cellulose glycolate, tetrafluoroethylene, polyvinylidene difluoride (PVDF), polyolefins, SBR rubber-like, polyurethanes etc.The conductive additive that the present invention uses comprises the carbon black be widely used at present, acetylene black, graphite-like additive, carbon nanotube additive etc.The collector that the present invention uses comprises the Copper Foil be widely used at present, aluminium foil, nickel screen, stainless steel foil etc.
The hybrid mode of refinery coke matrix activated carbon, binding agent and conductive additive uses method conventional at present; Prepare refinery coke matrix activated carbon, binding agent and conductive additive mixed slurry as by sizing mixing and method slurry is applied on collector and by will mix refinery coke matrix activated carbon, binding agent and conductive additive mixed active material heating compression moulding method.
Compared with the prior art, the present invention has following beneficial effect:
The present invention obtains preoxidation presoma-preoxidation refinery coke by carrying out pre-oxidation treatment to the refinery coke powder being crushed to certain particle size (median size (D50) is 1 ~ 50 μm).In this preoxidation process, sulfide-oxidation makes sulphur content reduce, and forms pore in irregular shape or crack, thus strengthens with the exposure level of activator and contribute to the formation of reactivation process central hole structure.Meanwhile, pre-oxidation treatment also can remove volatile matter remaining in refinery coke, reduces volatile matter to the consumption of activator, improves activation efficiency.
The present invention is by adjusting the granularity of raw material and raw material being carried out to the pre-treatment of special process, thus strengthen the exposure level with activator, improve the uniformity of activation, reduce activation condition complexity, and prepare while controlling cost there is high specific surface area and heavy body, have the rational activated carbon for super capacitors material of pore size distribution concurrently.Simultaneously, the present invention uses rational purifying and thermal treatment process, while introduce metallic impurity in deactivation process, activated carbon surface oxygen-containing functional group can be controlled in lower level, and material can be made to circulate rear capability retention more than 90% at next ten thousand weeks impulse electricity of organic electrolyte.
In addition, in the preferred technical solution of the present invention, present invention achieves the preparation achieving high-specific surface area refinery coke matrix activated carbon under low activation temperature, short soak time, low alkali carbon ratio condition.
Refinery coke matrix activated carbon of the present invention, it is 1700 ~ 2500m that BET method calculates gained specific surface area
2/ g, aperture is the ratio of the shared all well of mesopore (Mesopore) of 2 ~ 50nm is 20 ~ 40%, median size is 5 ~ 20 μm, Boehm volumetry test surfaces oxygen-containing functional group total content <0.1mmol/g, contained total heavy metal foreign matter content is lower than 100ppm, anion-content is lower than 50ppm, and inorganic system specific storage is greater than 240F/g, and organic system specific storage is greater than 140F/g.
Accompanying drawing explanation
Fig. 1 is the structural representation adopting refinery coke matrix activated carbon of the present invention to be applied to ultracapacitor, wherein, and 1-collector, 2-pole piece, 3-barrier film.
The XRD figure of the refinery coke matrix activated carbon material that Fig. 2 obtains for the embodiment of the present invention 1.
Fig. 3 is the refinery coke matrix activated carbon scanning electron microscope (SEM) photograph that the embodiment of the present invention 1 obtains.
Fig. 4 is the graph of pore diameter distribution of the refinery coke matrix activated carbon that the embodiment of the present invention 1 obtains with comparative example 1.
Embodiment
It is as follows that the present invention enumerates embodiment, is described in further detail the present invention, but embodiments of the present invention are not limited thereto.For a person skilled in the art, the present invention can have various modifications and variations, within the spirit and principles in the present invention all, and any amendment done, equivalent replacement or improvement etc., all should be included within protection scope of the present invention.
The present invention adopts following methods to carry out properties test to the refinery coke matrix activated carbon that embodiment 1 ~ 6 and comparative example 1 ~ 3 obtain:
(1) the S:4800 sem observation absorbent charcoal material pattern of Hitachi, Ltd is adopted;
(2) adopt the full-automatic specific surface area of ASAP2020V3.04H of Micromeritics Instrument Corp. U.S.A and lacunarity analysis instrument test absorbent charcoal material specific surface area and and pore size distribution; The calculating of BET specific surface area is with reference to following formula, by being can obtain a straight line within the scope of 0.05-0.35 at P/P0, Vm (individual layer saturated extent of adsorption) can be tried to achieve by slope and intercept, specific surface area=VmN0S/22400W (N0 is A Fojia get Luo constant, and S is a binding molecule sectional area)
Wherein P: adsorbate dividing potential drop; P0: sorbent material saturated vapor pressure; V: the actual adsorptive capacity of sample; Vm: individual layer saturated extent of adsorption; The constant that C is relevant to sample adsorption ability;
(3) the OPTIMA2100DV Inductively coupled plasma optical emission spectrometer (ICP) of U.S. PerkinElmer is adopted to test absorbent charcoal material metals content impurity;
(4) X'pertPROX x ray diffractometer x (XRD) the testing stone oil coke matrix activated carbon material crystalline degree of Dutch PANalytical is adopted;
(5) Boehm volumetry is adopted to utilize the difference of quantity of alkali consumption in titration process, the content of quantitative analysis refinery coke matrix activated carbon material surface oxygen-containing functional group; By with known (1) NaOH, (2) Na of concentration
2cO
3(3) NaHCO
3filter, respectively from nNaOH, nNa with the titration of HCl standardized solution after standardized solution and refinery coke matrix activated carbon example reaction 24h
2cO
3and nNaHCO
3between beat-frequency meter calculate the content of carboxyl, weak acid and phenolic hydroxyl group.
(6) performance of the CT2001C1 blue electrical testing system testing electrical condenser of company of Lan electricity electronics limited-liability company is adopted;
Pole piece refinery coke matrix activated carbon and conductive additive and binding agent made is assembled (shown in Fig. 1) according to the order of pole piece/barrier film/pole piece, and wherein aqueous super capacitor is with reference to following typical assembling standard:
Gac: carbon black conductive agent (SP): the mass ratio of polyfluortetraethylene of binding element (PTFE)=87:10:3 carries out being mixed with into electrode slice, carries out charge and discharge cycles test in 6MKOH electrolytic solution;
Organic system ultracapacitor is with reference to following typical assembling standard:
Gac: carbon black conductive agent (SP): the mass ratio of binding agent polyvinylidene difluoride (PVDF) (PVDF)=85:10:5 carries out being mixed with into electrode slice, at 1MEt
4nBF
4charge-discharge test is carried out in/PC (propylene carbonate of the tetraethyl-ammonium tetrafluoroborate containing 1mol/L) electrolytic solution;
The specific storage of ultracapacitor presses following formulae discovery according to constant current charge-discharge test result;
C＝It/(U1－U2)
In formula: C---electrostatic capacity, F; I---constant discharge current, A; U1, U2---sampled voltage, V; Discharge time needed for t---U1 to U2, S.
Embodiment 1
Revolution oxidized still (Xianyang blue light thermal technology science and technology) is put into the charing petroleum coke powder 50g of size-grade distribution D50 about 8 ~ 10 μm by through comminution by gas stream, pass into the pressurized air 30 ~ 60min of 200L/h, then be warmed up to 350 DEG C with the heat-up rate of 20 DEG C/min, after insulation 1h, be quickly cooled to room temperature to obtain preoxidation presoma in oxidizing atmosphere protection; Be NaOH by refinery coke preoxidation presoma according to mass ratio: the ratio of preoxidation presoma=3:1 mixes puts into crucible; in box-type furnace (Hefei day new high temperature) with the nitrogen protection of 50L/h flow under be warmed up to 800 DEG C with the heat-up rate of 20 DEG C/min; insulation activation was quickly cooled to room temperature to obtain activated material presoma at inert atmosphere protection after 1 hour, activated material is turned to slurry and uses 5wt% dilute hydrochloric acid to regulate pH to slightly acidic.After rare HCl of filtrate 5wt% is heated to 90 DEG C, hot water to clean to pH neutrality between 100 ~ 150 DEG C dry 24 hours repeatedly, and through 850 DEG C of high temperature sinterings 4 hours i.e. obtained refinery coke matrix activated carbon sample, specific surface area is 2390m
2/ g.
By embodiment 1 gained refinery coke matrix activated carbon according to refinery coke matrix activated carbon: carbon black conductive agent (SP): the mass ratio of binding agent polyvinylidene difluoride (PVDF) (PVDF)=85:10:5 carries out being mixed with into electrode slice, at the Et of 1M
4nBF
4carry out charge-discharge test in/PC (the tetraethyl-ammonium tetrafluoroborate containing 1mol/L propylene carbonate) electrolytic solution, under the current density of 50mA/g as calculated ratio capacitance be 165F/g; According to refinery coke matrix activated carbon: carbon black conductive agent (SP): the mass ratio of polyfluortetraethylene of binding element (PTFE)=87:10:3 carries out being mixed with into electrode slice, in the KOH electrolytic solution of 6M, carry out charge and discharge cycles test, under the current density of 50mA/g, obtain ratio capacitance is as calculated 310F/g.At the Et of 1M
4nBF
4in/PC organic electrolyte, after 10,000 impulse electricity circulations, capability retention is 94%.The XRD figure of the embodiment illustrated in fig. 21 refinery coke matrix activated carbon material obtained, as seen from the figure, this sample is the not completely dissolve of class graphite microcrystal after preoxidation and activation treatment, also can be observed class graphite microcrystal peak near 26 degree.
The embodiment illustrated in fig. 31 refinery coke matrix activated carbon scanning electron microscope (SEM) photograph obtained, as seen from the figure, corrosion irregular class graphite flake layer columnar structure out can be observed in the activated rear surface of refinery coke class raw material.
The ratio that the embodiment illustrated in fig. 41 refinery coke matrix activated carbon pore size distribution result obtained calculates all well shared by the mesopore (Mesopore) that gained aperture is 2 ~ 50nm through HK (Horvath-Kawazoe) method is 36%.
Embodiment 2
Except change Pre oxidation is 250 DEG C, the refinery coke raw material identical with embodiment 1 is carried out preoxidation under other pre-oxidizing conditions and embodiment 1 same case, obtains preoxidation presoma.Be NaOH by preoxidation presoma according to mass ratio: the ratio of preoxidation presoma=3:1 mixes puts into crucible; to be warmed up to 800 DEG C with the heat-up rate of 20 DEG C/min under the nitrogen protection of 50L/h flow in box-type furnace; insulation activation was quickly cooled to room temperature to obtain activated material presoma at inert atmosphere protection after 1 hour; through the purifying identical with embodiment 1 and heat treatment operation, obtain refinery coke activated carbon sample.Its specific surface area is 2187m
2/ g, the ratio of aperture all well shared by the mesopore of 2 ~ 50nm is 28%, and organic system specific storage is 158F/g, and inorganic system specific storage is 270F/g.At the Et of 1M
4nBF
4in/PC organic electrolyte, after 10,000 impulse electricity circulations, capability retention is 93%.
Embodiment 3
Except control NaOH in reactivation process: except preoxidation presoma=2:1 (mass ratio), all the other adopt the condition identical with embodiment 1, obtain refinery coke matrix activated carbon.Its specific surface area is 1823m
2/ g, the ratio of aperture all well shared by the mesopore of 2 ~ 50nm is 16%, and organic system specific storage is 152F/g, and inorganic system specific storage is 271F/g.At the Et of 1M
4nBF
4in/PC organic electrolyte, after 10,000 impulse electricity circulations, capability retention is 87%.
Embodiment 4
Except control NaOH in reactivation process: except preoxidation presoma=4:1 (mass ratio), all the other adopt the condition identical with embodiment 1, obtain refinery coke matrix activated carbon.Its specific surface area is 2531m
2/ g, the ratio of aperture all well shared by the mesopore of 2 ~ 50nm is 31%, and organic system specific storage is 167F/g, and inorganic system specific storage is 308F/g.At the Et of 1M
4nBF
4in/PC organic electrolyte, after 10,000 impulse electricity circulations, capability retention is 94%.
Embodiment 5
Remove in box-type furnace to be warmed up to 750 DEG C with the heat-up rate of 20 DEG C/min under the nitrogen protection of 50L/h flow; insulation activation was quickly cooled to room temperature to obtain outside activated material presoma at inert atmosphere protection after 1 hour, and all the other adopt the condition identical with embodiment 1 to obtain refinery coke matrix activated carbon sample.Its specific surface area is 1976m
2/ g, the ratio of aperture all well shared by the mesopore of 2 ~ 50nm is 28%, and organic system specific storage is 147F/g, and inorganic system specific storage is 265F/g.At the Et of 1M
4nBF
4in/PC organic electrolyte, after 10,000 impulse electricity circulations, capability retention is 90%.
Embodiment 6
Remove in box-type furnace to be warmed up to 650 DEG C with the heat-up rate of 20 DEG C/min under the nitrogen protection of 50L/h flow; insulation activation was quickly cooled to room temperature to obtain outside activated material presoma at inert atmosphere protection after 1 hour, and all the other adopt the condition identical with embodiment 1 to obtain refinery coke matrix activated carbon sample.Its specific surface area is 1701m
2/ g, the ratio of aperture all well shared by the mesopore of 2 ~ 50nm is 26%, and organic system specific storage is 140F/g, and inorganic system specific storage is 239F/g.At the Et of 1M
4nBF
4in/PC organic electrolyte, after 10,000 impulse electricity circulations, capability retention is 85%.
Embodiment 7
Except directly add industrial dense HCl in acid cleaning process except, all the other adopt the condition identical with embodiment 1, obtain refinery coke matrix activated carbon.Its specific surface area is 2360m
2/ g, the ratio of aperture all well shared by the mesopore of 2 ~ 50nm is 30%, and organic system specific storage is 159F/g, and inorganic system specific storage is 308F/g.At the Et of 1M
4nBF
4in/PC organic electrolyte, after 10,000 impulse electricity circulations, capability retention is 86%.
Gac specific surface area and the ratio capacitance data of above-described embodiment 1 ~ 6 preparation are as shown in table 1.
Table 1
As can be seen from Table 1, the refinery coke matrix activated carbon BET specific surface area that embodiment 1 obtains and specific storage all higher than to embodiment 2, illustrate that the higher Pre oxidation that embodiment 1 adopts can ensure activation effect.
The each side data of the refinery coke matrix activated carbon that embodiment 1 and embodiment 3,5 and 6 obtain all have obvious reduction, illustrate that reduction activation temperature to 750 DEG C and 650 DEG C have certain abated effect for activation effect.
Embodiment 4 and embodiment 1 compare the refinery coke matrix activated carbon of gained each side data with 3 all have obvious reduction, illustrate that higher activation alkali coke ratio has positive promoter action for activation effect, specific storage and specific surface area progressively become large along with the raising of activation alkali coke ratio.
Comparative example 1
Put into revolution oxidized still by through mechanical disintegration to the petroleum coke powder 50g of size-grade distribution D50 about 500 μm, obtain preoxidation presoma by the pre-oxidation treatment identical with embodiment 1; Be NaOH by refinery coke preoxidation presoma according to mass ratio: the ratio of preoxidation presoma=3:1 mixes puts into crucible; to be warmed up to 800 DEG C with the heat-up rate of 20 DEG C/min under the nitrogen protection of 50L/h flow in box-type furnace; insulation activation was quickly cooled to room temperature to obtain activated material presoma at inert atmosphere protection after 1 hour; through the purifying identical with embodiment 1, drying and heat treatment operation, obtain refinery coke matrix activated carbon sample.Its specific surface area is 2054m
2/ g, the ratio of aperture all well shared by the mesopore of 2 ~ 50nm is 18%, and organic system specific storage is 157F/g, and inorganic system specific storage is 255F/g.At the Et of 1M
4nBF
4in/PC organic electrolyte, after 10,000 impulse electricity circulations, capability retention is 88%.
Comparative example 2
To be NaOH to the petroleum coke powder 50g of size-grade distribution D50 about 500 μm according to mass ratio through comminution by gas stream: the ratio of refinery coke=3:1 mixes puts into crucible; to be warmed up to 800 DEG C with the heat-up rate of 20 DEG C/min under the nitrogen protection of 50L/h flow in box-type furnace; insulation activation was quickly cooled to room temperature to obtain activated material presoma at inert atmosphere protection after 1 hour; through the purifying identical with embodiment 1, drying and heat treatment operation, obtain refinery coke matrix activated carbon sample.Its specific surface area is 1501m
2/ g, the ratio of aperture all well shared by the mesopore of 2 ~ 50nm is 11%, and organic system specific storage is 116F/g, and inorganic system specific storage is 229F/g.At the Et of 1M
4nBF
4in/PC organic electrolyte, after 10,000 impulse electricity circulations, capability retention is 69%.
Comparative example 3
Be NaOH by through comminution by gas stream being the petroleum coke powder 50g of 8.5 μm to size-grade distribution D50 according to mass ratio: the ratio of refinery coke=3:1 mixes puts into crucible; to be warmed up to 800 DEG C with the heat-up rate of 20 DEG C/min under the nitrogen protection of 50L/h flow in box-type furnace; insulation activation was quickly cooled to room temperature to obtain activated material presoma at inert atmosphere protection after 1 hour; through the purifying identical with embodiment 1, drying and heat treatment operation, obtain refinery coke matrix activated carbon sample.Its specific surface area is 1795m
2/ g, the ratio of aperture all well shared by the mesopore of 2 ~ 50nm is 14%, and organic system specific storage is 133F/g, and inorganic system specific storage is 252F/g.At the Et of 1M
4nBF
4in/PC organic electrolyte, after 10,000 impulse electricity circulations, capability retention is 82%.
Comparative example 4
Be heated to 350 DEG C of heating and within 1 hour, do pre-oxidation treatment by putting into air through mechanical disintegration to the petroleum coke powder 50g that size-grade distribution D50 is 8.5 μm and obtain preoxidation presoma; Be NaOH by refinery coke preoxidation presoma according to mass ratio: the ratio of preoxidation presoma=3:1 mixes puts into crucible; to be warmed up to 800 DEG C with the heat-up rate of 20 DEG C/min under the nitrogen protection of 50L/h flow in box-type furnace; insulation activation was quickly cooled to room temperature to obtain activated material presoma at inert atmosphere protection after 1 hour; through the purifying identical with embodiment 1, dry and heat treatment operation, obtains refinery coke matrix activated carbon sample.Its specific surface area is 1642m
2/ g, the ratio of aperture all well shared by the mesopore of 2 ~ 50nm is 12%, and organic system specific storage is 120/g, and inorganic system specific storage is 232F/g.At the Et of 1M
4nBF
4in/PC organic electrolyte, after 10,000 impulse electricity circulations, capability retention is 86%.
Comparative example 5
Put into revolution oxidized still by through mechanical disintegration to the petroleum coke powder 50g that size-grade distribution D50 is 8.5 μm, obtain preoxidation presoma by the pre-oxidation treatment identical with embodiment 1, be NaOH by refinery coke preoxidation presoma according to mass ratio: the ratio of preoxidation presoma=3:1 mixes puts into crucible, to be warmed up to 800 DEG C with the heat-up rate of 20 DEG C/min under the nitrogen protection of 50L/h flow in box-type furnace, insulation activation was quickly cooled to room temperature to obtain activated material presoma at inert atmosphere protection after 1 hour, through the purifying identical with embodiment 1, drying operation and heat treatment operation, obtain activated carbon sample, again by gained activated carbon sample through 5% rare HCl be heated to 90 DEG C after hot water repeatedly to clean to pH neutrality between 100 ~ 150 DEG C dry 24 hours, obtain refinery coke matrix activated carbon sample.Its specific surface area is 2243m
2/ g, the ratio of aperture all well shared by the mesopore of 2 ~ 50nm is 23%, and organic system specific storage is 142F/g, and inorganic system specific storage is 276F/g, and in organic electrolyte, after 10,000 impulse electricity circulations, capability retention is 74%.
Specific surface area and the ratio capacitance data of gac prepared by above-mentioned comparative example 1-5 are as shown in table 2.
Table 2
As can be seen from Table 2, the gac BET specific surface area that embodiment 1 obtains and specific storage all higher than to comparative example 1, illustrate that the control particle diameter that embodiment 1 adopts can increase activation effect.
Embodiment 1 and comparative example 2 compare obtained gac each side data with comparative example 3 all have larger advantage, the suitable pre-oxidation treatment of sufficient proof is for strengthening with the exposure level of alkali activator and improving the uniformity activated, prepare while controlling cost and there is high specific surface area and heavy body, have the positive effect of pore size distribution rational activated carbon for super capacitors material aspect concurrently.
Simultaneously, comparative example 4 is compared with embodiment 1, specific surface area and specific storage lower, demonstrate and use closed rotary kiln to have positive effect for the lifting of activation effect, under same activation condition, embodiment 1 gained gac has higher specific surface area and specific storage.In addition, also can be obtained by embodiment 1, comparative example 1 and 4 contrast, only have to adopt simultaneously and control raw material particle size and carry out preoxidation in closed rotary kiln, just can obtain specific surface area ratio and the high refinery coke matrix activated carbon of specific storage.
For verifying that in encloses container, preoxidation is for the impact of refinery coke class raw material further, for embodiment 1, embodiment 2, and the preoxidation presoma of comparative example 4 operation gained has carried out specific surface area and volatile matter test, result is as shown in table 3.
Table 3
As known from Table 3, the volatile matter of the preoxidation presoma that embodiment 1 obtains comparatively refinery coke raw material lowers to some extent, granularity and specific surface area all have to be increased largely, define pore in irregular shape or crack in known pre-oxidation treatment process, thus strengthen with the exposure level of alkali activator and contribute to the formation of reactivation process central hole structure.Meanwhile, pre-oxidation treatment also except volatile matter remaining in the class that defocuses, can reduce volatile matter to the consumption of activator, improves activation efficiency.Embodiment 2 is compared with embodiment 1, and the increase degree of the specific surface area and granularity that reduce Pre oxidation preoxidation presoma weakens to some extent, but still has larger improvement compared with raw material.Shown in comparative example 4, directly preoxidation gained preoxidation presoma changes not quite compared with raw material in atmosphere, and volatile matter reduces to some extent, and the main pre-oxidizing conditions that is subject to limits caused by preoxidation effect heterogeneity.
The above-mentioned surface oxygen functional group calculation result to gac prepared by enforcement 1, comparative example 1 and comparative example 5 is as shown in table 4.
Table 4
Due to the existence of activated carbon surface oxygen-containing functional group particularly carboxyl, in ultracapacitor very easily there is oxygen evolution reaction in electrode, and this will cause ultracapacitor generation inflatable; Meanwhile, the precipitation of oxygen can cause electrode loose, and this declines causing the cyclicity of ultracapacitor.As known from Table 4, embodiment 1 is compared with comparative example 1, and raw material particle size has a certain impact for surface functional group content, and the controllability of its surface functional group of raw material that particle diameter is larger will be worse than small-particle.Embodiment 1, compared with comparative example 4, demonstrates preoxidation in encloses container and has a certain impact for final activated carbon surface functional group content, effectively can reduce activated carbon surface functional group content after thermal treatment by controlled pre-oxidizing conditions.The surface oxygen functional group content of the gac that the surface oxygen functional group content of the gac that embodiment 1 obtains obtains with comparative example 5 differs larger, embodiment 1 gained gac carboxyl-content through high-temperature heat treatment decreases, lactone group and content of phenolic hydroxyl groups also remain at low levels, and illustrate and use heat treated to have direct relation for control activated carbon sample surface functional group content.
The graph of pore diameter distribution of the gac that the embodiment 1 shown in Fig. 4 obtains with comparative example 1 is known to be strengthened with the exposure level of alkali activator through pre-oxidation treatment thus contributes to the formation of reactivation process central hole structure, use comparatively gentle activation condition simultaneously, thus prepare there is high specific surface area and heavy body, have the rational activated carbon for super capacitors material of pore size distribution concurrently.From the ratio of aperture all well shared by the mesopore of 2 ~ 50nm that the pore size distribution result of the various embodiments described above calculates, suitable preoxidation and the selection of activation condition can improve the ratio of all well shared by mesopore and can improve its specific storage.
The above-mentioned metallic impurity to gac prepared by enforcement 1 and comparative example 1 and anion-content test result as shown in table 5.
Table 5
As known from Table 5, remain at low levels compared with the gac that the metallic impurity of the gac that embodiment 1 obtains and anion-content and comparative example 1 obtain, the reduction mainly having benefited from particle diameter contributes to the washing away of impurity of pickling for activated carbon surface and pore interior absorption.Although embodiment 1 proves that compared with embodiment 7 pickle solution that concentration is higher can remove unnecessary metallic impurity, also can cause anionic impurity too high levels, the pickle solution that working concentration is lower also contributes to the existence reducing negatively charged ion in activated carbon sample.Equally, embodiment 1, compared with the foreign matter content result of comparative example 5, also contributing to the control of foreign matter content after the heat treated of carry out to a certain degree to the activated carbon sample after purifying.
Comparative example 6
Comparative example 6 is embodiment 1 disclosed in CN101028923A.The petroleum coke powder crossing 160 mesh sieves after comminution by gas stream is warmed up to 450 DEG C, is cooled to room temperature after being incubated 1.5h in air atmosphere and obtains preoxidation presoma; Be KOH by refinery coke preoxidation presoma according to mass ratio: the ratio of preoxidation presoma=1:1 mixes puts into crucible, is warmed up to 850 DEG C under nitrogen, insulation activation after 1 hour through cold through washing dry obtained refinery coke matrix activated carbon sample.Obtained activated carbon sample specific surface area is 2620m
2/ g, the ratio of aperture all well shared by the mesopore of 2 ~ 50nm is 14%, and organic system specific storage is 145F/g, and inorganic system specific storage is 326F/g, and in organic electrolyte, after 10,000 impulse electricity circulations, capability retention is 78%.
Comparative example 7
Comparative example 7 is embodiment 2 disclosed in CN101028923A.The petroleum coke powder crossing 100 mesh sieves after comminution by gas stream is warmed up to 400 DEG C, is cooled to room temperature after being incubated 2h in air atmosphere and obtains preoxidation presoma; Be KOH by refinery coke preoxidation presoma according to mass ratio: the ratio of preoxidation presoma=1.5:1 mixes puts into crucible, is warmed up to 830 DEG C under nitrogen, insulation activation after 1.5 hours through cold through washing dry obtained refinery coke matrix activated carbon sample.Obtained activated carbon sample specific surface area is 2754m
2/ g, the ratio of aperture all well shared by the mesopore of 2 ~ 50nm is 16%, and organic system specific storage is 152F/g, and inorganic system specific storage is 338F/g, and in organic electrolyte, after 10,000 impulse electricity circulations, capability retention is 71%.
Comparative example 8
Comparative example 8 is embodiment 3 disclosed in CN101028923A.The petroleum coke powder crossing 160 mesh sieves after comminution by gas stream is warmed up to 400 DEG C, is cooled to room temperature after being incubated 2h in air atmosphere and obtains preoxidation presoma; Be KOH by refinery coke preoxidation presoma according to mass ratio: the ratio of preoxidation presoma=0.5:1 mixes puts into crucible, is warmed up to 800 DEG C under nitrogen, insulation activation after 2 hours through cold through washing dry obtained refinery coke matrix activated carbon sample.Obtained activated carbon sample specific surface area is 2286m
2/ g, the ratio of aperture all well shared by the mesopore of 2 ~ 50nm is 11%, and organic system specific storage is 138F/g, and inorganic system specific storage is 292F/g, and in organic electrolyte, after 10,000 impulse electricity circulations, capability retention is 62%.
The surface oxygen functional group content measuring result that the above-mentioned technique described according to embodiment disclosed in CN101028923A 1 ~ 3 carries out gac prepared by comparative example 6 ~ 8 is respectively as shown in table 6.
Table 6
As known from Table 6, the gac specific surface area obtained according to embodiment disclosed in CN101028923A is higher, but infer because activation condition does not control pore size distribution mainly based on micropore, and not through corresponding heat treated, surface oxygen functional group is in higher level, cause the organic specific storage of active carbon with high specific surface area that obtains lower, within 10,000 weeks, Capacity fading is also very fast.
The above-mentioned technique described according to embodiment disclosed in CN101028923A 1 ~ 3 carry out the metallic impurity of gac prepared by comparative example 6 ~ 7 respectively and anion-content test result as shown in table 7.
Table 7
As known from Table 7, the gac obtained according to embodiment disclosed in CN101028923A after simple washing drying principal metal impurities and anion-content general higher, special metallic impurity are substantially identical with content in raw material refinery coke.Very easily there is various redox reaction and separate out and block activated carbon capillary in too high metallic impurity, directly cause gac Capacity fading very fast in ultracapacitor working cycle.Comparative example 6,7,8 further demonstrate that the various techniques that the present invention adopts have positive effect for the cyclical stability improving activated carbon electrodes with the internal resistance of reduction electrode, therefore the gac that the present invention obtains is the material of a excellent performance in ultracapacitor field, has broad application prospects.
Applicant states, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not namely mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a refinery coke matrix activated carbon, is characterized in that, it is 1700 ~ 2500m that BET method calculates gained specific surface area
2/ g, the ratio of aperture all well shared by the mesopore of 2 ~ 50nm is 20 ~ 40%, and median size is 5 ~ 20 μm, Boehm volumetry test surfaces oxygen-containing functional group total content <0.1mmol/g, contained total heavy metal foreign matter content is lower than 100ppm, and anion-content is lower than 50ppm.
2. a preparation method for refinery coke matrix activated carbon as claimed in claim 1, is characterized in that, comprise the following steps:
(1) be that the refinery coke powder of 1 ~ 50 μm is placed in closed furnace chamber by median size, pass into oxidizing gas, preoxidation is carried out in heating, obtains preoxidation presoma;
(2) step (1) gained preoxidation presoma and activator mix is even, and activate under protective atmosphere;
(3) by the washing of step (2) gained activation products and pickling, then pH is adjusted to for neutral rear dry;
(4) step (3) products therefrom is heat-treated under protective atmosphere, obtain refinery coke matrix activated carbon.
3. method as claimed in claim 2, it is characterized in that, be the refinery coke powder of 1 ~ 50 μm by refinery coke raw material pulverizing to median size;
Preferably, described pulverize use in ball milling, comminution by gas stream or Mechanical Crushing any one, be preferably comminution by gas stream;
Preferably, the ball-grinding machine of described ball milling is any one in ball mill by wet process, planetary ball mill, horizontal ball mill, drum-type grinding mill, vibration mill or sand mill;
Preferably, the abrading-ball of described ball milling is the mixing of any one or at least two kinds in Stainless Steel Ball, agate ball, Ceramic Balls or zirconia ball;
Preferably, described refinery coke is the carbides etc. such as needle coke, shot coke, sponge coke or pitch coke, and what preferably degree of graphitization was lower forges front refinery coke;
Preferably, the median size (D50) of described refinery coke powder is 5 ~ 10 μm.
4. as claimed in claim 2 or claim 3 method, is characterized in that, the described closed furnace chamber of step (1) is any one in box-type furnace, revolution oxidized still or tunnel pusher furnace, preferably turns round oxidized still;
Preferably, described preoxidation time is preferably 1 ~ 4h, and Pre oxidation is preferably 250 ~ 450 DEG C, and preferred Pre oxidation is 300 DEG C, and preoxidation time is 1 ~ 2h;
Preferably, step (1) is warming up to Pre oxidation with the temperature rise rate of 5 ~ 100 DEG C/min;
Preferably, step (1) described oxidizing gas is the combination of any one or at least two kinds in air, oxygen, ozone, nitrogen protoxide or chlorine, is preferably air;
Preferably, the flow of step (1) oxidizing gas is 200L/h;
Preferably, step (1) described preoxidation presoma specific surface area is>=50m
2/ g, organic volatile matter≤20%, preferred specific surface area is 50 ~ 200m
2/ g, organic volatile matter 10 ~ 17%.
5. the method as described in one of claim 2-4, is characterized in that, the mass ratio of the described preoxidation presoma of step (2) and activator is 1:3 ~ 1:5;
Preferably; step (2) described activator is alkali metal hydroxide; the mixing of any one or at least two kinds in preferred potassium hydroxide, sodium hydroxide, cesium hydroxide or calcium hydroxide, is preferably sodium hydroxide, more preferably sodium hydrate solid powder, particle or tablet.
6. the method as described in one of claim 2-5, is characterized in that, step (2) described soak time is 1 ~ 5h, is preferably 1 ~ 2h; Activation temperature is 550 ~ 850 DEG C, is preferably 700 ~ 850 DEG C;
Preferably, step (2) is warming up to activation temperature with the temperature rise rate of 5 ~ 100 DEG C/min;
Preferably, step (2) described protective atmosphere is the combination of any one or at least two kinds in nitrogen, argon gas, helium or neon, is preferably nitrogen.
7. the method as described in one of claim 2-6, is characterized in that, the described pickling of step (3) uses in one in hydrochloric acid, sulfuric acid or nitre aqueous acid or the combination of at least two kinds;
Preferably, the concentration of step (3) described spent pickling acid is 1wt% ~ 60wt%, is preferably 1wt% ~ 20wt%;
Preferably, step (3) described drying temperature is 100 ~ 150 DEG C, and time of drying is 2 ~ 24h.
8. the method as described in one of claim 2-7, is characterized in that, step (4) the heat treated time is 1 ~ 5h, is preferably 1 ~ 2h;
Preferably, step (4) thermal treatment temp is 450 ~ 850 DEG C, is preferably 750 ~ 850 DEG C.
9. the method as described in one of claim 2-8, is characterized in that, comprises the following steps:
A refinery coke raw material pulverizing to median size is the refinery coke powder of 1 ~ 50 μm by ();
B step (a) gained refinery coke powder is placed in closed furnace chamber by (), pass into oxidizing gas atmosphere, be warming up to Pre oxidation with 5 ~ 100 DEG C/min, carry out preoxidation, then in oxidizing atmosphere, be quickly cooled to room temperature, obtain preoxidation presoma;
C step (b) gained preoxidation presoma mixes with the mass ratio of activator by 1:3 ~ 1:5 by ();
D mixture that step (c) obtains by () under protective atmosphere under with 5 ~ 100 DEG C/min be warming up to 550 ~ 850 DEG C activation 1 ~ 5h, then under protective atmosphere, be quickly cooled to room temperature, obtain activation products;
E activation products that step (d) obtains by () carry out washing and pickling, then to be adjusted to pH be after neutrality, dry 2 ~ 24h between 100 ~ 150 DEG C;
F product that step (e) obtains by () is heat-treated, and heat treatment time is 1 ~ 5h, and be preferably 1 ~ 2h, thermal treatment temp is 450 ~ 850 DEG C, is preferably 750 ~ 850 DEG C, through cooling, obtains refinery coke matrix activated carbon.
10. a refinery coke matrix activated carbon as claimed in claim 1 is as the application of double electric layers supercapacitor and lithium ion super capacitor electrode materials.
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