CN106698427A - Activated carbon, preparation method thereof, and application of activated carbon in supercapacitor electrode - Google Patents
Activated carbon, preparation method thereof, and application of activated carbon in supercapacitor electrode Download PDFInfo
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- CN106698427A CN106698427A CN201710138654.4A CN201710138654A CN106698427A CN 106698427 A CN106698427 A CN 106698427A CN 201710138654 A CN201710138654 A CN 201710138654A CN 106698427 A CN106698427 A CN 106698427A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to activated carbon, a preparation method thereof, and application of the activated carbon in a supercapacitor electrode. The method comprises the following steps of firstly drying, smashing and sieving an activated carbon raw material; then uniformly mixing the treated activated carbon raw material and an activating agent according to a certain mass ratio, under the protection of an inert atmosphere, heating in a sealed furnace body for carrying out activating agentmelt-impregnation, and then continuously warming for activating; purifying, ball-milling and sieving an obtained activated product, and finally carrying out high-heat treatment under the protection of an inert atmosphere to obtain the activated carbon. The specific surface area of the activated carbon provided by the invention is larger than 2000m<2>/g, and the specific surface area and the pore size distribution are controllable. The mass ratio capacitance of a supercapacitor prepared by adopting the activated carbon provided by the invention and a TEABF4/PC organic system is larger than 130F/g. In addition, the activated carbon provided by the invention is simple in production process, low in preparation cost, short in period, good in comprehensive economic benefit, and easy to realize industrial production.
Description
Technical field
The invention belongs to electrode material for super capacitor field, it is related to a kind of activated carbon, its preparation method and in super electricity
The purposes of container electrode.
Background technology
The development core of supercapacitor technologies is electrode material, and exploitation high-performance, the electrode material of low cost are super
The important content of capacitor research work.Wherein, absorbent charcoal material is due to the service life with stabilization and large-scale industry
Metaplasia is produced basis and is widely adopted, and ultracapacitor high-energy/the urgent of high power density is essential with meeting electric automobile etc.
Ask.Activated carbon is that a kind of hole is flourishing, specific surface area is big, the functional form carbon material of relative inexpensiveness, is the super electricity of commercialization
The main electrode material of container.
The preparation of activated carbon generally by the pre- charing process of high temperature, thus need to increased the step in industrial production, improve
Cost, this is also a commonplace problem in current process for preparing active carbon.Meanwhile, charing is easy to cause activated carbon
Precursor construction is caved in, so as to destroy the structure of raw material itself, and then causes priming reaction uneven, and active carbon pore structure is chaotic
It is unordered.At present, analysis for preparation of activated carbon by chemical activation is typically with potassium hydroxide as activator, is preparing active carbon with high specific surface area
When, activator level and activation temperature higher higher is generally required, this will cause activation yield reduction, and energy consumption increases,
Improve production cost and seriously polluted；Additionally, obtained activated carbon pore size is mainly distributed in range of micropores, pore-size distribution is difficult
To regulate and control, the application in ultracapacitor is limited significantly.
The raw material for producing activated carbon mainly includes plant, petroleum coke class and macromolecule resin class.Generally, plant shell,
Petroleum coke and macromolecule resin matter are hard, poor processability；And compact structure, it is relatively difficult to activation.It is that raw material prepares work with them
Property charcoal when, need to first be pre-processed, to adjust internal structure, reduce activation difficulty；Simultaneously burn volatile substances to lose, form one
Fixed porosity, to increase the contact area with activator, improves the utilization rate of activation efficiency and activator.Such as Chinese patent
CN104891491B discloses a kind of preparation method of ultracapacitor with bamboo shoots based active carbon, Chinese patent CN
102838115B discloses a kind of preparation method of ultracapacitor High-specific Area Activated Carbon, Chinese patent CN
1291587A disclose it is a kind of with phenolic resin as raw material make electrode of super capacitor method for preparation of active carbon, but they
The characteristics of common carried out or coking firstly the need of to activated carbon raw material, or carbonization, or the pre-treatment step such as pre-oxidation.
Therefore, a kind of process is simple, low cost, specific surface area and the controllable activated carbon of pore-size distribution are developed, is super electricity
The technical barrier of container electrode Material Field.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide a kind of low cost, high-performance, specific surface area and hole
Footpath is distributed controllable activated carbon, its preparation method and the purposes in electrode of super capacitor.The present invention is by activated carbon raw material
The adjustment of granularity, melt impregnating process and activating process, promotes activator to the dipping melting of raw material and activation effect, increases
Strong contact, improves the uniformity and adequacy of priming reaction, while reducing reunion and the alveolation phenomenon of activator, this hair
The specific surface area of bright activated carbon is more than 2000m2/ g, the electrode of super capacitor being made of activated carbon of the invention is had very
Capacity high, quality specific capacitance is more than 130F/g.
It is that, up to above-mentioned purpose, the present invention is adopted the following technical scheme that：
In a first aspect, the present invention provides a kind of preparation method of activated carbon, the described method comprises the following steps：
(1) activated carbon raw material is mixed with activator, is heated, carried out at activator melt impregnation under inert gas shielding
Reason；
(2) continue to heat up, activation process is carried out to the melt impregnation product that step (1) is obtained；
(3) activation products that step (2) is obtained are heat-treated under inert gas shielding, are obtained activated carbon.
Preferably, step (1) described activated carbon raw material be plant shell, forge preceding petroleum coke or macromolecule resin in it is any
It is a kind of or at least two mixture.
Plant shell of the present invention is, for example, coconut husk, apricot shell, walnut shell and lychee exocarp etc..But it is not limited to above-mentioned enumerating
Plant shell, other plant shells that can reach same effect can also be used for the present invention.
Preferably, step (1) described activated carbon raw material is by the activated carbon raw material of pretreatment and/or without pretreatment
Activated carbon raw material, preferably without pretreatment activated carbon raw material.
" pretreatment " in " by the activated carbon raw material and/or the activated carbon raw material without pretreatment of pretreatment "
Be pretreatment mode commonly used in the art, such as carbonization treatment, coking treatment and pre-oxidation treatment etc..
The self structure and skeleton of activated carbon raw material of the invention are more orderly, and surface functional group content is high, with the present invention
Described activator can reach reaction well and activate through melt impregnation operation and activation procedure, reduce priming reaction and enter
Capable complexity, is conducive to the regulation and control of pore structure.
The raw material that the method for the present invention is directed to both can be to carry out pretreated work by the preprocess method of this area
Property carbon feedstock, or without this area preprocess method pre-process activated carbon raw material.Under both of these case, use
The method of the present invention first mixes with activator, heats, and melt impregnation treatment is carried out under inert gas shielding, continues to heat up and realizes
Activation, then be heat-treated can excellent performance activated carbon, the specific surface area of activated carbon is more than 2000m2/ g, and, using this hair
The electrode of super capacitor that bright activated carbon is made has capacity very high, and quality specific capacitance is more than 130F/g.
When the raw material for using is the activated carbon raw material without the preprocess method pretreatment of this area, not only ensure that
(activated carbon specific surface area is more than 2000m to excellent performance2/ g, the quality of the electrode of super capacitor being made of the activated carbon
Specific capacitance is more than 130F/g), and operation is reduced, without carrying out conventional pretreatment process, technique is more easy, reduces
Manpower and energy consumption, reduce cost.
Macromolecule resin of the present invention is, for example, phenolic resin, Corvic, makrolon and polyurethane etc..But
The above-mentioned macromolecule resin enumerated is not limited to, other macromolecule resins commonly used in the art can also be used for the present invention.
Preferably, step (1) described activator be alkali metal hydroxide, zinc chloride or phosphoric acid in any one or extremely
Few two kinds combination, preferably alkali metal hydroxide, more preferably NaOH.
Alkali metal hydroxide of the present invention is, for example, lithium hydroxide, NaOH, potassium hydroxide, rubidium hydroxide and hydrogen
Cesium oxide etc..
Preferably, the states of matter of step (1) described activator is solid powder, and the pattern of the activator is included but is not limited to
In particle, sheet or pearl any one or at least two combination.
Preferably, the particle diameter of step (1) described activator be 0.1mm~3mm, for example, 0.1mm, 0.3mm, 0.5mm,
1mm, 1.2mm, 1.5mm, 1.8mm, 2mm, 2.5mm, 2.75mm or 3mm etc., preferably 0.5mm~2mm.
Preferably, step (1) described activator is the NaOH Beads of 0.5mm~2mm.
Preferably, the mass ratio of step (1) activated carbon raw material and the activator is 1:(1~5), such as 1:1、1:
1.5、1:2、1:2.5、1:3、1:3.5、1:3.8、1:4、1:4.5 or 1:5 etc., preferably 1:(2~4).
Preferably, the method for the solid phase mixing is：Activated carbon raw material is mixed directly with activator, such as by activity
Carbon feedstock is put into a device with activator, simply rocks realization mixing.
Preferably, the method that the water is mixed is：After activated carbon raw material is well mixed with the activator aqueous solution, 120 DEG C
Moisture is evaporated.
Preferably, the method for the ball milling mixing is：Activated carbon raw material mix with activator after ball milling.
Preferably, step (1) described inert gas is any one in nitrogen, helium, neon, argon gas, Krypton or xenon
Kind or at least two combination, preferably nitrogen.
Preferably, the temperature of step (1) activator melt impregnation treatment is 200 DEG C~400 DEG C, for example, 200 DEG C,
220℃、230℃、240℃、255℃、265℃、280℃、300℃、315℃、330℃、340℃、350℃、365℃、380℃
Or 400 DEG C etc., preferably 320 DEG C.
Preferably, the heating rate for being warming up to the temperature of the activator melt impregnation treatment is 1 DEG C/min~10
DEG C/min, for example, 1 DEG C/min, 2 DEG C/min, 3 DEG C/min, 4 DEG C/min, 5 DEG C/min, 6.5 DEG C/min, 8 DEG C/min or 10 DEG C/
Min etc., preferably 2 DEG C/min~5 DEG C/min；
Preferably, the time of step (1) activator melt impregnation treatment is 1h~6h, for example, 1h, 1.5h, 2h,
2.5h, 3h, 3.5h, 4h, 4.5h, 5h or 6h etc., preferably 2h~4h.
Preferably, step (1) the activator melt impregnation treatment is carried out in closed stove body；
Preferably, the closed body of heater is in batch-type furnace, vacuum drying oven, rotary furnace, roller furnace, pusher furnace or tube furnace
Any one, preferably batch-type furnace；
Preferably, the temperature of step (2) described activation process be 500 DEG C~1000 DEG C, for example, 500 DEG C, 550 DEG C, 600
℃、625℃、650℃、675℃、700℃、720℃、740℃、755℃、770℃、780℃、800℃、825℃、850℃、
880 DEG C, 900 DEG C, 925 DEG C, 950 DEG C or 1000 DEG C etc., preferably 600 DEG C~800 DEG C.
Preferably, the heating rate for being warming up to the temperature of the activation process is 1 DEG C/min~10 DEG C/min, for example
For 1 DEG C/min, 2.5 DEG C/min, 3.5 DEG C/min, 4 DEG C/min, 5 DEG C/min, 6 DEG C/min, 8 DEG C/min, 9 DEG C/min or 10 DEG C/
Min etc., preferably 2 DEG C/min~5 DEG C/min.
Preferably, the time of step (2) described activation process be 0.5h~5h, such as 0.5h, 1h, 1.5h, 2h, 3h,
3.5h, 4h or 5h etc., preferably 1h~3h.
Preferably, step (3) described inert gas is any one in nitrogen, helium, neon, argon gas, Krypton or xenon
Kind or at least two combination, preferably nitrogen.
Preferably, the temperature of step (3) described heat treatment be 400 DEG C~1100 DEG C, for example, 400 DEG C, 450 DEG C, 500
℃、550℃、600℃、650℃、700℃、750℃、775℃、800℃、850℃、900℃、950℃、1000℃、1050℃
Or 1100 DEG C etc., preferably 600 DEG C~1000 DEG C.
Preferably, the heating rate for being warming up to the temperature of the heat treatment is 1 DEG C/min~10 DEG C/min, for example,
1 DEG C/min, 2 DEG C/min, 3 DEG C/min, 5 DEG C/min, 7 DEG C/min, 8 DEG C/min or 10 DEG C/min etc., preferably 2 DEG C/min~5
℃/min。
Preferably, the time of step (3) described heat treatment be 0.5h~6h, for example, 0.5h, 1h, 1.5h, 2h, 2.5h,
3h, 3.5h, 4h, 4.2h, 4.5h, 4.8h, 5h, 5.5h or 6h etc., preferably 1h~3h.
Used as the optimal technical scheme of the method for the invention, methods described carries out step before being additionally included in step (1)
(1)’：The step of being dried to activated carbon raw material, crushed and sieved.
When the present invention carries out step (1) ', the activated carbon in step (1) then replaces with the activity after step (1) ' treatment
Carbon Materials.
Preferably, the mesh number of screen cloth for using of sieving is 10 mesh~100 mesh, such as 10 mesh, 20 mesh, 30 mesh, 40 mesh,
60 mesh, 80 mesh or 100 mesh, preferably 30 mesh.By controlling the particle diameter of activated carbon raw material, activator can be strengthened former with activated carbon
The contact of material, improves the uniformity and adequacy of melt impregnation and priming reaction, can also reduce reunion and the bubble of activator
Change, so as to reduce the consumption of alkali.
As the optimal technical scheme of the method for the invention, methods described be additionally included in after step (2) step (3) it
Before carry out step (3) '：The activation products that step (2) is obtained are washed, are purified, ball milling/crushing and sieving the step of.
Wherein, described " ball milling/crushing " refers to ball milling or crushing.
Preferably, the step of purifying is：Carry out being purified to pH=6~7 using hot hydrochloric acid solution and hot water.
Preferably, the concentration of the hot hydrochloric acid solution be 1wt%~5wt%, for example, 1wt%, 2wt%, 2.5wt%,
3wt%, 3.5wt%, 4wt% or 5wt% etc..
Preferably, the temperature of the purifying is 80 DEG C~90 DEG C, for example, 80 DEG C, 82 DEG C, 85 DEG C, 87 DEG C, 88 DEG C or 90
DEG C etc..
Preferably, the particle diameter D of the product by being obtained after step (3) '50It is 4 μm~15 μm, for example, 4 μm, 5 μm, 6 μ
M, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm or 12 μm etc., preferably 4 μm~10 μm.
When the present invention carries out step (3) ', the activation products in step (3) then replace with the work after step (3) ' treatment
Change product.
Used as the further preferred technical scheme of the preparation method of activated carbon of the present invention, methods described includes following step
Suddenly：
(1)’：Activated carbon raw material without pretreatment is dried, is crushed with and cross 10 mesh~100 mesh sieves, obtained
Activated carbon raw material after sieving；
(1) activated carbon raw material after the sieving for obtaining step (1) ' and activator in mass ratio 1:(1~5) mix, plus
Heat, in 200 DEG C~400 DEG C activator melt impregnation treatment 1h~6h under inert gas shielding；
(2) continue to heat up, activation process is carried out in 500 DEG C~1000 DEG C to the melt impregnation product that step (1) is obtained；
(3)’：The activation products that step (2) is obtained are washed, are purified, ball milling and sieving the step of, after being processed
Activation products；
(3) activation products after the treatment for obtaining step (3) ' under inert gas shielding in 400 DEG C~1100 DEG C heat
Treatment 0.5h~6h, obtains activated carbon.
In this optimal technical scheme, by the activated carbon raw material granularity without pretreatment, activator level, melting leaching
The adjustment of stain technique and activating process, promotes activator to the dipping melting of the activated carbon raw material without pretreatment and lives
Change effect, enhance contact, the uniformity and adequacy of priming reaction are improve, while reducing reunion and the alveolation of activator
Phenomenon, the activated carbon for preparing has specific surface area and pore-size distribution controllable, and the super capacitor prepared using it
The characteristics of device capacity is high, the specific surface area of activated carbon is more than 2000m2/ g, the super capacitor being made of activated carbon of the invention
Device electrode has capacity very high, and quality specific capacitance is more than 130F/g..
Second aspect, the present invention provides the activated carbon that method is prepared as described in relation to the first aspect.
The specific surface area of activated carbon of the invention is more than 2000m2/g。
The third aspect, the present invention provides purposes of the activated carbon in electrode of super capacitor as described in second aspect.
Compared with the prior art, the present invention has the advantages that：
(1) present invention (can be not pretreated, or carbon to activated carbon raw material from the activator of low cost
Change, coking or pre-oxidation treatment are crossed) mixed by simple solid phase method, alkali watery fusion impregnation process, activation process and
Heat treatment, has prepared specific surface area and pore-size distribution has been controllable, excellent performance activated carbon.The ratio table of activated carbon of the invention
Area is more than 2000m2/ g, the electrode of super capacitor being made of activated carbon of the invention has capacity very high, mass ratio
Electric capacity is more than 130F/g.
(2) present invention using plant shell, forge the self structures such as preceding petroleum coke and macromolecule resin and skeleton more in order,
, used as activated carbon raw material, activated carbon raw material, self structure and skeleton are more orderly, surface official for surface functional group content material high
Energy mass contg is high, with activator directly through melt impregnation and priming reaction, it is possible to decrease the complexity that priming reaction is carried out, is easy to
The regulation and control of pore structure.
(3) melt impregnation and one step of activation are completed in the present invention, are adjusted activated carbon raw material particle diameter by progressive one and are melted
Melt dipping and activation parameter, promote dipping of the activator to activated carbon raw material, enhance contact, improve melt impregnation with
And the uniformity and adequacy of priming reaction, while reunion and the alveolation of activator can be reduced, base amount can be not only reduced,
The quality of the activated carbon product for preparing can also be improved.
(4) method for preparing activated carbon of the invention has with low cost, process is simple, the requirement to equipment and experiment condition
Relatively low, pollution small, short preparation period and the good advantage of overall economic efficiency, it is easy to accomplish industrialized production.
Brief description of the drawings
Fig. 1 is the SEM figures of the coconut based activated Carbon Materials obtained by the embodiment of the present invention 1；
Fig. 2 is the tangent plane SEM figures of the coconut based activated Carbon Materials obtained by the embodiment of the present invention 1；
Fig. 3 is the XRD of the petroleum coke matrix activated carbon material obtained by the embodiment of the present invention 2；
Fig. 4 is the discharge and recharge of the ultracapacitor that the petroleum coke matrix activated carbon material obtained by the embodiment of the present invention 2 is made
Curve map.
Specific embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by specific embodiment.
Embodiment 1
By through the coconut husk powder material 100g of Mechanical Crushing to 30 mesh and activator NaOH in mass ratio 1:2 solid phases are mixed
Close uniform, load in corundum crucible, under nitrogen atmosphere protection, in middle temperature type resistance furnace, heated up with the speed of 2 DEG C/min
Activator melt impregnation, isothermal holding 2h are carried out to 320 DEG C；Continuation is warming up to 700 DEG C and is activated with the speed of 2 DEG C/min,
Insulation 1h；After after batch-type furnace cooling, activation material precursor is taken out, purified, ball milling, sieving are finally protected in nitrogen atmosphere
Under, in middle temperature type resistance furnace, being warming up to 870 DEG C with the speed of 2 DEG C/min carries out high temperature sintering, is heat-treated 1h, final to obtain
To coconut based activated Carbon Materials.
Fig. 1 is the SEM figures of the coconut based activated Carbon Materials of the gained of the present embodiment 1, and as seen from the figure, activated carbon shows
The granule-morphology of equally distributed micron-scale.
Fig. 2 is the tangent plane SEM figures of the coconut based activated Carbon Materials obtained by the present embodiment 1, as seen from the figure, activated carbon
Internal structure is closely knit, and the macroporous structure on surface comes from NaOH activation corrosion effect at high temperature.
The specific surface area of the coconut shell based activated carbon of the present embodiment is 2240m2/g。
Using the coconut shell based activated carbon and TEABF of the present embodiment4The mass ratio of ultracapacitor prepared by/PC organic systems
Electric capacity is 138.5F/g.
Embodiment 2
By through the petroleum coke raw material 100g of Mechanical Crushing to 30 mesh and activator NaOH in mass ratio 1:3 solid phase mixings
Uniformly, load in corundum crucible, under nitrogen atmosphere protection, in middle temperature type resistance furnace, be warming up to the speed of 2 DEG C/min
320 DEG C carry out activator melt impregnation, isothermal holding 2h；Continuation is warming up to 800 DEG C and is activated with the speed of 2 DEG C/min, protects
Warm 1h；After after batch-type furnace cooling, activation material precursor is taken out, purified, ball milling, sieving, finally under nitrogen atmosphere protection,
In in middle temperature type resistance furnace, being warming up to 400 DEG C with the speed of 2 DEG C/min carries out high temperature sintering, is heat-treated 1h, finally gives stone
Oil coke matrix activated carbon material.
Fig. 3 is the XRD of the petroleum coke matrix activated carbon material obtained by the present embodiment 2, and as seen from the figure, activated carbon exists
25 ° and 43 ° nearby have two diffraction maximums wide, corresponding to (002) and (100) diffraction pattern of amorphous carbon.
Fig. 4 is that the petroleum coke matrix activated carbon material obtained by the present embodiment 2 is made electrode of super capacitor and is assembled into
The charging and discharging curve figure of ultracapacitor, as seen from the figure, charging and discharging curve is triangular in shape and near symmetrical, shows reason
Think the feature of capacitance behavior.
The specific surface area of the petroleum coke matrix activated carbon of the present embodiment is 2573m2/g。
Using the petroleum coke matrix activated carbon and TEABF of the present embodiment4The quality of ultracapacitor prepared by/PC organic systems
Specific capacitance is 133.1F/g.
Embodiment 3
By through the phenolic resin starting material 100g of Mechanical Crushing to 30 mesh and activator NaOH in mass ratio 1:2 solid phases are mixed
Close uniform, load in corundum crucible, under nitrogen atmosphere protection, in middle temperature type resistance furnace, heated up with the speed of 2 DEG C/min
Activator melt impregnation, isothermal holding 2h are carried out to 320 DEG C；Continuation is warming up to 750 DEG C and is activated with the speed of 2 DEG C/min,
Insulation 1h；After after batch-type furnace cooling, activation material precursor is taken out, purified, ball milling, sieving are finally protected in nitrogen atmosphere
Under, in middle temperature type resistance furnace, being warming up to 600 DEG C with the speed of 2 DEG C/min carries out high temperature sintering, is heat-treated 1h, final to obtain
To phenolic resin-based activated carbon.
The specific surface area of the phenolic resin-based activated carbon of the present embodiment is 2161m2/g。
Using the phenolic resin-based activated carbon and TEABF of the present embodiment4The matter of ultracapacitor prepared by/PC organic systems
Amount specific capacitance is 130.8F/g.
Embodiment 4
By through the coconut husk powder material 100g of Mechanical Crushing to 20 mesh and activator potassium hydroxide in mass ratio 1:4 water are mutually mixed
Close uniform, load in corundum crucible, under argon gas atmosphere protection, in middle temperature type resistance furnace, heated up with the speed of 4 DEG C/min
Activator melt impregnation, isothermal holding 3h are carried out to 380 DEG C；Continuation is warming up to 900 DEG C and is activated with the speed of 4 DEG C/min,
Insulation 2h；After after batch-type furnace cooling, activation material precursor is taken out, purified, ball milling, sieving are finally protected in argon gas atmosphere
Under, in middle temperature type resistance furnace, being warming up to 1000 DEG C with the speed of 3 DEG C/min carries out high temperature sintering, is heat-treated 2h, final to obtain
To coconut based activated Carbon Materials.
The specific surface area of the coconut shell based activated carbon of the present embodiment is 2358m2/g。
Using the coconut shell based activated carbon and TEABF of the present embodiment4The mass ratio of ultracapacitor prepared by/PC organic systems
Electric capacity is 133.2F/g.
Embodiment 5
By through the phenolic resin starting material 100g of Mechanical Crushing to 80 mesh and activator potassium hydroxide in mass ratio 1:1.5 ball millings
It is well mixed, load in corundum crucible, under nitrogen atmosphere protection, in middle temperature type resistance furnace, with the speed liter of 5 DEG C/min
Warm to 400 DEG C carry out activator melt impregnation, isothermal holding 1h；Continuation is warming up to 650 DEG C and is lived with the speed of 3 DEG C/min
Change, be incubated 3h；After after batch-type furnace cooling, activation material precursor is taken out, purified, ball milling, sieving are finally protected in nitrogen atmosphere
Under shield, in middle temperature type resistance furnace, being warming up to 700 DEG C with the speed of 4 DEG C/min carries out high temperature sintering, is heat-treated 2.5h, most
Phenolic resin-based activated carbon is obtained eventually.
The specific surface area of the phenolic resin-based activated carbon of the present embodiment is 2009m2/g。
Using the phenolic resin-based activated carbon and TEABF of the present embodiment4The matter of ultracapacitor prepared by/PC organic systems
Amount specific capacitance is 130.2F/g.
Embodiment 6
Except " through the petroleum coke raw material of Mechanical Crushing to 30 mesh " is replaced with " through the petroleum coke raw material of Mechanical Crushing to 30 mesh
In the case where air mass flow is for the atmosphere of 400L/h, 400 DEG C are warming up to the speed of 2 DEG C/min, keep 2h, the pre-oxidation oil for obtaining
It is burnt " outward, other preparation methods and condition are same as Example 2.
The specific surface area of the petroleum coke matrix activated carbon of the present embodiment is 2324m2/g。
Using the petroleum coke matrix activated carbon and TEABF of the present embodiment4The quality of ultracapacitor prepared by/PC organic systems
Specific capacitance is 131.6F/g.
Comparative example 1
Except will " in middle temperature type resistance furnace, being warming up to 320 DEG C with the speed of 2 DEG C/min carries out activator melt impregnation,
Isothermal holding 2h；Continuation is warming up to 700 DEG C and is activated with the speed of 2 DEG C/min, is incubated 1h " replace with " in middle incubator formula electricity
In resistance stove, it is warming up to 700 DEG C with the speed of 2 DEG C/min and is activated, is incubated 3h " outward, other preparation methods and condition and implementation
Example 1 is identical.
The specific surface area of the coconut shell based activated carbon of the present embodiment is 1975m2/g。
Using TEABF4/ PC organic systems prepare the mass ratio electricity of electrode of super capacitor and the ultracapacitor being assembled into
It is 118.8F/g to hold.
By comparative example 1 and comparative example 1, the activated carbon of the embodiment 1 prepared using the method for the present invention
More preferably, its specific surface area improves 13.4% to performance than comparative example 1, and specific capacity improves 16.9%.
Applicant states that the present invention illustrates method detailed of the invention by above-described embodiment, but the present invention not office
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (10)
1. a kind of preparation method of activated carbon, it is characterised in that the described method comprises the following steps：
(1) activated carbon raw material is mixed with activator, is heated, activator melt impregnation treatment is carried out under inert gas shielding；
(2) continue to heat up, activation process is carried out to the melt impregnation product that step (1) is obtained；
(3) activation products that step (2) is obtained are heat-treated under inert gas shielding, are obtained activated carbon.
2. method according to claim 1, it is characterised in that step (1) described activated carbon raw material is plant shell, forge before
In petroleum coke or macromolecule resin any one or at least two mixture；
Preferably, step (1) described activated carbon raw material is the activated carbon raw material by pre-processing and/or the work without pretreatment
Property carbon feedstock, preferably without pretreatment activated carbon raw material；
Preferably, step (1) described activator is any one in alkali metal hydroxide, zinc chloride or phosphoric acid or at least two
The combination planted, preferably alkali metal hydroxide, more preferably NaOH；
Preferably, the alkali metal hydroxide is preferably NaOH and/or potassium hydroxide；
Preferably, the states of matter of step (1) described activator is solid powder, the pattern of the activator include particle, sheet or
In pearl any one or at least two combination；
Preferably, the particle diameter of step (1) described activator is 0.1mm~3mm, preferably 0.5mm~2mm；
Preferably, step (1) described activator is the NaOH Beads of 0.5mm~2mm；
Preferably, the mass ratio of step (1) activated carbon raw material and the activator is 1:(1~5), preferably 1:(2~
4)；
Preferably, step (1) it is described mix the mode that uses for solid phase mixing, water are mixed or ball milling mixing in any one
Or at least two combination, preferably solid phase mixing；
Preferably, the method for the solid phase mixing is：Activated carbon raw material is mixed directly with activator；
Preferably, the method that the water is mixed is：After activated carbon raw material is well mixed with the aqueous solution of activator, 120 DEG C
Moisture is evaporated；
Preferably, the method for the ball milling mixing is：Ball milling after activated carbon raw material is mixed with activator；
Preferably, step (1) described inert gas be nitrogen, helium, neon, argon gas, Krypton or xenon in any one or
At least two combination, preferably nitrogen；
Preferably, the temperature of step (1) the activator melt impregnation treatment is 200 DEG C~400 DEG C, preferably 320 DEG C；
Preferably, be warming up to activator melt impregnation treatment temperature heating rate for 1 DEG C/min~10 DEG C/
Min, preferably 2 DEG C/min~5 DEG C/min；
Preferably, the time of step (1) the activator melt impregnation treatment is 1h~6h, preferably 2h~4h；
Preferably, step (1) the activator melt impregnation treatment is carried out in closed stove body；
Preferably, the closed body of heater is any in batch-type furnace, vacuum drying oven, rotary furnace, roller furnace, pusher furnace or tube furnace
One kind, preferably batch-type furnace.
3. method according to claim 1 and 2, it is characterised in that the temperature of step (2) described activation process is 500 DEG C
~1000 DEG C, preferably 600 DEG C~800 DEG C；
Preferably, the heating rate for being warming up to the temperature of the activation process is 1 DEG C/min~10 DEG C/min, preferably 2
DEG C/min~5 DEG C/min；
Preferably, the time of step (2) described activation process is 0.5h~5h, preferably 1h~3h.
4. the method according to claim any one of 1-3, it is characterised in that step (3) described inert gas is nitrogen, helium
In gas, neon, argon gas, Krypton or xenon any one or at least two combination, preferably nitrogen；
Preferably, the temperature of step (3) described heat treatment is 400 DEG C~1100 DEG C, preferably 600 DEG C~1000 DEG C；
Preferably, the heating rate of temperature of the heat treatment is warming up to for 1 DEG C/min~10 DEG C/min, preferably 2 DEG C/
Min~5 DEG C/min；
Preferably, the time of step (3) described heat treatment is 0.5h~6h, preferably 1h~3h.
5. the method according to claim any one of 1-4, it is characterised in that before methods described is additionally included in step (1)
Carry out step (1) '：The step of being dried to activated carbon raw material, crushed and sieved；
Preferably, the mesh number of the screen cloth for using that sieves is 10 mesh~100 mesh, preferably 30 mesh.
6. the method according to claim any one of 1-5, it is characterised in that methods described is additionally included in after step (2)
Step (3) ' is carried out before step (3)：The activation products that step (2) is obtained are washed, are purified, ball milling/crushing and sieving
The step of.
7. method according to claim 6, it is characterised in that be the step of step (3) ' described purifying：Using hot hydrochloric acid
Solution and hot water carry out being purified to pH=6~7；
Preferably, the concentration of the hot hydrochloric acid solution is 1wt%~5wt%；
Preferably, the temperature of the purifying is 80 DEG C~90 DEG C；
Preferably, the particle diameter D of the product by being obtained after step (3) '50It is 4 μm~15 μm, preferably 4 μm~10 μm.
8. the method according to claim any one of 1-7, it is characterised in that the described method comprises the following steps：
(1)’：Activated carbon raw material without pretreatment is dried, is crushed with and is sieved, the activated carbon after being sieved is former
Material；
(1) activated carbon raw material after the sieving for obtaining step (1) ' and activator in mass ratio 1:(1~5) mix, heating,
In 200 DEG C~400 DEG C activator melt impregnation treatment 1h~6h under inert gas shielding；
(2) continue to heat up, activation process is carried out in 500 DEG C~1000 DEG C to the melt impregnation product that step (1) is obtained；
(3)’：The activation products that step (2) is obtained are washed, are purified, ball milling and sieving the step of, the work after being processed
Change product；
(3) activation products after the treatment for obtaining step (3) ' are heat-treated under inert gas shielding in 400 DEG C~1100 DEG C
0.5h~6h, obtains activated carbon.
9. the activated carbon that a kind of use claim 1-8 any one methods describeds are prepared；
Preferably, the specific surface area of the activated carbon is more than 2000m2/g。
10. purposes of the activated carbon as claimed in claim 9 in electrode of super capacitor.
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| CN111573667A (en) * | 2020-06-28 | 2020-08-25 | 中国石油化工股份有限公司 | Energy storage carbon material, supercapacitor and preparation method thereof |
| CN112017871A (en) * | 2020-08-31 | 2020-12-01 | 深圳职业技术学院 | Composite electrode material and preparation method and application thereof |
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| CN113307266B (en) * | 2021-06-04 | 2022-10-14 | 国际竹藤中心 | Modified activated carbon, preparation method thereof and supercapacitor |
| CN113697807A (en) * | 2021-07-23 | 2021-11-26 | 中国石油大学(北京) | Method for preparing capacitance carbon and circularly regenerating template by using chloride as template |
| CN115707653A (en) * | 2021-08-19 | 2023-02-21 | 中国石油化工股份有限公司 | Preparation method and application of sulfur-nitrogen-boron-doped petroleum coke-based activated carbon |
| CN115707653B (en) * | 2021-08-19 | 2024-03-29 | 中国石油化工股份有限公司 | Preparation method and application of sulfur-nitrogen-boron doped petroleum coke-based activated carbon |
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