CN108996501A - Modified absorbent charcoal material, preparation method and purposes - Google Patents
Modified absorbent charcoal material, preparation method and purposes Download PDFInfo
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- CN108996501A CN108996501A CN201710418281.6A CN201710418281A CN108996501A CN 108996501 A CN108996501 A CN 108996501A CN 201710418281 A CN201710418281 A CN 201710418281A CN 108996501 A CN108996501 A CN 108996501A
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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
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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
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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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
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- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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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
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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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 present invention provides a kind of modified active Carbon Materials, which is characterized in that the modified active Carbon Materials include activated carbon particles, and the graphene sheet layer being adsorbed in the activated carbon particles.The present invention is modified active carbon using grapheme material, at least partially by covalent bond that the two is crosslinked together, realizes the purpose on the activated carbon by grapheme material firm connection, plays the role of enhancing specific surface area, enhance the adsorption capacity of active carbon；From dispersibility, grapheme material and the secured of active carbon are effectively combined, and are reduced the dispersibility of grapheme material, are improved the uniformity of modified absorbent charcoal material in use；For the modified absorbent charcoal material of redox graphene, electric conductivity enhancing, specific surface area increases, good dispersion.
Description
Technical field
The invention belongs to modified function Material Fields, and in particular to a kind of absorbent charcoal material of modification, preparation method and use
On the way.
Background technique
Absorbent charcoal material is that have very big specific surface area, to gas, solution by the resulting amorphous carbon of working process
In inorganic or organic substance and colloidal solid etc. have good adsorption capacity.Absorbent charcoal material mainly includes active carbon
(Activated Carbon, AC) and activated carbon fibre (Activated Carbon Fibers, ACF) etc..Absorbent charcoal material is made
For a kind of adsorbent of function admirable, mainly since it is with unique absorption surface architectural characteristic and surface chemistry institute
It determines.The chemical property of absorbent charcoal material is stablized, and high mechanical strength is acidproof, alkaline-resisting, heat-resisting, not soluble in water and organic solvent,
Use can be regenerated, chemical industry, environmental protection, food processing, metallurgy, drug purification, military chemistry protection etc. are had been widely used for
Every field.
The prior art, to the method for modifying of active carbon, is mostly to use to mix graphene and active carbon high-temp by graphene
The mode of conjunction, this mode can be in conjunction with the material of graphene and active carbon, but its dispersing uniformity is poor, the two mixed effect
Bad, to the performance improvement of absorbent charcoal material, effect is limited.
This field needs to develop a kind of grapheme material modified active Carbon Materials, can be by grapheme material and active carbon
Material firm connection obtains good dispersibility, specific surface area and electric property etc..
Summary of the invention
In view of the deficiencies of the prior art, the present invention relates to a kind of absorbent charcoal material of modification, the modified active Carbon Materials
Including activated carbon particles, and the graphene sheet layer being adsorbed in the activated carbon particles.
Absorption of the present invention includes physical absorption and chemisorption, and the physical absorption is also referred to as Van der Waals absorption, particle
Between be to be adsorbed by intermolecular force；The chemisorption is the transfer that electronics occurs between particle, exchange or total
Have, forms the absorption of sorption chemical key.Absorption of the present invention includes physical absorption and chemisorption, it can be understood as simultaneously
With physical absorption and chemisorption, or have chemisorption.
Preferably, in the modified active Carbon Materials, at least partly graphene sheet layer is adsorbed on the work by chemical bond
On property charcoal particle.
Grapheme material and Activated carbon matrix are crosslinked by chemical bond, and compared to Van der Waals force, chemical bond crosslinking is more firm
Gu imparting the higher specific surface area of absorbent charcoal material, superior electricity with the grapheme material of absorbent charcoal material firm connection
Learn performance.
Preferably, in the modified active Carbon Materials, the secondary particle including modified active Carbon Materials, the modified active
It include at least two activated carbon particles being crosslinked by graphene sheet layer in the secondary particle of Carbon Materials.
Secondary particle of the present invention be understood that for by monomer particle (such as activated carbon particles, graphene sheet layer particle,
The particle etc. of activated carbon adsorption graphene) obtained particle of reuniting.And the second level grain of modified active Carbon Materials of the present invention
In son, there is the secondary particle at least two activated carbon particles (monomer particle) composition being crosslinked by graphene sheet layer.
In the secondary particle of arbitrary modified active Carbon Materials, type, the quantity of monomer particle are not specifically limited, example
It is logical with 1 (2,3,4,5 etc.) graphene sheet layer such as to can be 2 (3,4,5) activated carbon particles
It crosses chemisorption or physical absorption is reunited.
Preferably, the partial size of the secondary particle of the modified active Carbon Materials is greater than the partial size of activated carbon particles.
It is most of (to can be understood as 70% or more or 80% or more in the absorbent charcoal material of modification of the present invention
Or 90% or more) particle exists in the form of secondary particle.
Preferably, the partial size of the secondary particle of the modified active Carbon Materials is at 20 μm hereinafter, such as 2 μm, 3 μm, 4 μm, 5
μm, 6 μm, 7 μm, 8 μm, 9 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm etc., preferably at 12 μm hereinafter,
Further preferably at 5 μm or less.
Since the partial size of monomer particle (mainly activated carbon particles) has bigger difference (such as common activated carbon particles
At 1 μm or more, and the partial size of bamboo charcoal is mostly at 1 μm or less), the size of obtained secondary particle also has biggish difference.
Optionally, the partial size of the secondary particle of the modified active Carbon Materials is between 3~7 μm, such as 4 μm, 5 μm, 6 μm
Deng preferably between 4~6 μm.
Optionally, the size of the modified activated carbon particle diameter be 1 μm hereinafter, such as 0.2 μm, 0.3 μm, 0.4 μm,
0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm etc., preferably 0.5-0.8 μm.
Preferably, the specific surface area of the modified active Carbon Materials is 1000~3000m2/ g, preferably 2200~3000m2/
G, the modified active Carbon Materials have continuously distributed pore structure in 0.7~10nm, and average pore size is 2~10nm, middle boring ratio
Example is 10~50%.
The second object of the present invention is to a kind of preparation method of modified active Carbon Materials as described in the first purpose is provided, it is special
Sign is that described method includes following steps:
(1) active carbon is activated, obtains the active carbon for being modified with oxygen-containing functional group；
(2) active carbon for being modified with oxygen-containing functional group is mixed with the grapheme material containing functional group, crosslinking agent is added,
After cross-linked polymeric, modified active Carbon Materials are obtained.
The modified active carbon of graphene oxide has more oxygen-containing functional group and excellent specific surface area, and chemical property
Stablize, has the effect of in adsorbing domain excellent.In the modified active carbon of graphene oxide, contain the graphene-based of functional group
A large amount of functional groups (a variety of electronegativity oxygen-containing functional groups of such as epoxy group, hydroxyl, carboxyl, carbonyl) are distributed in face and edge, lead to
Cross Electrostatic Absorption can effectively Liquidity limit, the modified active carbon of graphene oxide to cationic dyes and heavy metal from
The adsorption capacity of son is much higher than traditional carbon adsorbing material and exchanger resin ion；A large amount of oxygen-containing functional group assigns modified activated carbon
Splendid hydrophily, as well as the good hydrophily of graphene oxide, there is be difficult to separate after absorption in practical applications
The phenomenon that, and by being crosslinked other groups in surface of graphene oxide, active adsorption sites can be increased and recycling point of being more convenient for
From.
Optionally, step (3) are carried out after step (2): carries out restoring operation after cross-linked polymeric.
After the modified absorbent charcoal material reduction of graphene oxide, the modified active raw material of wood-charcoal of redox graphene is obtained
Material, large specific surface area, mechanical property and thermal conductivity are strong.In the modified absorbent charcoal material of redox graphene, compared to
The modified absorbent charcoal material of graphene oxide, oxygen-containing functional group are reduced, and charge mobility increases, and pore structure is orderly reasonable, can use
In electrode material for super capacitor, the functional group of modified active carbon surface and its quantity, to leakage current characteristic, specific capacitance, pressure resistance and
Service life, which has, to be directly affected, and these parameters are the intuitive index of capacitor quality judgement, such as hydroxyl in water-medium
Concentration is higher, and electrode leakage current is bigger, depot poorer, and carboxyl concentration is higher, and material static current potential is higher, oxygen evolution reaction
Possibility is bigger, and electrode is more unstable；Increasing for charge mobility is conducive to electrode material performance more conductive capability, realizes
The quick transmitting of charge；Orderly reasonable pore structure, is conducive to the absorption and transfer of electrolyte ion in different systems, Jin Erfa
Wave more preferably capacitance characteristic.
Preferably, the particle size of step (1) described active carbon at 10 μm hereinafter, such as 2 μm, 3 μm, 4 μm, 5 μm, 6 μm,
7 μm, 8 μm, 9 μm etc., preferably at 5 μm hereinafter, further preferably at 3 μm or less.
Optionally, the particle size of the active carbon is 3~7 μm, preferably 4~6 μm.
Optionally, the particle size of the active carbon is at 1 μm hereinafter, it is preferred that at 0.5~0.8 μm.
The present invention is not specifically limited the source of active carbon, and the active carbon that anyone skilled in the art can obtain is equal
It can be used for the present invention, can be commercially available, can also be prepared by any method that can be known.
Preferably, the carbon source for preparing active carbon includes shell fruit stone, bamboo material, coal quality, petroleum-type product, agricultural
It is any a kind or at least two kinds of of combination in byproduct, macromolecule, preferably coconut husk, petroleum coke, phenolic resin, any in moso bamboo
1 kind or at least two kinds of of combination.
Preferably, the shell fruit stone includes coconut husk, olive shell, walnut shell, any a kind or at least two kinds of in almond
Combination.
Preferably, the bamboo material includes moso bamboo and/or bamboo.
Preferably, the coal quality includes mud coal, lignite, any a kind or at least two kinds of of combination in bituminous coal.
Preferably, the petroleum-type product includes pitch, any a kind or at least two kinds of of combination in petroleum coke.
Preferably, the agricultural by product includes rice husk, stalk, any a kind or at least two kinds of of combination in furfural dregs.
Preferably, the macromolecule includes phenolic resin, any a kind or at least two kinds of of combination in furane resins.
Grapheme material of the present invention is any material with graphene sheet layer that those skilled in the art can be known
Material, including graphene, graphene oxide, functional group's graphite alkene etc..For the preparation method of the grapheme material, the present invention
It is not specifically limited, the method that can be removed by graphite, the method restored after graphite oxide, the method etc. of chemical vapor deposition
Deng.
Preferably, the grapheme material is the material with graphene sheet layer structure, including graphene, graphene oxide
And any a kind or at least two kinds of of combination in Graphene derivative.
Preferably, the graphene includes that graphite is prepared by stripping method, and graphene oxide is prepared by reduction
It arrives, graphite is prepared by redox, and carbonaceous gas is prepared by CVD method, passes through high temperature by raw material of biomass
Cracking process is prepared.
Preferably, step (2) active carbon for being modified with oxygen-containing functional group and the grapheme material containing functional group are mixed
The mass ratio of conjunction be 100:0.1~20, such as 100:1,100:2,100:3,100:4,100:5,100:6,100:7,100:8,
100:9、100:10、100:11、100:12、100:13、100:14、100:15、100:16、100:17、100:18、100:19
Deng, preferred 100:0.8~8, more preferable 100:2~5.
Preferably, the step of step (1) described activation are as follows: mix active carbon with activator.
After active carbon to be modified is mixed with activator, active group, realization and graphene can be formed on the activated carbon
The combination of material.
Preferably, the activator includes oxidant, preferably nitric acid, sulfuric acid, phosphoric acid, sodium hypochlorite, appointing in hydrogen peroxide
The combination of a kind or at least two kinds of of meaning.
Preferably, the additive amount of the activator is 0.1~10 times of activated carbon weight, such as 0.5 times, 0.7 times, 1.3
Times, 1.8 times, 2.3 times, 2.8 times, 3.3 times, 3.8 times, 4.3 times, 4.8 times, 5.3 times, 5.8 times, 6.3 times, 6.8 times, 7.3 times,
7.8 times, 8.3 times, 8.8 times, 9.3 times, 9.8 times etc..
Preferably, the temperature of the activation is 35~85 DEG C, such as 36 DEG C, 42 DEG C, 48 DEG C, 52 DEG C, 58 DEG C, 62 DEG C, 68
DEG C, 72 DEG C, 78 DEG C, 82 DEG C etc., the activation time is 0.5~10h, for example, 0.6h, 1.2h, 1.7h, 2.2h, 2.7h, 3.2h,
3.7h, 4.2h, 4.7h, 5.2h, 5.7h, 6.2h, 6.7h, 7.2h, 7.7h, 8.2h, 8.7h, 9.2h, 9.7h etc..
Preferably, step (2) functional group's graphite alkene material includes graphene oxide and/or amination graphene.
Preferably, the crosslinking agent include ethylene glycol, polyethylene glycol, ethanol amine, ethylenediamine, aliphatic diamine, melamine,
Any a kind or at least two kinds of of combination in two mercaptan, mercaptoethanol.
Preferably, the additive amount of the crosslinking agent is 0.1~10 times of grapheme material weight, for example, 0.5 times, 0.7 times,
1.3 times, 1.8 times, 2.3 times, 2.8 times, 3.3 times, 3.8 times, 4.3 times, 4.8 times, 5.3 times, 5.8 times, 6.3 times, 6.8 times, 7.3
Again, 7.8 times, 8.3 times, 8.8 times, 9.3 times, 9.8 times etc..
Preferably, the pH value of the cross-linked polymeric is 4~8, such as 5,6,7 etc., and the temperature of cross-linked polymeric is 30~90 DEG C,
Such as 35 DEG C, 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C etc., the time is 0.5~5h, example
Such as 0.6h, 1.2h, 1.7h, 2.2h, 2.7h, 3.2h, 3.7h, 4.2h, 4.7h.
Preferably, the reduction includes chemical reduction method, charing reduction method or Microwave reduction method.
Preferably, the chemical method is to be contacted using chemical reducing agent with modified absorbent charcoal material, the electronation
Agent includes hydrazine hydrate, L-AA, sodium borohydride, sodium citrate, any a kind or at least two kinds of of combination in sodium hydroxide.
Preferably, the charing reduction method be carbonized under non-oxidizing atmosphere, the carbonization temperature be 500~
1000 DEG C, carbonization time is 0.5~6h.
Preferably, the Microwave reduction method is to carry out microwave reduction under non-oxidizing atmosphere, microwave power is 1.5~
0.8kW, microwave time are 1~15min.
Preferably, step (3) after the reduction of modified active Carbon Materials, will be washed constant to conductivity, dry.
Preferably, the drying temperature is 40~120 DEG C.
The three of the object of the invention are to provide a kind of purposes of the absorbent charcoal material of modification as described in the first purpose, described to change
Property absorbent charcoal material be used for supercapacitor, water process, sea water desalination, water desalination field.
Preferably, the modified active Carbon Materials are used as adsorbent material, the sea water desalination adsorbent material, water desalination of water process
Adsorbent material.
Preferably, the reduzate of the absorbent charcoal material of the modification by restoring operation is used as the electricity of supercapacitor
Pole material.
The four of the object of the invention are to provide a kind of supercapacitor, the electrode material of the supercapacitor include purpose it
The absorbent charcoal material of modification described in one.
Compared with prior art, the invention has the following beneficial effects:
(1) present invention is modified active carbon using grapheme material, is crosslinked the two at least partially by covalent bond
Together, the purpose on the activated carbon by grapheme material firm connection is realized, enhancing specific surface area is played, enhances active carbon
Adsorption capacity effect；
(2) from dispersibility, grapheme material and the secured of active carbon are effectively combined, and reduce grapheme material
Dispersibility improves the uniformity of modified absorbent charcoal material in use；
(3) absorbent charcoal material modified for redox graphene, electric conductivity enhancing, specific surface area increase, dispersibility
It is good.
Detailed description of the invention
Fig. 1 is 5000 times of amplification of electron microscope of the absorbent charcoal material for the modification that embodiment 4 obtains；
Fig. 2 is 20000 times of amplification of electron microscope of the absorbent charcoal material for the modification that embodiment 4 obtains；
Fig. 3 is 3000 times of amplification of electron microscope of the absorbent charcoal material for the modification that embodiment 7 obtains；
Fig. 4 is 30000 times of amplification of electron microscope of the absorbent charcoal material for the modification that embodiment 7 obtains；
Fig. 5 is the constant current charge-discharge figure in water system.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.
Those skilled in the art are not construed as to this hair it will be clearly understood that the described embodiments are merely helpful in understanding the present invention
Bright concrete restriction.
Embodiment 1
A kind of absorbent charcoal material of modification, preparation method include the following steps:
(1) 10g active carbon to be modified (1~10 μm) is dispersed in 500mL 0.1M sulfuric acid solution, is stirred at 80 DEG C
1h is mixed, precipitating cleaning is then obtained into activated carbon to pH close to 7；
(2) activated carbon is dispersed in the 1wt% glycol water of 100mL, then under 80 DEG C of counterflow conditions
The 0.5wt% graphene oxide water solution of 150mL is instilled, and continues to stir 12h, obtains the modified active raw material of wood-charcoal of graphene oxide
Expect dispersion liquid；
(3) the modified absorbent charcoal material dispersion liquid of graphene oxide is filtered, precipitating is cleaned with clear water, later that precipitating is dry
Dry, grinding obtains the modified absorbent charcoal material of graphene oxide.
Embodiment 2
The difference from embodiment 1 is that step (3) are as follows: the absorbent charcoal material dispersion modified to graphene oxide at room temperature
The 20wt% hydrazine hydrate of 5mL is added in liquid, it is then with deionized water that precipitating cleaning is constant to washing lotion conductivity, finally by filter cake
It is ground after 80 DEG C of dryings, obtains graphene modified activated carbon.
Embodiment 3
A kind of absorbent charcoal material of modification, preparation method include the following steps:
(1) 5g active carbon (1~10 μm) is dispersed in 500mL 0.1M sulfuric acid solution, 5h is stirred at 40 DEG C, so
Precipitating cleaning is obtained into activated carbon to pH close to 7 afterwards；
(2) activated carbon is dispersed in the 10wt% glycol water of 100mL, then under 80 DEG C of counterflow conditions
The 0.5wt% graphene oxide water solution of 150mL is instilled, and continues to stir 12h, obtains the modified active raw material of wood-charcoal of graphene oxide
Expect dispersion liquid；
(3) the modified absorbent charcoal material dispersion liquid of graphene oxide is obtained graphene oxide and changed in 60 DEG C of constant temperature dryings
The absorbent charcoal material of property.
Embodiment 4
Difference with embodiment 3 is, step (3) are as follows: by the modified absorbent charcoal material dispersion liquid of graphene oxide in 60
DEG C constant temperature drying, then be placed in the lower 1000 DEG C of microwave treatment 60min of nitrogen protection and restored, then with deionization by microwave reduction
Product cleaning will finally grind after 80 DEG C of dryings of filter cake to filtrate stable conductivity, obtain graphene modified activated carbon.
Fig. 1 and Fig. 2 is the electron microscope of the different magnification ratios of the absorbent charcoal material for the modification that embodiment 4 obtains.
It can be seen that the absorbent charcoal material of modification provided by the invention in graphene thin layer and active carbon from Fig. 1 and Fig. 2
Grain composite construction, wherein graphite flake layer is crosslinked on active carbon particle by chemical bond, improves of active carbon from microcosmic
Granule density, and active carbon is fixed on graphene sheet layer by crosslinking agent, restrained effectively the pi-pi accumulation of graphene itself,
Realize charcoal particle-GR thin layer-charcoal particle microscopic appearance feature interconnected.
Embodiment 5
Be with the distinctive points of embodiment 2: step (3) are as follows: by the modified absorbent charcoal material dispersion liquid of graphene oxide in
60 DEG C of constant temperature dryings, then be placed in the lower 1000 DEG C of microwave treatment 60min of nitrogen protection and restored, then with deionization by microwave also
Former product cleaning will finally grind after 80 DEG C of dryings of filter cake to filtrate stable conductivity, obtain graphene modified activated carbon.
Embodiment 6
A kind of absorbent charcoal material of modification, preparation method include the following steps:
(1) 5g active carbon (1~10 μm) is dispersed in 500mL 0.1M phosphoric acid solution, 5h is stirred at 40 DEG C, so
Precipitating cleaning is obtained into activated carbon to pH close to 7 afterwards；
(2) activated carbon is dispersed in 100mL 10wt% melamine aqueous solution, then in 80 DEG C of counterflow conditions
Lower instillation 150mL 0.5wt% graphene oxide water solution, and continue to stir 12h, obtain the modified active carbon of graphene oxide
Material dispersion liquid；
(3) the modified absorbent charcoal material dispersion liquid of graphene oxide is obtained graphene oxide and changed in 60 DEG C of constant temperature dryings
The absorbent charcoal material of property.
Embodiment 7
Difference with embodiment 6 is, step (3) are as follows: by the modified absorbent charcoal material dispersion liquid of graphene oxide in 60
DEG C constant temperature drying, then be placed in the lower 600 DEG C of charings 10h of nitrogen protection and restored, reduzate is cleaned to filtrate with deionization
Stable conductivity will finally grind after 80 DEG C of dryings of filter cake, obtain graphene modified activated carbon.
Fig. 3 and Fig. 4 is the electron microscope of the different magnification ratios of the absorbent charcoal material for the modification that embodiment 7 obtains.
From figs. 3 and 4 it can be seen that the absorbent charcoal material of modification provided by the invention is in graphene thin layer and active carbon
Grain composite construction, wherein graphite flake layer is crosslinked on active carbon particle by chemical bond, improves of active carbon from microcosmic
Granule density, and active carbon is fixed on graphene sheet layer by crosslinking agent, restrained effectively the pi-pi accumulation of graphene itself,
Realize charcoal particle-GR thin layer-charcoal particle microscopic appearance feature interconnected.
Embodiment 8
Difference with embodiment 3 is, the activator of step (1) is liquor natrii hypochloritis, in the liquor natrii hypochloritis
The quality of sodium hypochlorite is 10g, and activation temperature is 35 DEG C, time 10h.
Embodiment 9
Difference with embodiment 4 is, the activator of step (1) is liquor natrii hypochloritis, in the liquor natrii hypochloritis
The quality of sodium hypochlorite is 10g, and activation temperature is 35 DEG C, time 10h.
Embodiment 10
Difference with embodiment 3 is that the activator of step (1) is nitric acid solution, the matter of nitric acid in the nitric acid solution
Amount is 50g, and activation temperature is 50 DEG C, time 1h.
Embodiment 11
Difference with embodiment 4 is that the activator of step (1) is nitric acid solution, the matter of sulfuric acid in the nitric acid solution
Amount is 10g, and activation temperature is 50 DEG C, time 1h.
Embodiment 12
Difference with embodiment 3 is that the 10wt% glycol water of step (2) 100mL replaces with 100mL's
50wt% glycol water, cross-linked polymeric temperature are 30 DEG C, time 3h.
Embodiment 13
Difference with embodiment 4 is that the 10wt% glycol water of step (2) 100mL replaces with 100mL's
50wt% glycol water, cross-linked polymeric temperature are 30 DEG C, time 3h.
Embodiment 14
A kind of absorbent charcoal material of modification, preparation method include the following steps:
(1) 5g active carbon (1~10 μm) is dispersed in 500mL 0.1M sulfuric acid solution, 5h is stirred at 40 DEG C, so
Precipitating cleaning is obtained into activated carbon to pH close to 7 afterwards；
(2) activated carbon is dispersed in the 10wt% glycol water of 100mL, then under 80 DEG C of counterflow conditions
The 0.5wt% for instilling 100mL removes graphene aqueous solution, and continues to stir 12h, obtains graphene modified absorbent charcoal material point
Dispersion liquid；
(3) the modified absorbent charcoal material dispersion liquid of graphene is obtained into the modified activity of graphene in 60 DEG C of constant temperature dryings
Carbon Materials.
Comparative example 1
Using absorbent charcoal material to be modified used in embodiment as comparative example 1.
Comparative example 2
Absorbent charcoal material to be modified is placed in the lower 600 DEG C of charings 10h of nitrogen protection and is restored in embodiment, will with deionization
Reduzate is cleaned to filtrate stable conductivity, will finally be ground after 80 DEG C of dryings of filter cake, is obtained high temperature modified active carbon.
Comparative example 3
5g active carbon (1~10 μm) and 0.1g stripping method graphene are mixed and ground 1h, obtains the modified work of graphene
Property Carbon Materials.
Performance test
(1) the specific surface area: " side of gas absorption BET principle measurement solid matter specific surface area GB/T 19587-2004
Method "；
(2) resistivity: GB24525-2009 " carbon material determination of resistivity method "
(3) specific capacitance: respectively with the to be modified of the graphene modified activated carbon and comparative example 1 of embodiment 7 and embodiment 11
Active carbon is scattered in 1.5mL dehydrated alcohol as electrode material, sequentially adds conductive black and polytetrafluoroethylene (PTFE) bonding
Agent, electrode material and conductive black and binder mass ratio are 8:1:1, and drop coating is done to foam nickel base electrode after ultrasonic mixing
It is working electrode after dry, mercuric oxide electrode is reference electrode, and platinized platinum is to electrode, and electrolyte is 6M KOH.
(4) methylene blue solution for configuring 1.mg/mL, weighs 1g adsorbent, is placed in the centrifugation of 70ml methylene blue solution
After being protected from light 360min in constant-temperature table (25 DEG C, 250r/min) in pipe, centrifuge separation, supernatant is measured with UV-Vis to be inhaled
Luminosity calculates adsorbance according to the following formula:
qe=(C0–Ce)·V/m
Wherein, C0And CeRespectively methylene blue initial concentration and equilibrium concentration (mg/mL)；M is modified active Carbon Materials matter
Amount；V is methylene blue solution volume (mL)；qeFor equilibrium adsorption capacity (mg/g).
Test result such as table 1:
Table 1 is the performance test results of the absorbent charcoal material for the modification that embodiment and comparative example improves
From the performance test results as can be seen that the surface area of modified absorbent charcoal material becomes larger, stone is activated and aoxidized
Black alkene introduces certain oxygen-containing functional group, significantly increases the adsorbance of methylene blue；Graphene oxide modified active raw material of wood-charcoal
Expect that resistivity increases, reduction treatment or the absorbent charcoal material resistivity reduction being directly modified using graphene, institute's modified electrode
The transmitting that charge and electrolyte ion are promoted in water system realizes the increase of specific capacitance, for restoring method, microwave reduction
The product obtained with high temperature reduction has preferable resistivity and specific capacitance.
The Applicant declares that the present invention illustrates the process method of the present invention through the above embodiments, but the present invention not office
It is limited to above-mentioned processing step, that is, does not mean that the present invention must rely on the above process steps to be carried out.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to raw material selected by the present invention
Addition, selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (14)
1. a kind of modified active Carbon Materials, which is characterized in that the modified active Carbon Materials include activated carbon particles, and absorption
Graphene sheet layer in the activated carbon particles.
2. absorbent charcoal material as described in claim 1, which is characterized in that at least partly graphene sheet layer passes through chemical bond
It is adsorbed in the activated carbon particles.
3. modified active Carbon Materials as claimed in claim 1 or 2, which is characterized in that in the modified active Carbon Materials, including
The secondary particle of modified active Carbon Materials includes being crosslinked in the secondary particle of the modified active Carbon Materials by graphene sheet layer
At least two activated carbon particles.
4. the modified active Carbon Materials as described in one of claims 1 to 3, which is characterized in that the modified active Carbon Materials
The partial size of secondary particle is greater than the partial size of activated carbon particles；
Preferably, the partial size of the secondary particle of the modified active Carbon Materials is at 20 μm hereinafter, it is preferred that at 12 μm hereinafter, further
It is preferred that at 5 μm or less；
Optionally, the partial size of the secondary particle of the modified active Carbon Materials is between 3~7 μm, preferably between 4~6 μm；
Optionally, the size of the modified activated carbon particle diameter is 1 μm hereinafter, it is preferred that 0.5-0.8 μm.
5. the modified active Carbon Materials as described in one of Claims 1 to 4, which is characterized in that the modified active Carbon Materials
Specific surface area is 1000~3000m2/ g, preferably 2200~3000m2/ g, the modified active Carbon Materials have in 0.7~10nm
Continuously distributed pore structure, average pore size are 2~10nm, and mesopore proportion is 10~50%.
6. a kind of preparation method of the modified active Carbon Materials as described in one of Claims 1 to 5, which is characterized in that the side
Method includes the following steps:
(1) active carbon is activated, obtains the active carbon for being modified with oxygen-containing functional group；
(2) active carbon for being modified with oxygen-containing functional group is mixed with the grapheme material containing functional group, crosslinking agent, crosslinking is added
After polymerization, modified active Carbon Materials are obtained；
Optionally, step (3) are carried out after step (2): carries out restoring operation after cross-linked polymeric.
7. preparation method as claimed in claim 6, which is characterized in that the particle size of step (1) described active carbon is at 10 μm
Hereinafter, it is preferred that at 5 μm hereinafter, further preferably at 3 μm or less；
Optionally, the particle size of the active carbon is 3~7 μm, preferably 4~6 μm；
Optionally, the particle size of the active carbon is at 1 μm hereinafter, it is preferred that at 0.5~0.8 μm；
Preferably, the carbon source for preparing active carbon includes shell fruit stone, bamboo material, coal quality, petroleum-type product, agriculture by-product
Any a kind or at least two kinds of of combination in product, macromolecule, preferably coconut husk, petroleum coke, phenolic resin, any a kind in moso bamboo
Or at least two kinds of combination；
Preferably, the shell fruit stone includes coconut husk, olive shell, walnut shell, any a kind or at least two kinds of of combination in almond；
Preferably, the bamboo material includes moso bamboo and/or bamboo；
Preferably, the coal quality includes mud coal, lignite, any a kind or at least two kinds of of combination in bituminous coal；
Preferably, the petroleum-type product includes pitch, any a kind or at least two kinds of of combination in petroleum coke；
Preferably, the agricultural by product includes rice husk, stalk, any a kind or at least two kinds of of combination in furfural dregs；
Preferably, the macromolecule includes phenolic resin, any a kind or at least two kinds of of combination in furane resins；
Preferably, the grapheme material is the material with graphene sheet layer structure, including graphene, graphene oxide and stone
Any a kind or at least two kinds of of combination in black ene derivative；
Preferably, the graphene includes that graphite is prepared by stripping method, and graphene oxide is prepared by reduction, stone
Ink is prepared by redox, and carbonaceous gas is prepared by CVD method, passes through high-temperature cracking method by raw material of biomass
It is prepared.
8. preparation method as claimed in claims 6 or 7, which is characterized in that step (2) work for being modified with oxygen-containing functional group
Property the mass ratio that is mixed with the grapheme material containing functional group of charcoal be 100:0.1~20, preferred 100:0.8~8, more preferably
100:2~5.
9. preparation method as claimed in one of claims 6 to 8, which is characterized in that the step of step (1) described activation are as follows: will
Active carbon is mixed with activator；
Preferably, the activator includes oxidant, preferably nitric acid, sulfuric acid, phosphoric acid, sodium hypochlorite, any a kind in hydrogen peroxide
Or at least two kinds of combination；
Preferably, the additive amount of the activator is 0.1~10 times of activated carbon weight；
Preferably, the temperature of the activation is 35~85 DEG C, and the activation time is 0.5~10h.
10. such as preparation method as claimed in one of claims 6 to 9, which is characterized in that step (2) described crosslinking agent includes second two
Alcohol, polyethylene glycol, propylene glycol, polypropylene glycol, butanediol, cyclopentadienyl alcohol, cyclohexanediol, ethanol amine, ethylenediamine, fat two
Amine, melamine, two mercaptan, any a kind or at least two kinds of of combination in mercaptoethanol；
Preferably, the additive amount of the crosslinking agent is 0.1~10 times of grapheme material weight；
Preferably, the pH value of the cross-linked polymeric is 4~8, and the temperature of cross-linked polymeric is 30~90 DEG C, and the time is 0.5~12h.
11. the preparation method as described in one of claim 6~10, which is characterized in that the reduction includes chemical reduction method, charcoal
Change reduction method or Microwave reduction method；
Preferably, the chemical method is to be contacted using chemical reducing agent with modified absorbent charcoal material, the chemical reducing agent packet
Include hydrazine hydrate, L-AA, sodium borohydride, sodium citrate, any a kind or at least two kinds of of combination in sodium hydroxide；
Preferably, the charing reduction method is to be carbonized under non-oxidizing atmosphere, and the carbonization temperature is 500~1000
DEG C, carbonization time is 0.5~6h；
Preferably, the Microwave reduction method is that microwave reduction is carried out under non-oxidizing atmosphere, and microwave power is 5.1~0.7kW,
The microwave time is 1~15min, and microwave reduction temperature is 800~1200 DEG C.
12. the preparation method as described in one of claim 6~11, which is characterized in that step (3) by modified active Carbon Materials also
After original, drying constant to conductivity is washed；
Preferably, the drying temperature is 40~120 DEG C.
13. a kind of purposes of the modified active Carbon Materials as described in one of Claims 1 to 5, which is characterized in that described modified living
Property Carbon Materials be used for supercapacitor, water process, sea water desalination, water desalination field；
Preferably, the modified active Carbon Materials are used as adsorbent material, sea water desalination adsorbent material, the water desalination absorption of water process
Material；
Preferably, the modified active Carbon Materials by restoring operation are used as the electrode material of supercapacitor.
14. a kind of supercapacitor, which is characterized in that the electrode material of the supercapacitor includes one of Claims 1 to 5
The modified active Carbon Materials.
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