CN107134582A - A kind of high activity electrode material and its method of modifying - Google Patents
A kind of high activity electrode material and its method of modifying Download PDFInfo
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- CN107134582A CN107134582A CN201710411631.6A CN201710411631A CN107134582A CN 107134582 A CN107134582 A CN 107134582A CN 201710411631 A CN201710411631 A CN 201710411631A CN 107134582 A CN107134582 A CN 107134582A
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- 230000000694 effects Effects 0.000 title claims abstract description 50
- 239000007772 electrode material Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 121
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 57
- 239000010439 graphite Substances 0.000 claims abstract description 57
- 229920005989 resin Polymers 0.000 claims abstract description 52
- 239000011347 resin Substances 0.000 claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 46
- 238000012545 processing Methods 0.000 claims abstract description 37
- 239000000126 substance Substances 0.000 claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 25
- 239000011230 binding agent Substances 0.000 claims abstract description 22
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 21
- 238000005411 Van der Waals force Methods 0.000 claims abstract description 17
- 238000005087 graphitization Methods 0.000 claims abstract description 17
- 239000002657 fibrous material Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000004913 activation Effects 0.000 claims abstract description 14
- 238000003763 carbonization Methods 0.000 claims abstract description 14
- 238000001467 acupuncture Methods 0.000 claims abstract description 13
- 238000011282 treatment Methods 0.000 claims abstract description 13
- 238000003487 electrochemical reaction Methods 0.000 claims abstract description 7
- 238000010521 absorption reaction Methods 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims description 43
- 239000003575 carbonaceous material Substances 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 23
- 239000000835 fiber Substances 0.000 claims description 18
- 238000000967 suction filtration Methods 0.000 claims description 13
- 239000005011 phenolic resin Substances 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 239000002296 pyrolytic carbon Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims description 5
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 5
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 229920000297 Rayon Polymers 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920001187 thermosetting polymer Polymers 0.000 claims description 3
- 239000011344 liquid material Substances 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007639 printing Methods 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000000151 deposition Methods 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
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- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
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- 239000007791 liquid phase Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- -1 phenolic aldehyde Chemical class 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
- Inert Electrodes (AREA)
Abstract
The present invention provides a kind of high activity electrode material, applied to a kind of electrode material field in electrochemical reaction, it is made with basic material by following steps, the basic material is organic fibrous material, and the step includes basic material combing, acupuncture and forms pre- oxygen felt, high-temperature calcination carbonization treatment formation carbon felt and high-temperature calcination graphitization processing formation graphite felt；The basic material comb, acupuncture formed pre- oxygen felt, high-temperature calcination be carbonized to be formed carbon felt and high-temperature calcination graphitization processing formation graphite felt in, choose one of them and carry out activation, the activation is the chemical graft of the Van der Waals force absorption of physics or the organic resin of chemistry as binding agent.The present invention has high-specific surface area, and acidproof corrosion resistant feature, resinae product is also material cheap and easy to get, can be with large-scale industrial production.
Description
Technical field
The present invention relates to a kind of electrochemical field, and in particular to a kind of table of electrochemical field electrochemical reaction electrode material
Face is modified and its method of modifying.
Background technology
Electrochemical cell be it is a kind of using mutually changing between ion different valence state, in outside by electronic conduction, inside
Portion is by proton or ionic conduction, so as to form the chemical energy storage device of electric current.The electrode material one that electrochemical field is used
As be active carbon material, the electrolyte used is generally divided into organic bath and inorganic electrolyte, and two kinds of electrolyte typically all have
There is certain corrosivity, therefore it is required that electrode felt has higher corrosion resistance.Electrode material is weighed very much in electrochemical field
One of part wanted, because its physicochemical property has very big to the current density, power density, service life of electrochemical power source
Influence.Electrode material typically it is also desirable to have good electric conductivity and good electrification except requiring good corrosion resistance
Learn activity.And the size of electrode material specific surface area, there is large effect to its electro-chemical activity.
By taking all-vanadium flow battery as an example, the electrolyte of all-vanadium flow battery is the extremely corrosive concentrated sulfuric acid, therefore its electricity
Extremely to requiring high in terms of anticorrosion.Current large-scale use makees the mainly graphite felt of full vanadium battery electrode.Graphite felt has
The advantage such as specific surface area is big, corrosion-resistant, resistivity is low, cheap, mechanical strength is high.The activity on graphite felt surface can direct shadow
The integral battery door performance to all-vanadium flow battery is rung, therefore, the developing direction of current graphite felt is that its surface is modified, increased
Plus reactivity point, so as to improve the chemical property of all-vanadium flow battery comprehensively.Not exclusively flow battery field, in seawater
Desalination, sewage treatment area, the requirement to electrode felt is all very high, and the surface of electrode felt, which is modified, to have very important significance.
At present, the method that graphite felt surface is modified includes：Vapour phase oxidation process, liquid phase oxidation and electrochemical oxidation process, be
Several conventional surface treatment methods, will not introduce other impurities, and the electro-chemical activity of electrode felt also increases, still
It is that it is improved and few.And for example disclosed in the patent No. 201510937646.7, graphite oxide is prepared using laboratory, then oxygen
Graphite solution and graphite felt mixing are heated in a kettle., and graphite oxide is reduced into graphene-supported on graphite felt surface.This
Method is mainly laboratory preparation method, and manufacturing process need to use the raw materials such as the substantial amounts of concentrated sulfuric acid, water and alcohol, the graphene of preparation
It is very rare, it can only be prepared as laboratory sample, not possess the possibility of extensive application and preparation.The and for example patent No.
Disclosed in 200910093955.5, using the method for chemical vapor deposition in graphite felt surface deposition of carbon nanotubes, the method
It is numerous and diverse be difficult to walk, it is necessary to which raw material are carried out a variety of processing after, could be processed in chemical vapor deposition stove, it is with high costs, no
With practical industrial operation feasibility.
More than the electrode material based on prior art several modified shortcomings prepared, therefore, are modified on graphite felt surface,
The place also lifted.
The content of the invention
For drawbacks described above, it is an object of the invention to provide a kind of high activity electrode material and method of modifying, in graphite felt
During necessity of preparation, simple modified operation is added, simply, modified feedstock is cheap and easy to get, with good for method of modifying
Industrial operability, to solve the technical problem of prior art.
To achieve the above object, present invention employs following technical scheme：
A kind of high activity electrode material, applied to the electrode material field in electrochemical reaction, with basic material by adding
Work step is made suddenly, and the basic material is organic fibrous material, and the step includes basic material combing, acupuncture and forms pre- oxygen
Felt, high-temperature calcination carbonization treatment formation carbon felt and high-temperature calcination graphitization processing formation graphite felt；The basic material comb,
Acupuncture forms pre- oxygen felt, high-temperature calcination and is carbonized to be formed in carbon felt and high-temperature calcination graphitization processing formation graphite felt, chooses wherein
One of carry out activation, the activation for physics Van der Waals force absorption or chemistry organic resin be used as bonding
The chemical graft of agent.
According to the high activity electrode material described in present pre-ferred embodiments, the basic material be polyacrylonitrile fibre,
Pitch fibers, viscose rayon, phenolic fibre, the one of which of carbon fiber or many of composition.
According to the high activity electrode material described in present pre-ferred embodiments, the Van der Waals force of the physics is adsorbed as：
It is material modified to disperse to form aqueous dispersions in aqueous, fibrous material is immersed in the aqueous dispersions, by vacuumizing,
Printing or suction filtration processing carry out Van der Waals force load, dry afterwards, described material modified for high activity Carbon Materials, the high activity
Carbon Materials be graphite powder, graphene, nano-carbon powder, activated carbon powder, CNT, pyrolytic graphite, pyrolytic carbon, vapour deposition carbon in
One or several kinds.
According to the high activity electrode material described in present pre-ferred embodiments, the chemical organic resin is used as binding agent
Chemical graft be：Material modified and organic resin is configured to resin dispersion liquid, fibrous material is immersed in the resin point
In dispersion liquid, by vacuumizing or suction filtration, it is described it is material modified be high activity Carbon Materials, the high activity Carbon Materials be graphite powder,
One or several kinds in graphene, nano-carbon powder, activated carbon powder, CNT, pyrolytic graphite, pyrolytic carbon, vapour deposition carbon,
The organic resin is one kind or several in the thermosetting resins such as epoxy resin, phenolic resin, polyacrylic acid, polyamide
Kind；Select high-temperature calcination graphitization processing formation graphite felt to carry out after chemical graft, carbonization treatment need to be carried out, make binding agent carbon
Change.
According to the high activity electrode material described in present pre-ferred embodiments, the aqueous dispersions of the high activity Carbon Materials
Carbon material concentration is 0.001wt% to 20wt%.
According to the high activity electrode material described in present pre-ferred embodiments, the resin dispersion liquid of the high activity Carbon Materials
Carbon material concentration be 0.001wt% to 20wt%.
According to the high activity electrode material described in present pre-ferred embodiments, the resin dispersion liquid is immersed in fiber
Solid masses is less than the 20% of felt body itself quality.
A kind of method of modifying of high activity electrode material, is modified with organic fiber, including：
Step 1:Organic fiber raw material is arranged, combed；
Step 2：Carry out acupuncture and form pre- oxygen felt；
Step 3：Carry out high-temperature calcination carbonization treatment formation carbon felt；
Step 4：Carry out high-temperature calcination graphitization processing formation graphite felt；
Choose one of them step and carry out activation, the activation is adsorbed or changed for the Van der Waals force of physics
Organic resin as binding agent chemical graft.
According to the method for modifying described in present pre-ferred embodiments, selecting step 4 carries out the organic resin of chemistry as viscous
When tying the chemical graft of agent, in addition to step 4-1, carbonization treatment is carried out, binding agent is carbonized.
According to the method for modifying described in present pre-ferred embodiments, the Van der Waals force of the physics is adsorbed as：Modified material
Material is scattered to form aqueous dispersions in aqueous, and fibrous material is immersed in the aqueous dispersions, by vacuumizing, print or
Suction filtration processing carries out Van der Waals force load, dries afterwards；The chemical organic resin is as the chemical graft of binding agent：
Material modified and organic resin is configured to resin dispersion liquid, and fibrous material is immersed in the resin dispersion liquid, true by taking out
Empty or suction filtration.
The design philosophy of the application is to provide a kind of a kind of method of increase graphite felt surface-active, and stone is manufactured in industry
In each procedure of black felt, in combing, acupuncture, carbon felt, graphite felt four-stage, select one and handled, the mode of processing is logical
Physics or chemistry method is crossed in its area load other materials, to obtain modified graphite felt.In addition, graphite felt is made
Into the graphite felt with direction active gradient, the effect with anti-polarization.The overall every chemical property for improving graphite felt, be
It provides bigger advantage as battery electrode, industrial electrolysis and the electrode material of smelting.
Technology as a result of more than causes the present invention compared with prior art, has the following advantages that and good effect：
Firstth, support materials and solvent are used as using active carbon material, organic resin and water, it is to avoid graphite felt is treated
Other elements impurity is mixed into journey；
Secondth, absorbent charcoal material has a high-specific surface area, acidproof corrosion resistant feature, and resinae product is also cheap and easy to get
Material；
3rd, processing procedure is in combing, pre- oxygen felt, carbon felt and graphite felt four-stage, and the reaction for not using complexity is set
Standby and processing mode, therefore can be with large-scale industrial production；
4th, in relatively simple mode in graphite felt supported active carbon material, can significantly increase graphite felt
Electrochemical reaction activity, chemism is high, and higher power is obtained in the case of same current density, or in identical work(
Higher current density is obtained under rate.
Brief description of the drawings
Fig. 1 is vacuumize process schematic diagram；
Fig. 2 is that suction filtration handles schematic diagram；
Fig. 3 is roller coating schematic diagram.
Embodiment
Several preferred embodiments of the present invention are described in detail below in conjunction with accompanying drawing, but the present invention is not restricted to
These embodiments.The present invention covers any replacement, modification, equivalent method and side made in the spirit and scope of the present invention
Case.Thoroughly understand in order that the public has to the present invention, be described in detail in present invention below preferred embodiment specific thin
Section, and description without these details can also understand the present invention completely for a person skilled in the art.
The application refers to a kind of high activity electrode material, applied to the electrode material field in electrochemical reaction, with basis
Raw material is made by a series of procedure of processings, and the step includes basic material combing, acupuncture and forms pre- oxygen felt, high-temperature calcination carbon
Change processing and form carbon felt and high-temperature calcination graphitization processing formation graphite felt；Pre- oxygen is formed in basic material combing, acupuncture
Felt, high-temperature calcination are carbonized to be formed in carbon felt and high-temperature calcination graphitization processing formation graphite felt, choose one of step and carry out
Activation, the activation is the chemistry of the Van der Waals force absorption of physics or the organic resin of chemistry as binding agent
Grafting, does not use the consersion unit and processing mode of complexity, therefore can be with large-scale industrial production.
During processing and manufacturing, the basic material is polyacrylonitrile fibre, pitch fibers, viscose rayon, phenolic aldehyde fibre
Dimension, the one of which of carbon fiber or many of organic fibrous material composition.
The method for saying physics below, the Van der Waals force of the physics is adsorbed as：The aqueous solution is dispersed in material modified
Middle formation aqueous dispersions, fibrous material are immersed in the aqueous dispersions, by vacuumize, print or suction filtration processing carry out model
De Huali load, dry afterwards, it is described it is material modified be high activity Carbon Materials, the high activity Carbon Materials are graphite powder, graphite
One or several kinds in alkene, nano-carbon powder, activated carbon powder, CNT, pyrolytic graphite, pyrolytic carbon, vapour deposition carbon, it is described
The carbon material concentration of the aqueous dispersions of high activity Carbon Materials is 0.001wt% to 20wt%.
Then method chemical is said, the chemical organic resin is as the chemical graft of binding agent：Modified
Material and organic resin are configured to resin dispersion liquid together, and fibrous material is immersed in the resin dispersion liquid, true by taking out
The processing of empty or suction filtration, it is described it is material modified be high activity Carbon Materials, the high activity Carbon Materials are graphite powder, graphene, nanometer
One or several kinds in carbon dust, activated carbon powder, CNT, pyrolytic graphite, pyrolytic carbon, vapour deposition carbon, organic tree
Fat is the one or more in the thermosetting resins such as epoxy resin, phenolic resin, polyacrylic acid, polyamide；If selection
If high-temperature calcination graphitization processing formation graphite felt carries out chemical graft, then after carrying out, also need to carry out carbonization treatment, make bonding
Agent is carbonized.The carbon material concentration of the resin dispersion liquid of the high activity Carbon Materials is 0.001wt% to 20wt%.In addition, described
Resin dispersion liquid is immersed in 20% that solid masses in fiber is less than felt body quality itself.
The application further mentions a kind of method of modifying of high activity electrode material, is modified with organic fiber, including following
Step：
Step 1:Organic fiber raw material is arranged, combed；
Step 2：Carry out acupuncture and form pre- oxygen felt；
Step 3：Carry out high-temperature calcination carbonization treatment formation carbon felt；
Step 4：Carry out high-temperature calcination graphitization processing formation graphite felt；
In above step, choose one of them step and carry out activation, the activation is the model of physics
De Huali adsorb or chemistry organic resin as binding agent chemical graft.If selecting the Van der Waals force absorption of physics to carry out
If processing, by vacuumize, print or suction filtration processing carry out Van der Waals force load after, as long as drying process is all right；Such as
Fruit is if selecting step 4 carries out chemical graft of the organic resin of chemistry as binding agent, after progress, in addition it is also necessary to carry out step
4-1 carbonization treatments, make binding agent be carbonized.
In addition, carry out chemistry organic resin as binding agent chemical graft when, the organic resin binding agent used, its
The gross mass that solids content accounts for solution is less than 30%.
In summary, it is known that the application be from organic fibrous material to graphite felt during, to combing rank therein
Section, pre- oxygen felt stage, carbon felt stage and graphite felt stage, reprocessing is modified after shaping, so following examples are only right
This four steps is illustrated.
Embodiment one
After graphite felt formation, handled using phenolic resin as binding agent.
Dispersion liquid is prepared, 1-200g water soluble phenol resins and 1-100g activated carbons are put into 1L deionized waters, stirred
Mix 1-3 hours.Forming phenolic resin and activated carbon all has the resin dispersion liquid of concentration gradient.Graphite felt is cut into regular
Square, the length of side is cut out according to being actually needed, and 50*50mm is cut into here2, weigh M0.
As shown in figure 1, activated carbon resin dispersion liquid is poured into the higher container of sealing, graphite felt 10 is put into scattered
In liquid 20, closure is covered.
Using vavuum pump to carrying out vacuumize process with upper container, processing time is 1-3 hour.
The graphite felt handled well is taken out, 2-5 hour is dried at 150 DEG C.
Dried graphite felt is with 700-900 DEG C of processing in vacuum either inert gas stove, and processing time is 1-10
Individual hour.Weigh M1 after cooling.
M=M0-M1, is the quality for entering carbon outside.
The present invention is a kind of manufacture method of modified graphite felt, is characterized in by the use of organic resin as binding agent, other
Active carbon material is as material modified, and organic resin is carbonized in the environment of high temperature anaerobic.Graphite felt after modification is not mixed
Such as other species element impurities, active carbon material is introduced, can be very good to improve the chemical property of graphite felt.
Embodiment two
In the carbon felt stage, handled using physical method.
Aqueous dispersions are prepared, 1-100g activated carbons are put into 1L deionized water, stir 1-3 small on agitator
When, form the aqueous dispersions of stable and uniform.
Graphite felt is cut into regular square, the length of side is cut out according to being actually needed, and 50*50mm2 is cut into here, is claimed
Weight M0.
As shown in Fig. 2 filter paper is placed in Buchner funnel 40, carbon felt 11 is placed on filter paper, fallen in Buchner funnel
Enter activated carbon aqueous dispersions 50, pouring volume is 100ml.
Suction filtration is carried out using vavuum pump, untill the liquid in Buchner funnel is all drained.
Treated carbon felt 11 carries out graphitization processing under 1500-3000 DEG C of vacuum or inert gas environment.
Embodiment three
In the stage of combing, handled using physical method.
Aqueous dispersions are prepared, 1-100g activated carbons are put into 1L deionized water, stir 1-3 small on agitator
When, form the aqueous dispersions of stable and uniform.
A certain amount of basic material is taken, is put into opener and is handled, during processing, above-mentioned step is slowly added to
Activated carbon aqueous dispersions in rapid.The mass ratio of basic material and activated carbon aqueous dispersions is controlled 10:1-1:Between 1.
Treated fibrous material obtains modified graphite felt by acupuncture, carbonization, graphitization.
Example IV
In acupuncture stage, handled using epoxy resin as binding agent.
Dispersion liquid 60 is prepared, 1-200g water soluble phenol resins and 1-100g activated carbons are put into 1L deionized waters,
Stirring 1-3 hours.Forming phenolic resin and activated carbon all has the resin dispersion liquid of concentration gradient.As shown in figure 3, resin point
Dispersion liquid is poured into simple funnel 70, it is slowly flowed down.
Resin dispersion liquid is brushed the surface of fibrofelt 12 using roller before the needle-punching run of fibrofelt 12.
Then pre- oxygen felt carbonization, graphitization are carried out and obtains modified graphite felt.
Technology as a result of more than causes the present invention compared with prior art, has the following advantages that and good effect：
Firstth, support materials and solvent are used as using active carbon material, organic resin and water, it is to avoid graphite felt is treated
Other elements impurity is mixed into journey；
Secondth, absorbent charcoal material has a high-specific surface area, acidproof corrosion resistant feature, and resinae product is also cheap and easy to get
Material；
3rd, processing procedure is in combing, pre- oxygen felt, carbon felt and graphite felt four-stage, and the reaction for not using complexity is set
Standby and processing mode, therefore can be with large-scale industrial production；
4th, in relatively simple mode in graphite felt supported active carbon material, can significantly increase graphite felt
Electrochemical reaction activity, chemism is high, and higher power is obtained in the case of same current density, or in identical work(
Higher current density is obtained under rate..
According to embodiments of the invention as described above, these embodiments do not have all details of detailed descriptionthe, not yet
It is only described specific embodiment to limit the invention.Obviously, as described above, it can make many modifications and variations.This explanation
Book is chosen and specifically describes these embodiments, is in order to preferably explain the principle and practical application of the present invention, so that affiliated
Technical field technical staff can be used using modification of the invention and on the basis of the present invention well.The present invention is only by right
The limitation of claim and its four corner and equivalent.
Claims (10)
1. a kind of high activity electrode material, applied to the electrode material field in electrochemical reaction, it is characterised in that with basic former
Material is made by procedure of processing, and the basic material is organic fibrous material, and the step includes basic material combing, needling shape
Into pre- oxygen felt, high-temperature calcination carbonization treatment formation carbon felt and high-temperature calcination graphitization processing formation graphite felt；
The basic material is combed, acupuncture forms pre- oxygen felt, high-temperature calcination and is carbonized and to be formed at carbon felt and high-temperature calcination graphitization
Reason is formed in graphite felt, is chosen one of them and is carried out activation,
The activation is the chemical graft of the Van der Waals force absorption of physics or the organic resin of chemistry as binding agent.
2. high activity electrode material as claimed in claim 1, it is characterised in that the basic material be polyacrylonitrile fibre,
Pitch fibers, viscose rayon, phenolic fibre, the one of which of carbon fiber or many of composition.
3. high activity electrode material as claimed in claim 1, it is characterised in that the Van der Waals force of the physics is adsorbed as：
It is material modified to disperse to form aqueous dispersions in aqueous, fibrous material is immersed in the aqueous dispersions, by vacuumizing,
Printing or suction filtration processing carry out Van der Waals force load, dry afterwards, described material modified for high activity Carbon Materials, the high activity
Carbon Materials be graphite powder, graphene, nano-carbon powder, activated carbon powder, CNT, pyrolytic graphite, pyrolytic carbon, vapour deposition carbon in
One or several kinds.
4. high activity electrode material as claimed in claim 1, it is characterised in that the chemical organic resin is used as binding agent
Chemical graft be：Material modified and organic resin is configured to resin dispersion liquid, fibrous material is immersed in the resin point
In dispersion liquid, by vacuumizing or suction filtration, it is described it is material modified be high activity Carbon Materials, the high activity Carbon Materials be graphite powder,
One or several kinds in graphene, nano-carbon powder, activated carbon powder, CNT, pyrolytic graphite, pyrolytic carbon, vapour deposition carbon,
The organic resin is one kind or several in the thermosetting resins such as epoxy resin, phenolic resin, polyacrylic acid, polyamide
Kind；Select high-temperature calcination graphitization processing formation graphite felt to carry out after chemical graft, carbonization treatment need to be carried out, make binding agent carbon
Change.
5. high activity electrode material as claimed in claim 3, it is characterised in that the aqueous dispersions of the high activity Carbon Materials
Carbon material concentration is 0.001wt% to 20wt%.
6. high activity electrode material as claimed in claim 4, it is characterised in that the resin dispersion liquid of the high activity Carbon Materials
Carbon material concentration be 0.001wt% to 20wt%.
7. high activity electrode material as claimed in claim 4, it is characterised in that the resin dispersion liquid is immersed in fiber
Solid masses is less than the 20% of felt body itself quality.
8. a kind of method of modifying of high activity electrode material, it is characterised in that be modified with organic fiber, including：
Step 1:Organic fiber raw material is arranged, combed；
Step 2：Carry out acupuncture and form pre- oxygen felt；
Step 3：Carry out high-temperature calcination carbonization treatment formation carbon felt；
Step 4：Carry out high-temperature calcination graphitization processing formation graphite felt；
Choose one of them step and carry out activation,
The activation is the chemical graft of the Van der Waals force absorption of physics or the organic resin of chemistry as binding agent.
9. method of modifying as claimed in claim 8, it is characterised in that selecting step 4, carries out the organic resin of chemistry as viscous
When tying the chemical graft of agent, in addition to step 4-1, carbonization treatment is carried out, binding agent is carbonized.
10. method of modifying as claimed in claim 8, it is characterised in that the Van der Waals force of the physics is adsorbed as：Modified material
Material is scattered to form aqueous dispersions in aqueous, and fibrous material is immersed in the aqueous dispersions, by vacuumizing, print or
Suction filtration processing carries out Van der Waals force load, dries afterwards；The chemical organic resin is as the chemical graft of binding agent：
Material modified and organic resin is configured to resin dispersion liquid, and fibrous material is immersed in the resin dispersion liquid, true by taking out
Empty or suction filtration.
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| CN109671953A (en) * | 2017-10-13 | 2019-04-23 | 中国科学院大连化学物理研究所 | A kind of electrode material for all-vanadium flow battery and its preparation and application |
| CN109671957A (en) * | 2017-10-13 | 2019-04-23 | 中国科学院大连化学物理研究所 | A kind of electrode material for all-vanadium flow battery and its preparation and application |
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| CN113235307A (en) * | 2021-04-26 | 2021-08-10 | 因达孚先进材料(苏州)有限公司 | Hard heat-preservation viscose-based graphite felt and preparation method thereof |
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| CN109671953A (en) * | 2017-10-13 | 2019-04-23 | 中国科学院大连化学物理研究所 | A kind of electrode material for all-vanadium flow battery and its preparation and application |
| CN109671957A (en) * | 2017-10-13 | 2019-04-23 | 中国科学院大连化学物理研究所 | A kind of electrode material for all-vanadium flow battery and its preparation and application |
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| CN117810466B (en) * | 2023-12-25 | 2024-07-12 | 辽宁奥亿达新材料股份有限公司 | Preparation method of vanadium battery graphite felt |
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