CN106384833B - A kind of vanadium battery electrode component of modified carbon fiber felt and graphite collector composition - Google Patents
A kind of vanadium battery electrode component of modified carbon fiber felt and graphite collector composition Download PDFInfo
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- CN106384833B CN106384833B CN201610994060.9A CN201610994060A CN106384833B CN 106384833 B CN106384833 B CN 106384833B CN 201610994060 A CN201610994060 A CN 201610994060A CN 106384833 B CN106384833 B CN 106384833B
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- 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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0226—Composites in the form of mixtures
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- 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
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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
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- 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
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- Y02E60/50—Fuel cells
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Abstract
The present invention provides the vanadium battery electrode components that a kind of modified carbon fiber felt and graphite collector are constituted.Modified carbon fiber felt surface is formed with C=O bond group, the graphite collector is the composite material collector being made of expanded graphite and thermosetting resin, oxygen-containing group is contained on the expanded graphite surface, and the quality of the expanded graphite is the 15%~25% of afflux weight.Compared with prior art, the advantages that vanadium battery electrode component that modified carbon fiber felt and graphite collector are constituted according to the present invention has method and process simple, and graphite-filled amount is few, cheap.
Description
Technical field
The invention belongs to vanadium cell technical fields, it relates in particular to a kind of modified carbon fiber felt and graphite collector structure
At vanadium battery electrode component.
Background technique
Vanadium oxide reduction flow battery (referred to as full vanadium cell or vanadium cell) is a kind of chemical energy storage electricity of Novel pollution-free
Pond belongs to flow battery, solid-state reaction does not occur, and with electric current transfer capability, good, structure flexible design, cost are reasonable, grasp
Make the advantages that easy.
The main composition of vanadium cell has electrode, film, collector etc..Collector main effect in vanadium cell is to completely cut off just
Electrolyte liquid, and kinetic current export is come, thus, it is desirable that the collector of vanadium cell has good electric conductivity and barrier
Property, and since the electrolyte of vanadium cell is acidic environment, it is necessary to it is required that collector has preferable corrosion resistance.In people
In past research, the collector of the types such as metal class, graphite-like and conducing composite material class was attempted respectively, but long-term
It is found during use, in place of all kinds of equal Shortcomings of collector.For example, metal class collector there are corrosion resistances not
Well, the disadvantages of expensive.
By people it is long-term the study found that graphite-like collector in vanadium cell using cost performance is highest in collector
's.But graphite-like collector the disadvantages of there are corrosion resistance and poor mechanicalnesses.Therefore, in recent years, how people are for mention
The corrosion resistance and mechanicalness of high graphite-like collector have done a large amount of research.Common method is by graphite powder in certain pressure
Then the graphite of compression moulding is immersed in the solution of macromolecule polymeric material by compression moulding under power, pass through the side vacuumized
Formula makes macromolecular liquid infiltration into graphite collector after molding.For such method, due to macromolecule viscosity and its
His reason, macromolecular liquid can not be immersed in well in pressed graphite collector micropore, therefore, for collector
There is no very good raisings for corrosion resistance and mechanical performance.
In the processing method of current vanadium redox battery carbon fiber felt, oxidizing process (air common are
Oxidizing process, liquid phase oxidation, electrochemical oxidation process etc.), plasma processing method, surface deposition etc., but these processing methods
There is the shortcomings that energy consumption height, unsuitable large-scale production.
Summary of the invention
It is above-mentioned existing in the prior art one or more it is an object of the present invention to solving the problems, such as.For example, this hair
The bright first purpose is to provide the vanadium battery electrode component of a kind of modified carbon fiber felt and graphite collector composition.
To achieve the goals above, an aspect of of the present present invention provides a kind of modified carbon fiber felt and graphite collector is constituted
Vanadium battery electrode component.Modified carbon fiber felt surface is formed with C=O bond group, and the graphite collector is by swollen
The composite material collector that swollen graphite and thermosetting resin are constituted, oxygen-containing group, the expansion are contained in the expanded graphite surface
The quality of graphite is the 15%~25% of afflux weight.
The vanadium battery electrode component that modified carbon fiber felt according to the present invention and graphite collector are constituted, the modified carbon fiber
The C=O bond group of the surface formation of felt is tieed up by graphited carbonnitrogen bond incomplete on carbon fiber felt surface, the heterocycle of carbon containing nitrogen
Or not cyclic carbonnitrogen bond converts.
Compared with prior art, the vanadium battery electrode component that modified carbon fiber felt and graphite collector are constituted according to the present invention
The advantages that simple with method and process, graphite-filled amount is few, cheap.
Specific embodiment
Hereinafter, modified carbon fiber felt according to the present invention and graphite collection will be described in detail in conjunction with exemplary embodiment
The vanadium battery electrode component that fluid is constituted.
The vanadium cell electricity that modified carbon fiber felt and graphite collector in an exemplary embodiment of the present invention is constituted
Pole component, modified carbon fiber felt surface are formed with C=O bond group, and the graphite collector is by expanded graphite and heat
The composite material collector that thermosetting resin is constituted, oxygen-containing group, the quality of the expanded graphite are contained in the expanded graphite surface
It is the 15%~25% of afflux weight.
For the granularity of expanded graphite, as long as within the scope of the preparation of expanded graphite, it is preferred that expansion stone
The granularity of ink is 50 μm~150 μm.
It is too thin to bear incessantly pressure in the assembling process of vanadium cell and damage for the thickness of collector
It ruins；It is too thick to will increase corresponding production cost.So the thickness of collector can be 0.5mm~1.5mm.
More than, modified carbon fiber felt is combined together with graphite collector, in conjunction with method application conventional method.
The vanadium battery electrode that modified carbon fiber felt and graphite collector in an exemplary embodiment of the present invention are constituted
The preparation method of component, the modified carbon fiber felt includes:
1) carbon fiber felt carries out cleaning pretreatment
It is the impurity for removing carbon fiber felt surface to the purpose that carbon fiber felt carries out cleaning pretreatment.It can be with using ultrasonic wave
Wash away the washable impurity removed and hydrophobicity grease type attachment in some carbon fiber felt graphitizing processes on carbon fiber felt.
It is preferred, therefore, that can be finished by carbon fiber felt in the case where frequency is the frequency of 5kHz~15kHz ultrasound 15 minutes~30 minutes
Afterwards, it is put into baking oven drying.However the invention is not limited thereto, the method that can carry out cleaning pretreatment to carbon fiber felt also may be used.When
So, used carbon fiber felt can not also carry out carbon fiber felt cleaning pre- place on not influencing technical effect of the invention
Reason.
2) carbon fiber felt surface introduces C=O bond group
The concentrated sulfuric acid and distilled water volume are prepared than the mixed treating liquid A for 8:1~5:1.The carbon fiber that will be obtained after pretreatment
Dimension felt is completely immersed in mixed treating liquid A, after temperature is cooled to room temperature, is placed 12 hours~36 hours, is obtained mixed system
B.The vanadic anhydride of concentrated sulfuric acid quality 1%~5% in the mixed treating liquid A is slowly added into mixed system B, under room temperature
Stirring stops stirring, is cooled to room temperature, obtains mixed system C after vanadic anhydride is completely dissolved.In mixed system C
It is slowly added to the hydrogen peroxide of 5~10 times of the vanadic anhydride amount of substance, wherein the mass concentration of hydrogen peroxide is greater than 30%.It is double
It after oxygen water is added, reacts 2 hours~4 hours, takes out carbon fiber felt.
More than, the main function of mixed treating liquid A is to provide acidic environment and the part on removal carbon fiber felt surface is miscellaneous
Matter group.For mixed treating liquid A, as long as the acid that vanadic anhydride can be made to dissolve.However due to all-vanadium flow
The main component of battery electrolyte is the substance of containing sulfate radicals and vanadium, and sulfuric acid can dissolve vanadic anhydride, will not be to electricity
It solves and introduces other impurity in liquid, to will not influence service efficiency and the service life of vanadium cell, will not cause to vanadium cell can not
The influence of expectation.It is preferred, therefore, that mixed treating liquid A is 98% concentrated sulfuric acid of mass fraction and water volume ratio is 8:1~5:1's
Mixed liquor.
It " places 12 hours~36 hours, obtains mixed system B ", here, the main purpose of placement is removed on carbon fiber
It is partially soluble in the impurity of sulfuric acid.Standing time is longer, first is that after may insure that carbon fiber felt immerses mixed treating liquid A, system
Temperature be down to room temperature completely, second is that the removing of maximum possible is attached to the impurity on carbon fiber felt surface.
The vanadium battery electrode that modified carbon fiber felt and graphite collector in an exemplary embodiment of the present invention are constituted
Component, the composite material afflux preparation include:
1) preparation of expanded graphite
Weighing according to mass ratio is crystalline flake graphite: the concentrated sulfuric acid: potassium permanganate: hydrogen peroxide: vanadic anhydride=100:50:1:
The raw material of 25:1~100:25:5:50:3.
Crystalline flake graphite is added in the concentrated sulfuric acid, potassium permanganate is then added, is subsequently added into vanadic anhydride, is slowly stirred 10
Minute~20 minutes, so that above-mentioned substance is uniformly mixed；While being slowly stirred, hydrogen peroxide is added dropwise, reacts 2 after being added dropwise
Minute~5 minutes.Reaction temperature is increased to 50 DEG C~70 DEG C, is reacted 30 minutes~50 minutes while being slowly stirred, is stopped
Stirring, is cooled to room temperature, and adding volume is 2~4 times of reaction system volume of distilled water, after mixing evenly, vacuum filtration.It will filter
Graphite afterwards is dry after distilling water washing.
By the graphite after drying at lower roasting 15 minutes~30 minutes of 800 DEG C~950 DEG C, it is cooled to room temperature, obtains swollen
Swollen graphite.
More than, crystalline flake graphite can be commercial product.Preferably, the granularity of crystalline flake graphite can be 50 μm~100 μm.
In the preparation process of expanded graphite, the purpose of addition vanadic anhydride and hydrogen peroxide is therebetween can be anti-
It answers, generating has the peroxidating vfanadium compound of strong nucleophilicity can be with introducing portion oxygen-containing group while aoxidizing to graphite
Group.The oxygen-containing group being introduced into can be formed in the curing reaction in later period with the polar group of thermosetting resin new chemical bond or
Stronger physical absorption can enhance the binding ability of expanded graphite and thermosetting resin, so that it is guaranteed that using well
Graphite is not easy to be stripped out from thermo set matrix material in journey.
The purpose of remaining graphite washing is the impurity for removing graphite surface after suction filtration.For example, pumping can be washed with distilled water
The mode of filter is cleaned.However, the present invention is not limited thereto, other modes that can be cleaned also may be used.Preferably, with graphite after suction filtration
1~3 times of volume of distillation water washing, is then filtered by vacuum, and repeats step 3 time or more, until washes clean graphite surface
Impurity.
2) processing of delaminating is carried out to expanded graphite
By expanded graphite obtained above and distilled water according to the ratio that volume ratio is 1:1~1:3 in 15~35KHz frequency
Lower ultrasonic treatment 15 minutes~30 minutes, then filters, dry, pulverizes, and obtain delaminating treated expanded graphite.So
And the present invention to expanded graphite delaminate processing method it is without being limited thereto, other methods also may be used.
3) curing molding after the expanded graphite after delaminating is mixed with thermosetting resin fluid
It by mass, is thermosetting property by quality and the thermosetting resin and quality of standby afflux weight 75%~85% of drawing up
The diluent of resin quality 20%~40% uniformly mixes, and obtains dispersion liquid, and be added into dispersion liquid and draw up standby afflux constitution
15%~25% expanded graphite of amount obtains mixture.By mixture curing molding, expanded graphite and thermosetting resin are obtained
The composite material collector of composition.
More than, if thermosetting resin is the resin for itself being unable to heat cure, such as epoxy resin or its modified tree
When rouge, it is necessary to curing agent be added in the mixture.Curing agent is sells the resin solidification that can prevent itself from heat cure on the market
?.According to known in the art, the additional amount of curing agent is different according to the type of curing agent, and curing agent additional amount can be corresponding
Change, as long as can prevent itself from thermosetting resin solidify.Preferably, the curing agent can be solid for modified amine
Agent, additional amount can be the 16%~30% of required thermosetting resin quality.If thermosetting resin is with itself heat
The resin of curing performance, does not need the addition of curing agent in preparation process, for example, with itself Thermocurable can resin it is double
There is no need to add curing agent for maleimide resin, cyanate ester resin and their modified resin.Certainly, thermosetting resin
It is also possible to itself be unable to the combination of the resin and the resin with itself Thermocurable energy of heat cure, is also required for solidifying at this time
The addition of agent.
The effect of acetone is diluent, is in order to which thermosetting resin to be diluted.Do not influencing the technology of the present invention effect
On the basis of, other diluents also may be used.
For the curing molding of mixture, routine techniques can be by mixture curing molding.Preferably, by institute
It states mixture to be ultrasonically treated 10 minutes~30 minutes under conditions of frequency is 5kHz~20kHz, mold is subsequently poured into, normal
Solidify 24 hours~48 hours under temperature, vacuumized conditions.
Oxygen-containing group is contained on the expanded graphite surface, the expanded graphite can be draw up standby electrode quality 15%~
25%, thermosetting resin can be to draw up for the 75%~85% of electrode quality.
For the granularity of expanded graphite, as long as within the scope of the preparation of expanded graphite, it is preferred that expansion stone
The granularity of ink is 50 μm~150 μm.
For the thickness for the composite material collector that expanded graphite and thermosetting resin are constituted, it is too thin may be in vanadium
It bears not living pressure and damage in the assembling process of battery；It is too thick to will increase corresponding production cost.So expanded graphite and heat
The thickness for the composite material collector that thermosetting resin is constituted can be 0.5mm~1.5mm.Preferably, in order to collector have it is higher
Cost performance, the thickness for the composite material collector that expanded graphite and thermosetting resin are constituted can be 1mm~1.5mm.
Exemplary embodiment of the present invention is described in further detail below in conjunction with specific example.
Example 1
5cm × 8cm carbon fiber felt after cleaning pretreatment is immersed into 60ml, 98% concentrated sulfuric acid is mixed with 10ml distilled water
18 hours in acid solution.Then the vanadic anhydride of 2.5g is added, stirring to vanadic anhydride is completely dissolved.After cooling, delay
The slow hydrogen peroxide that 10.5ml mass concentration is added and is 50%, reacts 2 hours.After reaction, carbon fiber felt is taken out, distilled water is used
Washing is put into baking oven drying, obtains modified carbon fiber felt.
5g carbon fiber felt after cleaning treatment is completely immersed in the mixed liquor of 30ml pyrroles and 30ml acetone, after taking-up
It is placed 5 hours under room temperature.The mixed liquor for configuring 0.5g carbon nanotube and 20ml distilled water, is then ultrasonically treated 20 minutes
Obtain carbon nanotube liquid.It will be immersed in carbon nanotube liquid through pyrroles's treated carbon fiber felt, and 10ml then be added dropwise, concentration will be
50% hydrogen peroxide continues ultrasound and takes out carbon fiber felt after twenty minutes, dries after being washed with distilled water 4 times, obtain surface grafting
There is the carbon fiber felt of carbon nanotube.
It is that 98% concentrated sulfuric acid is added in beaker by the mass concentration of 50g, it is 50 μm that granularity, which is then added, and weight is 100g's
Crystalline flake graphite is uniformly mixed with the concentrated sulfuric acid in beaker.1g potassium permanganate is added in mixed liquor, 1g five is added after mixing
V 2 O is slowly stirred 10 minutes.Under conditions of being slowly stirred, 35% hydrogen peroxide of 25g is added, reacts 2 minutes.So
Afterwards, reaction temperature is increased to 50 DEG C, is slowly stirred lower reaction 30 minutes.After reaction, it is cooled to room temperature, is added in beaker and mixes
The distilled water stirring of 2 times of object product is closed, after mixing evenly, vacuum filtration, the graphite powder that obtains that treated.Then graphite composite powder is used
The distillation water washing of 1 times of product, vacuum filtration.Graphite powder repeats after being washed with distilled water three times, and it is small to be put into 60 DEG C of drying boxes dry 3
When.Graphite after drying is put into Muffle furnace, roasting temperature 30 minutes of 800 DEG C, after close Muffle furnace, by stone
Ink, which is cooled to room temperature, obtains expanded graphite.
1 times of its volume of distilled water of graphite after cooling is cleaned by ultrasonic 15 minutes under the frequency of 15KHz, then very
Empty pump filter is put into 70 DEG C of drying box dry 3h, is put into mortar after taking-up, is ground into the stone that granularity is 50 μm~100 μm
Ink powder is to get the expanded graphite to after delaminating.
It weighs 650g epoxy resin (trade mark E-51) to be put into beaker, 130g acetone reagent is added in the epoxy, stirs
It mixes uniformly, obtains mixed dispersion liquid.Graphite powder 100g after above-mentioned be disposed is added in mixed dispersion liquid, stirs evenly
Afterwards, 703 modified firming agent 130g are added, obtain final mixed dispersion liquid.
By final mixed dispersion liquid, ultrasound is poured into mold after 30 minutes under the frequency of 5KHz, in vacuum, room temperature
Under the conditions of solidify 24 hours, obtain the vanadium cell collector with a thickness of 1.1mm, volume resistivity is 0.2 Ω m.
The composite material collector that expanded graphite and thermosetting resin are constituted is assembled into list with modified carbon fiber felt
After battery, after 200 charge and discharge cycles, coulombic efficiency (discharge capacity and the ratio between the charging capacity with circulation) is battery
87.2%, energy efficiency 79.9%.
Example 2
7cm × 8cm carbon fiber felt after progress cleaning pretreatment is immersed into 70ml, 98% concentrated sulfuric acid and 10ml distilled water are mixed
36 hours in the acid solution of conjunction.Then the vanadic anhydride of 3.5g is added, it is cooling after vanadic anhydride is completely dissolved, slowly
The hydrogen peroxide solution that 20ml mass concentration is 70% is added, reacts 3 hours.After reaction, carbon fiber felt is taken out, distilled water is used
Washing, is put into baking oven and dries to obtain modified carbon fiber felt.
10g carbon fiber felt after cleaning treatment is completely immersed in the mixed liquor of 60ml pyrroles and 20ml acetone, after taking-up
It places 6 hours at normal temperature.The mixed liquor for configuring 0.8g carbon nanotube and 20ml distilled water, is then ultrasonically treated 25 points
Clock obtains carbon nanotube liquid.It will be immersed in carbon nanotube liquid through pyrroles's treated carbon fiber felt, and 10ml then be added dropwise, concentration will be
75% hydrogen peroxide continues ultrasound and takes out carbon fiber felt after 30 minutes, dries after being washed with distilled water 4 times, obtain surface grafting
There is the carbon fiber felt of carbon nanotube.
It is that 98% concentrated sulfuric acid is added in beaker by the mass concentration of 25g, it is 100 μm that granularity, which is then added, weight 100g
Crystalline flake graphite uniformly mixed with the concentrated sulfuric acid in beaker.5g potassium permanganate is added in mixed liquor, 3g is added after mixing
Vanadic anhydride is slowly stirred 20 minutes.Under conditions of being slowly stirred, 35% hydrogen peroxide of 50g is added, reacts 5 minutes.So
Afterwards, reaction temperature is increased to 70 DEG C, is slowly stirred lower reaction 50 minutes.After reaction, it is cooled to room temperature, is added in beaker and mixes
The distilled water stirring of 4 times of object product is closed, after mixing evenly, vacuum filtration, the graphite powder that obtains that treated.Then graphite composite powder is used
The distillation water washing of 3 times of product, vacuum filtration.Graphite powder repeats after being washed with distilled water three times, and it is small to be put into 70 DEG C of drying boxes dry 2
When.Graphite after drying is put into Muffle furnace, roasting temperature 15 minutes of 950 DEG C, after close Muffle furnace, by stone
Ink powder, which is cooled to room temperature, obtains expanded graphite.
3 times of its volume of distilled water of graphite after cooling is cleaned by ultrasonic 30 minutes under the frequency of 35KHz, then very
Empty pump filter is put into 70 DEG C of drying box dry 3h, is put into mortar after taking-up, be ground into the graphite powder that granularity is DEG C to get
Expanded graphite to after delaminating.
400g epoxy resin (trade mark E-51) is weighed to be put into beaker, in the epoxy be added 160g concentration be 160g without
Water-ethanol reagent, stirs evenly, and obtains mixed dispersion liquid.Graphite powder after above-mentioned be disposed is added in mixed dispersion liquid
100g is added 593 curing agent 100g, obtains final mixed dispersion liquid after mixing evenly.
By final mixed dispersion liquid, ultrasound is after ten minutes poured into mold under the frequency of 20KHz, in vacuum, room temperature
Under the conditions of solidify 48 hours, obtain the vanadium cell collector with a thickness of 0.98mm, volume resistivity is 0.3 Ω m.
The composite material collector that expanded graphite and thermosetting resin are constituted is assembled into list with modified carbon fiber felt
After battery, coulombic efficiency improves 10.4%, and energy efficiency improves 8.8%.After being assembled into monocell, battery is passing through 200 times
After charge and discharge cycles, coulombic efficiency (discharge capacity and the ratio between the charging capacity with circulation) is 88.4%, and energy efficiency is
80.2%.
In conclusion the vanadium battery electrode component that modified carbon fiber felt of the invention and graphite collector are constituted, has energy
Consume the advantages that low, reaction is mild, easy to operate and is suitable for industrial production.
Although those skilled in the art should be clear above by combining exemplary embodiment to describe the present invention
Chu can carry out exemplary embodiment of the present invention each without departing from the spirit and scope defined by the claims
Kind modifications and changes.
Claims (7)
1. the vanadium battery electrode component that a kind of modified carbon fiber felt and graphite collector are constituted, which is characterized in that the carbon modified
Fibrofelt surface is formed with C=O bond group, the graphite collector be made of expanded graphite with thermosetting resin it is compound
Oxygen-containing group is contained on material collector, the expanded graphite surface, and the quality of the expanded graphite is the 15% of afflux weight
~25%, the preparation method of the modified carbon fiber felt includes:
C=O bond group is introduced on carbon fiber felt surface；
Washing is introduced the carbon fiber felt of C=O bond group, and is dried,
It is wherein, described the step of carbon fiber felt surface introduces C=O bond group are as follows:
Carbon fiber felt is immersed in mixed treating liquid A, it is cooling, obtain mixed system B, the mixed treating liquid A be the concentrated sulfuric acid with
Distilled water volume is than the mixed liquor for 8:1~5:1；
Vanadic anhydride is added in mixed system B, until vanadic anhydride is completely dissolved, it is cooling, obtain mixed system C；
It is slowly added to hydrogen peroxide in mixed system C, sufficiently after reaction, takes out carbon fiber felt, wherein the addition of the hydrogen peroxide
Amount is 5~10 times of the vanadic anhydride material mass, and hydrogen peroxide mass concentration is greater than 30%.
2. the vanadium battery electrode component that modified carbon fiber felt according to claim 1 and graphite collector are constituted, feature
It is, the C=O bond group that the surface of the modified carbon fiber felt is formed is by graphited carbon incomplete on carbon fiber felt surface
Nitrogen key, the heterocycle of carbon containing nitrogen or not cyclic carbonnitrogen bond convert.
3. the vanadium battery electrode component that modified carbon fiber felt according to claim 1 and graphite collector are constituted, feature
It is, the granularity of the expanded graphite is 50 μm~150 μm.
4. the vanadium battery electrode component that modified carbon fiber felt according to claim 1 and graphite collector are constituted, feature
Be, the collector with a thickness of 0.5mm~1.5mm.
5. the vanadium battery electrode component that modified carbon fiber felt according to claim 1 and graphite collector are constituted, feature
It is, the additional amount of the vanadic anhydride is 1%~5% of concentrated sulfuric acid quality in the mixed treating liquid A.
6. the vanadium battery electrode component that modified carbon fiber felt according to claim 1 and graphite collector are constituted, feature
It is, the composite material afflux preparation includes:
Prepare expanded graphite；
Processing of delaminating is carried out to expanded graphite；
Curing molding after expanded graphite after delaminating is mixed with thermosetting resin fluid, obtains expanded graphite and thermosetting resin structure
At composite material collector,
Wherein, described the step of preparing expanded graphite are as follows:
By mass, crystalline flake graphite is weighed: the concentrated sulfuric acid: potassium permanganate: hydrogen peroxide: vanadic anhydride=100:50:1:25:1~
100:25:5:50:3；
Crystalline flake graphite is added in the concentrated sulfuric acid, potassium permanganate and vanadic anhydride are successively added during stirring, then exists
Hydrogen peroxide is added dropwise while stirring, being heated with stirring to reaction terminates, and it is cooling, it is dry after washing；
Graphite after drying is roasted at 800 DEG C~950 DEG C, obtains expanded graphite after cooling.
7. the vanadium battery electrode component that modified carbon fiber felt according to claim 6 and graphite collector are constituted, feature
It is, the granularity of the crystalline flake graphite is 50 μm~100 μm.
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| CN106505219B (en) * | 2016-11-11 | 2019-03-15 | 攀钢集团攀枝花钢铁研究院有限公司 | Vanadium redox flow battery electrode component |
| CN111933456A (en) * | 2020-08-11 | 2020-11-13 | 苏州柯诺思高新材料有限公司 | MnO (MnO)2Preparation method of/carbon fiber composite electrode and capacitor with same |
| CN114068959B (en) * | 2021-11-23 | 2023-10-27 | 成都先进金属材料产业技术研究院股份有限公司 | Method for improving activity of carbon fiber felt for vanadium battery |
| CN114094120B (en) * | 2021-11-23 | 2023-10-27 | 成都先进金属材料产业技术研究院股份有限公司 | Integrated graphite electrode for vanadium battery and vanadium battery |
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| CN1845368A (en) * | 2006-03-10 | 2006-10-11 | 清华大学深圳研究生院 | Current collection plate for all vanadium redox flow battery |
| CN103066287A (en) * | 2012-11-30 | 2013-04-24 | 承德万利通实业集团有限公司 | Treatment method of carbon felt for vanadium batteries |
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