CN110534757A - High performance carbon electrode and preparation method thereof - Google Patents
High performance carbon electrode and preparation method thereof Download PDFInfo
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- CN110534757A CN110534757A CN201910859384.5A CN201910859384A CN110534757A CN 110534757 A CN110534757 A CN 110534757A CN 201910859384 A CN201910859384 A CN 201910859384A CN 110534757 A CN110534757 A CN 110534757A
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
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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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a kind of high performance carbon electrodes and preparation method thereof, the step of carbonization the method includes the step of carbon fibre material/gel complex material is prepared by sol-gel method and by carbon fibre material/gel complex material.Carbon fibre material is immersed in sol precursor aging together during the preparation process by the present invention, allows colloidal sol can be in carbon fiber surface in-situ polymerization, to achieve the purpose that coat carbon nano-particle in carbon fiber surface.Thus the electrode prepared has high specific area and electrochemical surface area, electrochemical impedance is smaller, and it is more preferable to the catalytic performance of the electrochemical reversible of vanadium ion reaction, reaction rate can be accelerated and deepen the extent of reaction, keep all-vanadium flow battery performance more excellent.
Description
Technical field
The present invention relates to carbon electrode technical fields, specifically, being related to a kind of high performance carbon electrode and preparation method thereof.
Background technique
Flow battery is a kind of emerging electrochemical energy storage system, can operate with industry and new energy equipment is mating makes
With.Wherein electrode is the key that one of flow battery composition material, since electrode is anti-for the redox inside flow battery
Reacting environment should be provided, itself is simultaneously not involved in reaction, but the self performance of electrode material is to the Europe of kinetics, battery
Nurse resistance and redox reaction rate and the extent of reaction all have a direct impact, directly limit battery charge-discharge performance and
Stability.Up to the present, the flow battery battery material being most widely used is polypropylene/olefin base graphite felt (abbreviation carbon felt),
Carbon felt is a kind of porous material of three-dimensional, will not generate biggish pressure to the flowing of electrolyte, be conducive to the biography of active material
It leads.But the commercial scale that itself poor hydrophilicity and chemical property constrain untreated carbon felt uses.Therefore certainly
Since carbon felt is widely used as the electrode material of all-vanadium flow battery, constantly studied for the method for modifying of carbon felt.
In recent years, the modification gimmick based on carbon nanomaterial and carbon felt compound (carbon carbon is compound) is widely studied.Due to
Different carbon nanomaterials has a different advantageous property, such as high conductivity, excellent mechanical performance, biggish compares table
Area and stronger acidproof corrosion resistance etc., many different composite modified gimmicks of carbon carbon are studied and deliver, such as base
In the composite modified of graphene oxide, composite modified based on carbon nanotube and based on the composite modified of carbon nano-fiber.Although
Show excellent chemical property by the carbon felt that the above method is modified, but preparation cost is excessively high and preparation process mistake
The large-scale commercial that these are modified gimmick is constrained in complicated problem to use.
Existing composite carbon felt sample preparation methods have following several:
1. being based on graphene doping vario-property: the 1cm that is separated by of 2 8x 4cm sizes is placed in homemade electrolytic cell, and
6mg ml is added-1Graphene oxide suspension in, using two panels carbon felt as battery plus-negative plate, carried out under the voltage of 10V 3 small
When electrophoretic deposition operation be placed in 110 DEG C of baking oven overnight, in this way and make although carbon felt is taken out wash with distilled water
Obtained the composite carbon felt type product of graphene oxide doped.
2. the doping based on carbon nanotube: being dissolved in ethylenediamine by growth catalyst of the ferrocene of 2.5wt% as carbon
The source of nanotube prepares carbon nano tube-doped composite carbon felt type product by electrochemical vapor deposition.Specific operation process
It is as follows: untreated carbon felt being placed in the center of quartz ampoule, 800 DEG C are heated under the protection of Ar gas, is then slowly introducing
Ferrocene/ethylenediamine mixed solution, drops to 400 DEG C of sustained responses for quartz ampoule after reacting and starting, and is just prepared for carbon in this way and receives
The composite carbon felt type product of mitron doping.
3. the doping based on carbon nano-fiber: the carbon felt of pre-set dimension is placed in baking oven in 600 DEG C of roasting temperature 6
Hour, the nickel of 3wt% is added in carbon felt using nickel nitrate/alcohol mixed solution by equi-volume impregnating during this period, with
The composite carbon felt type product that carbon nano-fiber is generated in Carbon felt surface as carbon source carbon nano-fiber doping is made using acetylene afterwards.
However, can solve unmodified carbon fibre material electrode by nanoporous carbon/carbon fibre material complex method
The problems such as electrochemical surface area is lower, and specific surface area is lower, and chemical property is insufficient.And compound based on graphene oxide changes
Property, the composite modified and composite modifying method higher cost based on carbon nano-fiber based on carbon nanotube, preparation method is more
It is complicated.Therefore, it is badly in need of that a kind of operating process is relatively easy, the preparation method of relative inexpensiveness.
Summary of the invention
In view of the drawbacks of the prior art, the object of the present invention is to provide a kind of high performance carbon electrodes and preparation method thereof.
The purpose of the present invention is what is be achieved through the following technical solutions:
The present invention provides a kind of preparation methods of high performance carbon electrode, including carbon is prepared by sol-gel method
The step of fibrous material/gel complex material and the step of carbon fibre material/gel complex material is carbonized.
Preferably, the sol-gel method is prepared carbon fibre material/gel complex material specific step is as follows:
A1, it prepares novolac solution: under solvent condition, using formaldehyde and resorcinol as reactant, catalyst is added and carries out
Reaction, obtains novolac solution；
A2, carbon fibre material is immersed in novolac solution, aging process is carried out after sealing, the carbon fiber of gel must be coated
Material；
A3, it is submerged in organic solvent after taking out the carbon fibre material for coating gel, solvent displacement is carried out after sealing, done
Carbon fibre material/gel complex material is obtained after dry.
Preferably, in step A1, the ratio between amount of substance of the formaldehyde and resorcinol is 2:1；Resorcinol and catalysis
The molar ratio of agent is 500-1500；The mass percent of the novolac solution is 1-20%, more preferable 5%-18%.The present invention adopts
Surface is just able to achieve with the novolac solution of low concentration to be modified, and keeps the macroporous structure and high porosity of carbon fibre material；And if dense
Height is spent, then what is formed is fibre-reinforced porous carbon block.
Preferably, the catalyst is sodium carbonate.
Preferably, in step A1, the carbon fibre material includes graphite felt, carbon felt, carbon paper, at least one of carbon cloth；
The solvent is deionized water, and the catalyst is natrium carbonicum calcinatum；In step A4, the organic solvent is third
Ketone.
Preferably, in step A1, further include the steps that boric acid and/or urea are added into novolac solution；Every 100 parts of phenolic aldehyde
The boric acid and/or 0.1-5 parts of urea are added in solution.The better electrode of availability after addition boric acid and/or urea.Such as
Fruit concentration is lower than 0.1 part, and performance boost of the electrode in flow battery is unobvious, if it exceeds 5 parts, it will affect the formation of gel
With the packed structures of carbon nano-particle, electrode performance is caused to decline.
Preferably, in step A2, the temperature of the aging process is 30-60 DEG C, time 20-72h.
Preferably, in step A3, solvent displacement uses temperature specifically to handle 48-72h at 40-60 DEG C；
The drying carries out at room temperature, and drying time is 24-48 hours.
Preferably, the temperature of the carbonization be 800-2500 DEG C, carbonization time 2-6h.
Preferably, the method also includes the carbon electrode for obtaining carbonization treatment it is cooling after carry out cleaning removal of impurities, drying, cold
But the step of.
Preferably, the solvent that uses of cleaning removal of impurities is organic solvent, as n,N-Dimethylformamide solution, acetone,
Ethyl alcohol etc.；The condition of the drying are as follows: 1-4 hours dry at a temperature of 90-130 DEG C.
The present invention also provides a kind of high performance carbon electrodes prepared according to preceding method.
Carbon fibre material is immersed in sol precursor aging together during the preparation process by the present invention, the purpose done so
It is to allow organosol can be in carbon fiber surface in-situ polymerization, to reach the mesh in carbon fiber surface carbon coated nanoparticle
, the physical property that such way not will lead to carbon fibre material itself is lost, and it is good soft such as to remain carbon fibre material
Toughness and ductility, acquisition is the nano-material modified carbon fibre material of porous carbon；And if carbon fibre material is fixed on
Have in mold, using sol precursor carry out repeatedly with multiple dipping, the purpose for the arrangement is that being become using carbon fibre material
The skeleton and carrier of porous carbon nanoparticle, acquisition be fibre reinforced porous carbon materials, carbon fibre material is complete
Ductility and elasticity are lost, substance brittleness obtained is very big and incompressible, is easy to lead to sample in bending or compression process
Product are destroyed.More serious problem is, when the mass percent of novolac solution is more than 20% or the method by repeatedly impregnating
Obtained material is unable to satisfy the performance requirement of flow battery since liquid-dispersion ability is poor.
Compared with prior art, the present invention have it is following the utility model has the advantages that
1. it is more preferable using catalytic performance of the modified electrode of the present invention to the electrochemical reversible reaction of vanadium ion, it can accelerate
Reaction rate and the intensification extent of reaction.
2. it is bigger than unmodified electrode specific area using the modified electrode of the present invention, from 1.13m2 g-1It increases to
57.16m2 g-1；Electrochemical surface area is also higher, from 24.03cm2/ g increases to 32.64cm2/g。
3. it is smaller than the electrochemical impedance of unmodified electrode using the modified electrode of the present invention, it is reduced to from 1.84 Ω
0.21 Ω (active area 5*5cm).
4. its battery performance of the electrode as all-vanadium flow battery performance using the modified electrode of the present invention is more excellent
Different: modified electrode has more preferably charge-discharge energy efficiency at higher current densities, and energy efficiency is in 160mA cm-2Electricity
It is promoted from 57.16% to 75.83% under current density.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Embodiment 1
A kind of preparation method of high performance carbon electrode is present embodiments provided, including is prepared by sol-gel method
The step of carbon fibre material/gel complex material and the step of carbon fibre material/gel complex material is carbonized.Specific behaviour
It is as follows to make method:
(1) carbon felt of 5mm thickness is cut into appropriate size；
(2) carbon felt cut is immersed in appropriate configured novolac solution, and is sealed holding.The novolac solution
Specific formula is as follows: be in terms of 100 parts, with the ratio between amount of substance of formaldehyde and resorcinol for 2 to configure novolac solution parts by weight:
1, the molar ratio of resorcinol and sodium carbonate is 1300, in deionized water, using formaldehyde and resorcinol as reactant, carbon is added
Sour sodium is reacted, and the novolac solution that mass fraction is 5% is obtained；
(3) container being sealed is placed in baking oven and carries out aging process, temperature is 45 DEG C, time 26h；
(4) it after the completion of step to be aging, takes out the carbon felt in organic aerogel and is immersed in acetone soln, container is close
Envelope；
(5) container being sealed being placed in baking oven and carrying out solvent displacement set temperature is 45 DEG C, continues 60h；
(6) carbon felt after solvent is replaced is taken out, is dried at room temperature for 24 hours；
(7) dried carbon felt is placed in resistance furnace, is continually fed into nitrogen protection, in 1000 DEG C of at a temperature of high temperature
Be carbonized 5h, and heating rate is 2 DEG C of min-1；
(8) it after the carbon felt after being carbonized is cooled to room temperature, takes out carbon felt and is immersed in n,N-Dimethylformamide solution,
85 DEG C at a temperature of heating 2 hours cleaning to remove remaining organic impurities in carbon felt；
(9) take out the carbon felt after cleaning, be placed in baking oven, 110 DEG C at a temperature of it is 2 hours dry；
(10) carbon felt after drying is taken out, is placed on cooling stand-by at room temperature.
The specific area of the modified carbon felt of gained is 13.2m2 g-1, electrochemical surface area 27.0cm2/ g, electrochemistry
Impedance is 1.41 Ω；And the specific area of unmodified carbon felt is only 1.13m2 g-1, electrochemical surface area 24.03cm2/ g,
Electrochemical impedance is 1.84 Ω.And the resiliently compressible rate of the modified carbon felt of gained reaches 20% or more.
Using the modified carbon felt as the electrode of all-vanadium flow battery, test in 160mA cm-2Current density under
Charge-discharge energy efficiency is 70.32%；And the result that unmodified carbon felt is accordingly tested is that charge-discharge energy efficiency is
57.16%.
Embodiment 2
A kind of preparation method of high performance carbon electrode is present embodiments provided, including is prepared by sol-gel method
The step of carbon fibre material/gel complex material and the step of carbon fibre material/gel complex material is carbonized.Specific behaviour
It is as follows to make method:
(1) carbon felt of 5mm thickness is cut into appropriate size；
(2) carbon felt cut is immersed in appropriate configured novolac solution, and is sealed holding.The novolac solution
Specific formula is as follows: be in terms of 100 parts, with the ratio between amount of substance of formaldehyde and resorcinol for 2 to configure novolac solution parts by weight:
1, the molar ratio of resorcinol and sodium carbonate is 1500, in deionized water, using formaldehyde and resorcinol as reactant, carbon is added
Sour sodium is reacted, and the novolac solution that mass fraction is 10% is obtained；
(3) container being sealed is placed in baking oven and carries out aging process, temperature is 55 DEG C, time 20h；
(4) it after the completion of step to be aging, takes out the carbon felt in organic aerogel and is immersed in acetone soln, container is close
Envelope；
(5) container being sealed being placed in baking oven and carrying out solvent displacement set temperature is 43 DEG C, continues 72h；
(6) carbon felt after solvent is replaced is taken out, is dried at room temperature for 28 hours；
(7) dried carbon felt is placed in resistance furnace, is continually fed into nitrogen protection, in 1100 DEG C of at a temperature of high temperature
Be carbonized 4h, and heating rate is 2 DEG C of min-1；
(8) it after the carbon felt after being carbonized is cooled to room temperature, takes out carbon felt and is immersed in n,N-Dimethylformamide solution,
80 DEG C at a temperature of heating 3 hours cleaning to remove remaining organic impurities in carbon felt；
(9) take out the carbon felt after cleaning, be placed in baking oven, 120 DEG C at a temperature of it is 3 hours dry；
(10) carbon felt after drying is taken out, is placed on cooling stand-by at room temperature.
The specific area of the modified carbon felt of gained is 53.1m2 g-1, electrochemical surface area 30.0cm2/ g, electrochemistry
Impedance is 1.21 Ω；And the specific area of unmodified carbon felt is only 1.13m2 g-1, electrochemical surface area 24.03cm2/ g,
Electrochemical impedance is 1.84 Ω.And the resiliently compressible rate of the modified carbon felt of gained reaches 20% or more.
Using the modified carbon felt as the electrode of all-vanadium flow battery, test in 160mA cm-2Current density under
Charge-discharge energy efficiency is 72.32%；And the result that unmodified carbon felt is accordingly tested is that charge-discharge energy efficiency is
57.16%.
Embodiment 3
A kind of preparation method of high performance carbon electrode is present embodiments provided, including is prepared by sol-gel method
The step of carbon fibre material/gel complex material and the step of carbon fibre material/gel complex material is carbonized.Specific behaviour
It is as follows to make method:
(1) carbon felt of 5mm thickness is cut into appropriate size；
(2) carbon felt cut is immersed in appropriate configured novolac solution, and is sealed holding.The novolac solution
Specific formula is as follows: be in terms of 100 parts, with the ratio between amount of substance of formaldehyde and resorcinol for 2 to configure novolac solution parts by weight:
1, the molar ratio of resorcinol and sodium carbonate is 500, in deionized water, using formaldehyde and resorcinol as reactant, carbon is added
Sour sodium is reacted, and the novolac solution that mass fraction is 18% is obtained；
(3) container being sealed is placed in baking oven and carries out aging process, temperature is 60 DEG C, time 20h；
(4) it after the completion of step to be aging, takes out the carbon felt in organic aerogel and is immersed in acetone soln, container is close
Envelope；
(5) container being sealed being placed in baking oven and carrying out solvent displacement set temperature is 45 DEG C, continues 48h；
(6) carbon felt after solvent is replaced is taken out, is dried at room temperature for 48 hours；
(7) dried carbon felt is placed in resistance furnace, is continually fed into nitrogen protection, in 1000 DEG C of at a temperature of high temperature
Be carbonized 5h, and heating rate is 2 DEG C of min-1；
(8) it after the carbon felt after being carbonized is cooled to room temperature, takes out carbon felt and is immersed in n,N-Dimethylformamide solution,
85 DEG C at a temperature of heating 2 hours cleaning to remove remaining organic impurities in carbon felt；
(9) take out the carbon felt after cleaning, be placed in baking oven, 110 DEG C at a temperature of it is 2 hours dry；
(10) carbon felt after drying is taken out, is placed on cooling stand-by at room temperature.
The specific area of the modified carbon felt of gained is 43.2m2 g-1, electrochemical surface area 25.8cm2/ g, electrochemistry
Impedance is 1.52 Ω；And the specific area of unmodified carbon felt is only 1.13m2 g-1, electrochemical surface area 24.03cm2/ g,
Electrochemical impedance is 1.84 Ω.And the resiliently compressible rate of the modified carbon felt of gained reaches 20% or more.
Using the modified carbon felt as the electrode of all-vanadium flow battery, test in 160mA cm-2Current density under
Charge-discharge energy efficiency is 68.87%；And the result that unmodified carbon felt is accordingly tested is that charge-discharge energy efficiency is
57.16%.
Embodiment 4
A kind of preparation method of high performance carbon electrode is present embodiments provided, specific steps are substantially the same manner as Example 1,
It the difference is that only: in the step (2) in the present embodiment, further including the steps that 5 parts of urea are added into novolac solution.
The specific area of the modified carbon felt of gained is 13.6m2 g-1, electrochemical surface area 28.30cm2/ g, electrochemistry
Impedance is 1.35 Ω；And the specific area of unmodified carbon felt is only 1.13m2 g-1, electrochemical surface area 24.03cm2/ g,
Electrochemical impedance is 1.84 Ω.And the resiliently compressible rate of the modified carbon felt of gained reaches 20% or more.
Using the modified carbon felt as the electrode of all-vanadium flow battery, test in 160mA cm-2Current density under
Charge-discharge energy efficiency is 76.32%；And the result that unmodified carbon felt is accordingly tested is that charge-discharge energy efficiency is
57.16%.
Embodiment 5
A kind of preparation method of high performance carbon electrode is present embodiments provided, specific steps are substantially the same manner as Example 1,
It the difference is that only: in the step (2) in the present embodiment, further including the steps that 2 parts of boric acid are added into novolac solution.
The specific area of the modified carbon felt of gained is 14.1m2 g-1, electrochemical surface area 28.46cm2/ g, electrochemistry
Impedance is 1.23 Ω；And the specific area of unmodified carbon felt is only 1.13m2 g-1, electrochemical surface area 24.03cm2/ g,
Electrochemical impedance is 1.84 Ω.And the resiliently compressible rate of the modified carbon felt of gained reaches 20% or more.
Using the modified carbon felt as the electrode of all-vanadium flow battery, test in 160mA cm-2Current density under
Charge-discharge energy efficiency is 75.72%；And the result that unmodified carbon felt is accordingly tested is that charge-discharge energy efficiency is
57.16%.
Embodiment 6
A kind of preparation method of high performance carbon electrode is present embodiments provided, specific steps are substantially the same manner as Example 1,
It the difference is that only: in the step (2) in the present embodiment, further including the steps that 0.1 part of boric acid is added into novolac solution.
The specific area of the modified carbon felt of gained is 13.5m2 g-1, electrochemical surface area 28.51cm2/ g, electrochemistry
Impedance is 1.39 Ω；And the specific area of unmodified carbon felt is only 1.13m2 g-1, electrochemical surface area 24.03cm2/ g,
Electrochemical impedance is 1.84 Ω.And the resiliently compressible rate of the modified carbon felt of gained reaches 20% or more.
Using the modified carbon felt as the electrode of all-vanadium flow battery, test in 160mA cm-2Current density under
Charge-discharge energy efficiency is 72.32%；And the result that unmodified carbon felt is accordingly tested is that charge-discharge energy efficiency is
57.16%.
Embodiment 7
A kind of preparation method of high performance carbon electrode is present embodiments provided, specific steps are substantially the same manner as Example 1,
The difference is that only: in the step (2) in the present embodiment, the novolac solution mass fraction of preparation is 1%.
The specific area of the modified carbon felt of gained is 3.24m2 g-1, electrochemical surface area 24.35cm2/ g, electrochemistry
Impedance is 1.75 Ω；And the specific area of unmodified carbon felt is only 1.13m2 g-1, electrochemical surface area 24.03cm2/ g,
Electrochemical impedance is 1.84 Ω.And the resiliently compressible rate of the modified carbon felt of gained reaches 20% or more.
Using the modified carbon felt as the electrode of all-vanadium flow battery, test in 160mA cm-2Current density under
Charge-discharge energy efficiency is 59.35%；And the result that unmodified carbon felt is accordingly tested is that charge-discharge energy efficiency is
57.16%.
Embodiment 8
A kind of preparation method of high performance carbon electrode is present embodiments provided, specific steps are substantially the same manner as Example 3,
The difference is that only: in the step (2) in the present embodiment, the novolac solution mass fraction of preparation is 20%.
The specific area of the modified carbon felt of gained is 53.2m2 g-1, electrochemical surface area 28.8cm2/ g, electrochemistry
Impedance is 1.76 Ω；And the specific area of unmodified carbon felt is only 1.13m2 g-1, electrochemical surface area 24.03cm2/ g,
Electrochemical impedance is 1.84 Ω.And the resiliently compressible rate of the modified carbon felt of gained is less than 10%.
Using the modified carbon felt as the electrode of all-vanadium flow battery, test in 160mA cm-2Current density under
Charge-discharge energy efficiency is 61.93%；And the result that unmodified carbon felt is accordingly tested is that charge-discharge energy efficiency is
57.16%.
Embodiment 9
A kind of preparation method of high performance carbon electrode is present embodiments provided, specific steps are substantially the same manner as Example 1,
The difference is that only: the carbon fibre material used in the present embodiment is graphite felt.
The specific area of the modified carbon felt of gained is 13.5m2 g-1, electrochemical surface area 26.8cm2/ g, electrochemistry
Impedance is 1.32 Ω；And the specific area of unmodified carbon felt is only 1.78m2 g-1, electrochemical surface area 22.17cm2/ g,
Electrochemical impedance is 1.56 Ω.And the resiliently compressible rate of the modified graphite felt of gained reaches 20% or more.
Using the modified carbon felt as the electrode of all-vanadium flow battery, test in 160mA cm-2Current density under
Charge-discharge energy efficiency is 71.23%；And the result that unmodified graphite felt is accordingly tested is that charge-discharge energy efficiency is
59.41%.
Embodiment 10
A kind of preparation method of high performance carbon electrode is present embodiments provided, specific steps are substantially the same manner as Example 1,
The difference is that only: the carbon fibre material used in the present embodiment is carbon paper.
The specific area of the modified carbon felt of gained is 15.21m2 g-1, electrochemical surface area 28.75cm2/ g, electrification
Impedance is 0.35 Ω；And the specific area of unmodified carbon paper is only 3.42m2 g-1, electrochemical surface area 26.54cm2/
G, electrochemical impedance are 0.68 Ω.And the resiliently compressible rate of the modified carbon paper of gained reaches 20% or more.
Using the modified carbon felt as the electrode of all-vanadium flow battery, test in 160mA cm-2Current density under
Charge-discharge energy efficiency is 75.32%；And the result that unmodified carbon paper felt is accordingly tested is that charge-discharge energy efficiency is
63.55%.
Comparative example 1
A kind of preparation method of high performance carbon electrode is present embodiments provided, specific steps are substantially the same manner as Example 3,
The difference is that only: in the step (2) in the present embodiment, the novolac solution mass fraction of preparation is 25%.
The specific area of the modified carbon felt of gained is 122.66m2 g-1, electrochemical surface area 15.8cm2/ g, electrification
Impedance is 3.13 Ω；And the specific area of unmodified carbon felt is only 1.13m2 g-1, electrochemical surface area 24.03cm2/
G, electrochemical impedance are 1.84 Ω.And the resiliently compressible rate of the modified carbon felt of gained is less than 2%.
Using the modified carbon felt as the electrode of all-vanadium flow battery, test in 160mA cm-2Current density under
Charge-discharge energy efficiency is 44.26%；And the result that unmodified carbon felt is accordingly tested is that charge-discharge energy efficiency is
57.16%.
There are many concrete application approach of the present invention, the above is only a preferred embodiment of the present invention.More than it should be pointed out that
Embodiment is merely to illustrate the present invention, and the protection scope being not intended to restrict the invention.For the common skill of the art
For art personnel, without departing from the principle of the present invention, several improvement can also be made, these improvement also should be regarded as this hair
Bright protection scope.
Claims (10)
1. a kind of preparation method of high performance carbon electrode, which is characterized in that including carbon fiber is prepared by sol-gel method
The step of material/gel complex material and the step of carbon fibre material/gel complex material is carbonized.
2. the preparation method of high performance carbon electrode according to claim 1, which is characterized in that the sol-gel legal system
For carbon fibre material/gel complex material is obtained, specific step is as follows:
A1, it prepares novolac solution: in a solvent, formaldehyde and resorcinol is added as reactant, adds catalyst, obtains phenol
Aldehyde solution；
A2, carbon fibre material is immersed in novolac solution, aging process is carried out after sealing, the carbon fiber material of gel must be coated
Material；
A3, it is submerged in organic solvent after taking out the carbon fibre material for coating gel, solvent displacement is carried out after sealing, after dry
Obtain carbon fibre material/gel complex material.
3. the preparation method of high performance carbon electrode according to claim 2, which is characterized in that in step A1, the formaldehyde
It is 2:1 with the ratio between the amount of substance of resorcinol；The molar ratio of resorcinol and catalyst is 500-1500；The novolac solution
Mass percent be 1-20%.
4. the preparation method of high performance carbon electrode according to claim 2, which is characterized in that in step A1, the carbon fiber
Tieing up material includes graphite felt, carbon felt, carbon paper, at least one of carbon cloth；
The solvent is deionized water, and the catalyst is natrium carbonicum calcinatum；In step A3, the organic solvent is acetone.
5. the preparation method of high performance carbon electrode according to claim 2, which is characterized in that in step A1, further include to
The step of boric acid and/or urea are added in novolac solution；The boric acid and/or urea 0.1-5 is added in every 100 parts of novolac solutions
Part.
6. the preparation method of high performance carbon electrode according to claim 2, which is characterized in that in step A2, the aging
The temperature of processing is 30-60 DEG C, time 20-72h.
7. the preparation method of high performance carbon electrode according to claim 2, which is characterized in that in step A3, the solvent
Displacement uses temperature specifically to handle 48-72h at 40-60 DEG C；
The drying carries out at room temperature, and drying time is 24-48 hours.
8. the preparation method of high performance carbon electrode according to claim 1, which is characterized in that the temperature of the carbonization is
800-2500 DEG C, carbonization time 2-6h.
9. the preparation method of high performance carbon electrode according to claim 1, which is characterized in that the method also includes by carbon
The step of cleaning removal of impurities, drying, cooling is carried out after the carbon electrode that change is handled is cooling.
10. a kind of high performance carbon electrode of any one of -9 the method preparations according to claim 1.
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