CN104319409A - High-activity asymmetric electrode for all-vanadium redox flow battery and preparation method thereof - Google Patents

High-activity asymmetric electrode for all-vanadium redox flow battery and preparation method thereof Download PDF

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CN104319409A
CN104319409A CN201410543082.4A CN201410543082A CN104319409A CN 104319409 A CN104319409 A CN 104319409A CN 201410543082 A CN201410543082 A CN 201410543082A CN 104319409 A CN104319409 A CN 104319409A
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flow battery
nano
bismuth
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redox flow
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刘建国
魏冠杰
严川伟
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Institute of Metal Research of CAS
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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
    • 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
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
    • 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
    • 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

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Abstract

The invention relates to the field of battery manufacturing and energy source storage, in particular to a high-activity asymmetric electrode for an all-vanadium redox flow battery and a preparation method thereof. The high-activity asymmetric electrode uses a carbon nanotube/carbon nanofiber composite electrode material as a positive electrode, and a bismuth-based catalyst/carbon nanofiber composite electrode material as a negative electrode, and the composite electrode materials used by the positive electrode and the negative electrode are prepared by an electrospinning technology and a subsequent carbonization process. A required nanofiber membrane is firstly prepared by the electrospinning technology, then is pre-oxidized in the air and is carbonized in an inert atmosphere tubular atmosphere furnace to obtain the required composite electrode material. The asymmetric electrode prepared by the method provided by the invention has the advantages of not only improving the reactivity of the positive and negative electrodes but also reducing the reaction rate difference between the positive and negative electrodes. In addition, the bismuth-based catalyst/carbon nanofiber composite electrode material is used as the negative electrode, so that the side hydrogen evolution reaction can be effectively inhibited, and thus the capacity retention rate of the battery can be improved.

Description

A kind of high activity asymmetry electrode used for all-vanadium redox flow battery and preparation method thereof
Technical field
The present invention relates to battery manufacture and energy storage field, be specially a kind of high activity asymmetry electrode used for all-vanadium redox flow battery and preparation method thereof.
Background technology
All-vanadium flow battery is a kind of novel secondary battery utilizing the chemical change of vanadium ion different valence state to carry out energy storage, its both positive and negative polarity active material is the sulfuric acid solution of vanadium, electrode reaction all betides liquid phase, greatly reduce electrochemical polarization, its rated power and rated power all can design separately, can reach instantaneous charging by changing electrolyte, 100% deep discharge also can not damage battery to some extent.Based on above advantage, it can be widely used in the aspects such as the energy storage such as wind energy, solar energy, peak load regulation network, uninterrupted power supply.
At present, all-vanadium flow battery electrode structure used is mainly symmetrical electrode structure, by the graphite felt of carbon element class or charcoal felt simultaneously as positive pole and negative pole.But, both because vanadium redox flow battery electrode reaction is lower at the electro-chemical activity on charcoal felt surface, also because the negative reaction speed of battery on charcoal felt is slower than positive pole, made battery performance be subject to severely restricts.So, need to change this symmetry electrode being both positive and negative polarity with charcoal felt, while improving electrode reaction activity, reduce both positive and negative polarity reaction rate difference, thus efficiently and effectively improves energy content of battery efficiency.
Summary of the invention
The object of the present invention is to provide a kind of high activity asymmetry electrode used for all-vanadium redox flow battery and preparation method thereof, solve the problems such as the vanadium redox flow battery electrode reaction existed in prior art is low in electrode material surface activity, both positive and negative polarity reaction rate is not mated, the liberation of hydrogen side reaction of negative pole is serious.
Technical scheme of the present invention is:
A kind of high activity asymmetry electrode used for all-vanadium redox flow battery, using carbon nanotube/nano carbon fiber combination electrode material as the positive pole of all-vanadium flow battery, bismuth-based catalysts/carbon nano-fiber combination electrode material is as the negative pole of all-vanadium flow battery.
The preparation method of described high activity asymmetry electrode used for all-vanadium redox flow battery, comprises the following steps and process:
1) preparation of spinning solution: join in dimethyl formamide with certain proportion by polyacrylonitrile, stirs under water bath condition;
Wherein, the mean molecule quantity of polyacrylonitrile is 50000 ~ 200000, and the mass ratio of polyacrylonitrile and dimethyl formamide is 5:95 to 20:80, and bath temperature is 40 ~ 80 DEG C;
2) bismuth salt or carbon nano-tube are joined 1 in proportion) described in spinning solution in, by stir or ultrasonic mode make it be uniformly dispersed;
Wherein, the mass ratio of the polyacrylonitrile in the bismuth salt added or carbon nano-tube and solution is 1:100 to 10:1;
3) by step 2) the composite spinning liquid that obtains utilizes electrostatic spinning technique to obtain nano fibrous membrane, and the thickness of nano fibrous membrane is 0.01 ~ 5 millimeter;
4) by step 3) nano fibrous membrane that obtains carries out pre-oxidation and carbonization through atmosphere furnace;
Wherein, Pre oxidation is 200 ~ 300 DEG C, and the time is 0.5 ~ 4 hour; Carburizing temperature is 600 ~ 1500 DEG C, and the time is 0.5 ~ 10 hour, and inert protective atmosphere is nitrogen or argon gas;
5) by step 4) the carbon nanotube/nano carbon fiber combination electrode material that obtains is contained in all-vanadium flow battery positive pole, and bismuth-based catalysts/carbon nano-fiber combination electrode material is contained in its negative pole.
The preparation method of described high activity asymmetry electrode used for all-vanadium redox flow battery, step 1) in, the mixing time of polyacrylonitrile in dimethyl formamide 0.5 ~ 24 hour.
The preparation method of described high activity asymmetry electrode used for all-vanadium redox flow battery, step 2) in, bismuth salt or the mixing time of carbon nano-tube in composite spinning liquid are 1 ~ 24 hour, and ultrasonic time is 0.5 ~ 10 hour.
The preparation method of described high activity asymmetry electrode used for all-vanadium redox flow battery, step 2) in, bismuth salt is bismuth chloride, bismuth nitrate or bismuth citrate, and carbon nano-tube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes.
The preparation method of described high activity asymmetry electrode used for all-vanadium redox flow battery, step 3) in, electrostatic spinning process parameter is: needle aperture is 0.3 ~ 2.0 millimeter, syringe capacity is 5 ~ 500 milliliters, spinning solution flow velocity is 0.2 ~ 5 ml/hour, the rotating speed of transfer roller is 100 ~ 1000 revs/min, voltage between syringe needle and transfer roller is 10 ~ 50 kilovolts, distance on syringe needle and transfer roller between nano fibrous membrane collecting board is 10 ~ 50 centimetres, spinning temperature is 20 ~ 50 DEG C, and spinning humidity is 20 ~ 70%RH.
The preparation method of described high activity asymmetry electrode used for all-vanadium redox flow battery, on transfer roller, the collecting board of nano fibrous membrane is the one in carbon paper, graphite paper, charcoal cloth, aluminium foil, tinfoil paper, alumina foil, the thickness of carbon paper, graphite paper is 30 ~ 300 microns, the thickness of charcoal cloth 100 ~ 1000 microns, the thickness of aluminium foil, tinfoil paper, alumina foil is 10 ~ 100 microns.
The preparation method of described high activity asymmetry electrode used for all-vanadium redox flow battery; step 4) in; the programming rate of pre-oxidation treatment is 2 ~ 25 DEG C/min, and the programming rate of carbonization treatment is 2 ~ 25 DEG C/min, and the gas flow in inertia protection is 20 ~ 100 ml/min.
The preparation method of described high activity asymmetry electrode used for all-vanadium redox flow battery, final electrode used for all-vanadium redox flow battery makes positive pole by carbon nanotube/nano carbon fiber combination electrode material, and bismuth-based catalysts/carbon nano-fiber combination electrode material makes the high activity asymmetry electrode of negative pole.
Design philosophy of the present invention is:
The spinning solution of the present invention first needed for preparation experiment, then bismuth salt or carbon nano-tube are mixed with spinning solution, by the method for electrostatic spinning, prepare required nano fibrous membrane.Then in atmosphere pre-oxidation (temperature 200 ~ 300 DEG C) is carried out to nano fibrous membrane, carbonization in inert atmosphere tube-type atmosphere furnace (temperature 600 ~ 1500 DEG C), the combination electrode material that both positive and negative polarity is used respectively.Finally, carbon nanotube/nano carbon fiber combination electrode material is contained in all-vanadium flow battery positive pole, bismuth-based catalysts/carbon nano-fiber combination electrode material is contained in its negative pole, namely forms high activity asymmetry electrode.Because carbon nanotube/nano carbon fiber combination electrode material has excellent electro-chemical activity to the reaction of all-vanadium flow battery positive pole, and bismuth-based catalysts/carbon nano-fiber combination electrode material anticathode reaction has excellent electro-chemical activity.So the asymmetry electrode adopting the inventive method to prepare can not only improve the reactivity of positive pole and negative pole, also can reduce reaction rate difference therebetween simultaneously, thus improve the energy efficiency of battery greatly.In addition, bismuth-based catalysts/carbon nano-fiber combination electrode material is used as negative pole, can effectively suppresses liberation of hydrogen side reaction, thus improve the capability retention of battery.
Advantage of the present invention and beneficial effect as follows:
1. the high activity asymmetry electrode that the present invention proposes can improve the reactivity of positive pole and negative pole simultaneously, also can reduce reaction rate difference therebetween, thus improves the energy efficiency of battery greatly.
2. the high activity asymmetry electrode of the present invention's proposition, can suppress liberation of hydrogen side reaction effectively, thus improves the capability retention of battery.
3. the electrospinning device used by the present invention is simple, and experiment condition is content with very little, and method cheap, be easy to operation.
4. vanadium redox flow battery electrode reaction of the present invention is high in electrode material surface activity, electrode material stable performance.
Embodiment
In the specific embodiment of the present invention, the preparation method of high activity asymmetry electrode used for all-vanadium redox flow battery, comprises the following steps and process:
1) preparation of spinning solution: joined in certain proportion in dimethyl formamide by polyacrylonitrile, stirs under water bath condition;
Wherein, the mean molecule quantity of polyacrylonitrile is 50000 ~ 200000, the mass ratio of polyacrylonitrile and dimethyl formamide is 5:95 to 20:80 (being preferably 10:90 to 15:85), bath temperature is 40 ~ 80 DEG C, and the mixing time of polyacrylonitrile in dimethyl formamide is 0.5 ~ 24 hour (being preferably 3 ~ 6 hours).
2) bismuth salt or carbon nano-tube are joined step 1 in proportion) described in spinning solution in, by stir or ultrasonic mode make it be uniformly dispersed.Bismuth salt or the carbon nano-tube mixing time in spinning solution is 1 ~ 24 hour (being preferably 6 ~ 18 hours), and ultrasonic time is 0.5 ~ 10 hour (being preferably 2 ~ 6 hours).
Wherein, bismuth salt is bismuth chloride, bismuth nitrate or bismuth citrate, and carbon nano-tube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes; The mass ratio of the polyacrylonitrile in the bismuth salt added or carbon nano-tube and solution is 1:100 to 10:1 (being preferably 1:100 to 1:1);
3) by step 2) the composite spinning liquid that obtains utilizes electrostatic spinning technique to obtain nano fibrous membrane, and the thickness of nano fibrous membrane is 0.01 ~ 5 millimeter (being preferably 0.5 ~ 5 millimeter);
Wherein, electrostatic spinning process parameter is: needle aperture is 0.3 ~ 2.0 millimeter, syringe capacity is 5 ~ 500 milliliters, spinning solution flow velocity is 0.2 ~ 5 ml/hour, the rotating speed of transfer roller is 100 ~ 1000 revs/min, and the voltage between syringe needle and transfer roller is 10 ~ 50 kilovolts, and the distance on syringe needle and transfer roller between nano fibrous membrane collecting board is 10 ~ 50 centimetres, spinning temperature is 20 ~ 50 DEG C, and spinning humidity is 20 ~ 70%RH (Relative Humidity).On transfer roller, the collecting board of nano fibrous membrane is the one in carbon paper, graphite paper, charcoal cloth, aluminium foil, tinfoil paper, alumina foil, the thickness of carbon paper, graphite paper is 30 ~ 300 microns, the thickness of charcoal cloth 100 ~ 1000 microns, the thickness of aluminium foil, tinfoil paper, alumina foil is 10 ~ 100 microns.
4) by step 3) nano fibrous membrane that obtains carries out pre-oxidation and carbonization through atmosphere furnace;
Wherein, Pre oxidation is 200 ~ 300 DEG C, and programming rate is 2 ~ 25 DEG C/min, and the time is 0.5 ~ 4 hour; Carburizing temperature is 600 ~ 1500 DEG C, and programming rate is 2 ~ 25 DEG C/min, and the time is 0.5 ~ 10 hour, and inert protective atmosphere is nitrogen or argon gas, and gas flow is 20 ~ 100 ml/min;
5) by step 4) the carbon nanotube/nano carbon fiber combination electrode material that obtains is contained in all-vanadium flow battery positive pole, and bismuth-based catalysts/carbon nano-fiber combination electrode material is contained in its negative pole;
Final electrode used for all-vanadium redox flow battery makes positive pole by carbon nanotube/nano carbon fiber combination electrode material, and bismuth-based catalysts/carbon nano-fiber combination electrode material makes the high activity asymmetry electrode of negative pole.
The present invention's experiment material used (as: polyacrylonitrile, bismuth salt or carbon nano-tube etc.) is commercially available, and without the need to subsequent purification process, gas is high-purity gas (purity >=99.999%).
Below by embodiment, the present invention is described in further detail.
Embodiment 1
1) mass fraction be 10% polyacrylonitrile join under agitation in dimethyl formamide, bath temperature be at 60 DEG C stir within 2 hours, obtain spinning solution, the mean molecule quantity of polyacrylonitrile is 150000.
2) get each 100 grams of two parts of spinning solutions, bismuth chloride is joined in a spinning solution, multi-walled carbon nano-tubes is joined in another part of spinning solution.Add polyacrylonitrile in bismuth chloride and its solution mass ratio be 1:50, add polyacrylonitrile in multi-walled carbon nano-tubes and its solution mass ratio be 1:100.Stir after 12 hours, more ultrasonic 6 hours, obtain two kinds of uniform composite spinning liquid.
3) will through step 2) two kinds of composite spinning liquid obtaining join in the syringe of 20ml respectively, and carry out electrostatic spinning separately and obtain nano fibrous membrane, the thickness of the present embodiment nano fibrous membrane is 0.5 millimeter.Spinning parameter is: needle aperture is 0.3 millimeter, on syringe needle and transfer roller, the distance of nano fibrous membrane collecting board is 12 centimetres, spinning voltage between them is 25kV, collecting board is carbon paper thick after 200 microns, the rotating speed of transfer roller is 200 revs/min, spinning solution flow velocity is 0.5 ml/hour, and spinning temperature is 40 DEG C, and humidity is 50%RH.
4) will through step 3) two kinds of nano fibrous membranes obtaining are put into pre-oxidation and carbonization in tube-type atmosphere furnace, and Pre oxidation is 250 DEG C, and programming rate is 20 DEG C/min, and temperature retention time is 2 hours, and atmosphere is air; Carburizing temperature is 900 DEG C, and programming rate is 10 DEG C/min, and temperature retention time is 2 hours, and inert protective atmosphere is nitrogen, and gas flow is 60 ml/min.
5) by through step 4) multi-walled carbon nano-tubes/carbon nano-fiber combination electrode material of obtaining is contained in all-vanadium flow battery positive pole, and bismuth-based catalysts/carbon nano-fiber combination electrode material is contained in negative pole, carries out charge-discharge performance test.
In the present embodiment, the high activity asymmetry electrode used for all-vanadium redox flow battery prepared owing to utilizing electrostatic spinning technique can improve the electro-chemical activity of both positive and negative polarity reaction simultaneously, also can reduce reaction rate difference therebetween, thus greatly improve the energy efficiency of battery.Be 100mA/cm in current density 2constant current charge-discharge test condition under, use the energy efficiency of the battery of this asymmetry electrode to bring up to 82.5% by untapped 78.9%, capability retention also brings up to 59% (through 100 charge and discharge cycles) by original 51%.
Embodiment 2
1) mass fraction be 11% polyacrylonitrile join under agitation in dimethyl formamide, bath temperature be at 80 DEG C stir within 2 hours, obtain spinning solution, the mean molecule quantity of polyacrylonitrile is 120000.
2) get each 100 grams of two parts of spinning solutions, bismuth nitrate is joined in a spinning solution, multi-walled carbon nano-tubes is joined in another part of spinning solution.Add polyacrylonitrile in bismuth nitrate and its solution mass ratio be 1:25, add polyacrylonitrile in multi-walled carbon nano-tubes and its solution mass ratio be 1:75.Stir after 18 hours, more ultrasonic 8 hours, obtain two kinds of uniform composite spinning liquid.
3) will through step 2) two kinds of composite spinning liquid obtaining join in the syringe of 20ml respectively, and carry out electrostatic spinning separately and obtain nano fibrous membrane, the thickness of the present embodiment nano fibrous membrane is 1.5 millimeters.Spinning parameter is: needle aperture is 0.9 millimeter, on syringe needle and transfer roller, the distance of nano fibrous membrane collecting board is 15 centimetres, spinning voltage between them is 30kV, collecting board is carbon paper thick after 200 microns, the rotating speed of transfer roller is 500 revs/min, spinning solution flow velocity is 1.0 mls/hour, and spinning temperature is 50 DEG C, and humidity is 50%RH.
4) by through step 3) nano fibrous membrane that obtains is put into pre-oxidation and carbonization in tube-type atmosphere furnace, and Pre oxidation is 300 DEG C, and programming rate is 20 DEG C/min, and temperature retention time is 3 hours, and atmosphere is air; Carburizing temperature is 1000 DEG C, and programming rate is 10 DEG C/min, and temperature retention time is 3 hours, and inert protective atmosphere is nitrogen, and gas flow is 80 ml/min.
5) by through step 4) multi-walled carbon nano-tubes/carbon nano-fiber combination electrode material of obtaining is contained in all-vanadium flow battery positive pole, and bismuth-based catalysts/carbon nano-fiber combination electrode material is contained in negative pole, carries out charge-discharge performance test.
In the present embodiment, in the present embodiment, the high activity asymmetry electrode used for all-vanadium redox flow battery prepared owing to utilizing electrostatic spinning technique can improve the electro-chemical activity of both positive and negative polarity reaction simultaneously, also can reduce reaction rate difference therebetween, thus greatly improve the energy efficiency of battery.Be 100mA/cm in current density 2constant current charge-discharge test condition under, use the energy efficiency of the battery of this asymmetry electrode to bring up to 83.6% by untapped 78.9%, capability retention also brings up to 64% (through 100 charge and discharge cycles) by original 51%.
Embodiment 3
1) mass fraction be 12% polyacrylonitrile join under agitation in dimethyl formamide, bath temperature be at 80 DEG C stir within 4 hours, obtain spinning solution, the mean molecule quantity of polyacrylonitrile is 150000.
2) get each 100 grams of two parts of spinning solutions, bismuth citrate is joined in a spinning solution, Single Walled Carbon Nanotube is joined in another part of spinning solution.Add polyacrylonitrile in bismuth citrate and its solution mass ratio be 1:15, add polyacrylonitrile in Single Walled Carbon Nanotube and its solution mass ratio be 1:50.Stir after 24 hours, more ultrasonic 8 hours, obtain two kinds of uniform composite spinning liquid.
3) will through step 2) two kinds of composite spinning liquid obtaining join in the syringe of 20ml respectively, and carry out electrostatic spinning separately and obtain nano fibrous membrane, the thickness of the present embodiment nano fibrous membrane is 3 millimeters.Spinning parameter is: needle aperture is 0.9 millimeter, on syringe needle and transfer roller, the distance of nano fibrous membrane collecting board is 16 centimetres, spinning voltage between them is 30kV, collecting board is charcoal cloth thick after 200 microns, the rotating speed of transfer roller is 800 revs/min, spinning solution flow velocity is 1.2 mls/hour, and spinning temperature is 40 DEG C, and humidity is 50%RH.
4) by through step 3) nano fibrous membrane that obtains is put into pre-oxidation and carbonization in tube-type atmosphere furnace, and Pre oxidation is 270 DEG C, and programming rate is 20 DEG C/min, and temperature retention time is 4 hours, and atmosphere is air; Carburizing temperature is 1100 DEG C, and programming rate is 10 DEG C/min, and temperature retention time is 4 hours, and inert protective atmosphere is nitrogen, and gas flow is 80 ml/min.
5) by through step 4) Single Walled Carbon Nanotube/carbon nano-fiber combination electrode material of obtaining is contained in all-vanadium flow battery positive pole, and bismuth-based catalysts/carbon nano-fiber combination electrode material is contained in negative pole, carries out charge-discharge performance test.
In the present embodiment, the high activity asymmetry electrode used for all-vanadium redox flow battery prepared owing to utilizing electrostatic spinning technique can improve the electro-chemical activity of both positive and negative polarity reaction simultaneously, also can reduce reaction rate difference therebetween, thus greatly improve the energy efficiency of battery.Be 100mA/cm in current density 2constant current charge-discharge test condition under, use the energy efficiency of the battery of this asymmetry electrode to bring up to 84.1% by untapped 78.9%, capability retention also brings up to 71% (through 100 charge and discharge cycles) by original 51%.
Embodiment result shows, positive pole of the present invention and negative pole combination electrode material used are by electrostatic spinning technique and the preparation of follow-up carbonization technique, the asymmetry electrode adopting the inventive method to prepare can not only improve the reactivity of positive pole and negative pole simultaneously, also can reduce reaction rate difference therebetween, thus improve the energy efficiency of battery greatly.In addition, bismuth-based catalysts/carbon nano-fiber combination electrode material is used as negative pole, can effectively suppresses liberation of hydrogen side reaction, thus improve the capability retention of battery.

Claims (9)

1. a high activity asymmetry electrode used for all-vanadium redox flow battery, it is characterized in that: using carbon nanotube/nano carbon fiber combination electrode material as the positive pole of all-vanadium flow battery, bismuth-based catalysts/carbon nano-fiber combination electrode material is as the negative pole of all-vanadium flow battery.
2. the preparation method of high activity asymmetry electrode used for all-vanadium redox flow battery according to claim 1, is characterized in that, comprise the following steps and process:
1) preparation of spinning solution: join in dimethyl formamide with certain proportion by polyacrylonitrile, stirs under water bath condition;
Wherein, the mean molecule quantity of polyacrylonitrile is 50000 ~ 200000, and the mass ratio of polyacrylonitrile and dimethyl formamide is 5:95 to 20:80, and bath temperature is 40 ~ 80 DEG C;
2) bismuth salt or carbon nano-tube are joined 1 in proportion) described in spinning solution in, by stir or ultrasonic mode make it be uniformly dispersed;
Wherein, the mass ratio of the polyacrylonitrile in the bismuth salt added or carbon nano-tube and solution is 1:100 to 10:1;
3) by step 2) the composite spinning liquid that obtains utilizes electrostatic spinning technique to obtain nano fibrous membrane, and the thickness of nano fibrous membrane is 0.01 ~ 5 millimeter;
4) by step 3) nano fibrous membrane that obtains carries out pre-oxidation and carbonization through atmosphere furnace;
Wherein, Pre oxidation is 200 ~ 300 DEG C, and the time is 0.5 ~ 4 hour; Carburizing temperature is 600 ~ 1500 DEG C, and the time is 0.5 ~ 10 hour, and inert protective atmosphere is nitrogen or argon gas;
5) by step 4) the carbon nanotube/nano carbon fiber combination electrode material that obtains is contained in all-vanadium flow battery positive pole, and bismuth-based catalysts/carbon nano-fiber combination electrode material is contained in its negative pole.
3. the preparation method of high activity asymmetry electrode used for all-vanadium redox flow battery according to claim 2, is characterized in that, step 1) in, the mixing time of polyacrylonitrile in dimethyl formamide 0.5 ~ 24 hour.
4. the preparation method of high activity asymmetry electrode used for all-vanadium redox flow battery according to claim 2, is characterized in that, step 2) in, bismuth salt or the mixing time of carbon nano-tube in composite spinning liquid are 1 ~ 24 hour, and ultrasonic time is 0.5 ~ 10 hour.
5. the preparation method of high activity asymmetry electrode used for all-vanadium redox flow battery according to claim 2, is characterized in that, step 2) in, bismuth salt is bismuth chloride, bismuth nitrate or bismuth citrate, and carbon nano-tube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes.
6. the preparation method of high activity asymmetry electrode used for all-vanadium redox flow battery according to claim 2, it is characterized in that, step 3) in, electrostatic spinning process parameter is: needle aperture is 0.3 ~ 2.0 millimeter, syringe capacity is 5 ~ 500 milliliters, spinning solution flow velocity is 0.2 ~ 5 ml/hour, the rotating speed of transfer roller is 100 ~ 1000 revs/min, voltage between syringe needle and transfer roller is 10 ~ 50 kilovolts, distance on syringe needle and transfer roller between nano fibrous membrane collecting board is 10 ~ 50 centimetres, spinning temperature is 20 ~ 50 DEG C, and spinning humidity is 20 ~ 70%RH.
7. the preparation method of high activity asymmetry electrode used for all-vanadium redox flow battery according to claim 6, it is characterized in that, on transfer roller, the collecting board of nano fibrous membrane is the one in carbon paper, graphite paper, charcoal cloth, aluminium foil, tinfoil paper, alumina foil, the thickness of carbon paper, graphite paper is 30 ~ 300 microns, the thickness of charcoal cloth 100 ~ 1000 microns, the thickness of aluminium foil, tinfoil paper, alumina foil is 10 ~ 100 microns.
8. the preparation method of high activity asymmetry electrode used for all-vanadium redox flow battery according to claim 2; it is characterized in that; step 4) in; the programming rate of pre-oxidation treatment is 2 ~ 25 DEG C/min; the programming rate of carbonization treatment is 2 ~ 25 DEG C/min, and the gas flow in inertia protection is 20 ~ 100 ml/min.
9. the preparation method of high activity asymmetry electrode used for all-vanadium redox flow battery according to claim 2, it is characterized in that, final electrode used for all-vanadium redox flow battery makes positive pole by carbon nanotube/nano carbon fiber combination electrode material, and bismuth-based catalysts/carbon nano-fiber combination electrode material makes the high activity asymmetry electrode of negative pole.
CN201410543082.4A 2014-10-15 2014-10-15 High-activity asymmetric electrode for all-vanadium redox flow battery and preparation method thereof Pending CN104319409A (en)

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CN106198453A (en) * 2016-08-25 2016-12-07 清华大学深圳研究生院 The online test method of the chief and vice reaction ratio of a kind of all-vanadium flow battery and device
CN106480548A (en) * 2015-08-24 2017-03-08 中国科学院金属研究所 A kind of preparation method of high-specific surface area lead charcoal composite nano fiber
CN106876733A (en) * 2015-12-12 2017-06-20 中国科学院大连化学物理研究所 A kind of CNT self-assembled nanometer fibrofelt and its preparation and application
CN106876721A (en) * 2015-12-13 2017-06-20 中国科学院大连化学物理研究所 A kind of porous carbon nanofiber electrode used for all-vanadium redox flow battery and its preparation and application
CN108598542A (en) * 2018-04-04 2018-09-28 苏州舒广袖新能源科技有限公司 A kind of all-vanadium flow battery based on boron doping carbon nanotube
CN110518260A (en) * 2019-08-29 2019-11-29 辽宁金谷炭材料股份有限公司 A kind of production method of modified vanadium cell porous electrode graphite felt
CN111477894A (en) * 2020-05-11 2020-07-31 辽宁大学 High-activity hydrogen evolution inhibition type carbon nanofiber electrode material, preparation method thereof and application thereof in vanadium battery
CN111477893A (en) * 2020-05-11 2020-07-31 辽宁大学 Electrospun carbon nanofiber composite material with functional components distributed in longitudinal gradient manner, preparation method of electrospun carbon nanofiber composite material and application of electrospun carbon nanofiber composite material in vanadium battery
CN111584895A (en) * 2020-05-25 2020-08-25 广州市香港科大霍英东研究院 Oriented ordered electrode and preparation method and application thereof
CN116924382A (en) * 2022-03-30 2023-10-24 中国科学院金属研究所 Preparation method of foam carbon-based flow battery electrode material with controllable structure

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CN106480548A (en) * 2015-08-24 2017-03-08 中国科学院金属研究所 A kind of preparation method of high-specific surface area lead charcoal composite nano fiber
CN106876733A (en) * 2015-12-12 2017-06-20 中国科学院大连化学物理研究所 A kind of CNT self-assembled nanometer fibrofelt and its preparation and application
CN106876721A (en) * 2015-12-13 2017-06-20 中国科学院大连化学物理研究所 A kind of porous carbon nanofiber electrode used for all-vanadium redox flow battery and its preparation and application
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CN106198453B (en) * 2016-08-25 2019-03-26 清华大学深圳研究生院 A kind of online test method and device of the chief and vice reaction ratio of all-vanadium flow battery
CN108598542A (en) * 2018-04-04 2018-09-28 苏州舒广袖新能源科技有限公司 A kind of all-vanadium flow battery based on boron doping carbon nanotube
CN110518260A (en) * 2019-08-29 2019-11-29 辽宁金谷炭材料股份有限公司 A kind of production method of modified vanadium cell porous electrode graphite felt
CN111477894A (en) * 2020-05-11 2020-07-31 辽宁大学 High-activity hydrogen evolution inhibition type carbon nanofiber electrode material, preparation method thereof and application thereof in vanadium battery
CN111477893A (en) * 2020-05-11 2020-07-31 辽宁大学 Electrospun carbon nanofiber composite material with functional components distributed in longitudinal gradient manner, preparation method of electrospun carbon nanofiber composite material and application of electrospun carbon nanofiber composite material in vanadium battery
CN111584895A (en) * 2020-05-25 2020-08-25 广州市香港科大霍英东研究院 Oriented ordered electrode and preparation method and application thereof
CN111584895B (en) * 2020-05-25 2022-02-11 广州市香港科大霍英东研究院 Oriented ordered electrode and preparation method and application thereof
CN116924382A (en) * 2022-03-30 2023-10-24 中国科学院金属研究所 Preparation method of foam carbon-based flow battery electrode material with controllable structure

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