CN104241661A - Preparation method for combination electrode for all-vanadium redox flow battery - Google Patents
Preparation method for combination electrode for all-vanadium redox flow battery Download PDFInfo
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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
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
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- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- D06B21/00—Successive treatments of textile materials by liquids, gases or vapours
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention relates to the field of battery manufacturing and energy storage, in particular to a preparation method of a bismuth-base catalyst/carbon nanofiber combination electrode for an all-vanadium redox flow battery. Firstly, spinning solution required for an experiment is prepared and then bismuth salt and the spinning solution are uniformly mixed. According to an electrostatic spinning method, a required nanofiber film is prepared and then the nanofiber film is pre-oxidized in the air and is carbonized in an inert atmosphere tube furnace so as to obtain the required bismuth-base electrocatalyst/carbon nanofiber combination electrode. After the obtained electrode material is cleaned and dried, testing of related electrochemical performance representation and charge-discharge properties can be carried out on the electrode material. The carbon fiber diameter, which is prepared according to the preparation method, is in the nano class; compared with a specific surface area of a conventionally used electrode material, the specific surface area of the bismuth-base catalyst/carbon nanofiber combination electrode is greatly increased. Moreover, the carbon nanofibers are compounded with a high-activity bismuth-base electrocatalyst, and thus, electrochemical activity of the electrode can be greatly improved, so that energy efficiency of the all-vanadium redox flow battery is greatly improved.
Description
Technical field
The present invention relates to battery manufacture and energy storage field, be specially a kind of preparation method of bismuth-based catalysts used for all-vanadium redox flow battery/carbon nano-fiber combination electrode.
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 material used is mainly graphite felt or the charcoal felt of carbon element class, the advantages such as this material has that resistivity is low, specific area large, chemistry and electrochemical stability.But vanadium redox flow battery electrode reaction is lower at the electro-chemical activity on its surface, so need to carry out activation processing to improve its electro-chemical activity to graphite felt or charcoal felt, and then improve battery performance.
Nowadays, there is the method for modifying much for charcoal felt or graphite felt electrode material, modify comprising liquid phase or gas chemistry process, electrochemical treatments, transition-metals and their oxides, but these methods are very limited for the electro-chemical activity improving carbon fiber, and easily destroy the superior physical properties of carbon fiber.In addition, be modified at transition-metals and their oxides on carbon fiber can not long-term existence on its surface, chemical property is unstable.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of bismuth-based catalysts used for all-vanadium redox flow battery/carbon nano-fiber combination electrode, solve the problems such as the vanadium redox flow battery electrode reaction existed in prior art is low in electrode material surface activity, the electrocatalysis characteristic instability of electrode material.
Technical scheme of the present invention is:
A preparation method for combination electrode used for all-vanadium redox flow battery, comprises the following steps and process:
1) preparation of spinning solution: polyacrylonitrile or polyethylene glycol are joined in dimethyl formamide or dimethylacetylamide in certain proportion, stirs under water bath condition;
Wherein, the mean molecule quantity of polyacrylonitrile is 50000 ~ 200000, the mean molecule quantity of polyethylene glycol is 2000 ~ 10000, and the mass ratio of polyacrylonitrile or polyethylene glycol and dimethyl formamide or dimethylacetylamide is 5:95 to 20:80, and bath temperature is 40 ~ 80 DEG C;
2) bismuth meal or bismuth salt are joined 1 in proportion) described in spinning solution in, by stir or ultrasonic mode make it be uniformly dispersed;
Wherein, bismuth salt is one or more in the inorganic salts of bismuth-containing or organic salt, and the polyacrylonitrile in the bismuth meal added or bismuth salt and solution or the mass ratio of polyethylene glycol are 1:100 to 10:1;
3) by 2) the composite spinning liquid electrostatic spinning technique that obtains obtains nano fibrous membrane;
4) by 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 4) electrode material of gained is directly with washed with de-ionized water or ultrasonic cleaning;
Wherein, ultrasonic time is 5 ~ 30 minutes.
The preparation method of described combination electrode used for all-vanadium redox flow battery, step 1) in, polyacrylonitrile or polyethylene glycol are in the mixing time 0.5 ~ 24 hour of dimethyl formamide or dimethylacetylamide.
The preparation method of described combination electrode used for all-vanadium redox flow battery, step 2) in, the mixing time of bismuth salt in composite spinning liquid is 1 ~ 24 hour, and ultrasonic time is 0.5 ~ 10 hour.
The preparation method of described combination electrode used for all-vanadium redox flow battery, step 2) in, the inorganic salts of bismuth-containing or organic salt comprise bismuth oxide, bismuth chloride, bismuth nitrate, bismuth citrate.
The preparation method of described combination 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, and spinning solution flow velocity is 0.2 ~ 5 ml/hour, and the rotating speed of transfer roller is 100 ~ 1000 revs/min, voltage between syringe needle and transfer roller is 10 ~ 50 kilovolts, distance between syringe needle and transfer roller is 10 ~ 50 centimetres, and spinning temperature is 20 ~ 50 DEG C, and spinning humidity is 20 ~ 70%RH.
The preparation method of described combination 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 combination 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 combination electrode used for all-vanadium redox flow battery, step 5) electrode material after cleaning, dry in vacuum drying chamber or air dry oven, baking temperature is 50 ~ 100 DEG C, processing time is 12 ~ 48 hours, and the electrode material thickness after oven dry is at 0.01 ~ 5 millimeter.
The preparation method of described combination electrode used for all-vanadium redox flow battery, final electrode material is the controlled membranaceous or block materials of the thickness that is entwined by carbon nano-fiber, or the membranaceous or block materials that the thickness that is entwined of the carbon nano-fiber containing catalyst is controlled.
Design philosophy of the present invention is:
The spinning solution of the present invention first needed for preparation experiment, then the organic salt of bismuth-containing or inorganic salts are mixed with spinning solution, by the method for electrostatic spinning, prepare required nano fibrous membrane.Then carry out pre-oxidation (temperature 200 ~ 300 DEG C) to nano fibrous membrane in atmosphere, carbonization in inert atmosphere tube furnace (temperature 600 ~ 1500 DEG C), obtains required bismuthino eelctro-catalyst/carbon nano-fiber combination electrode.After obtained electrode material is cleaned, drying, relevant Electrochemical Characterization and charge-discharge performance test can be carried out to it.Adopt all-vanadium flow battery combination electrode material prepared by method of the present invention, carbon fiber diameter is at Nano grade, and specific area compares traditional used electrode material to be increased greatly.Again due to by carbon nano-fiber and highly active eelctro-catalyst compound, the electro-chemical activity of electrode will significantly improve, thus the energy efficiency of raising all-vanadium flow battery greatly.In addition, by controlling electrostatic spinning process parameter and carburizing temperature and time, can the pattern etc. of effective control electrode material, the method is a kind of technology preparing the highly effective of combination electrode used for all-vanadium redox flow battery.
Advantage of the present invention and beneficial effect as follows:
1. the method for the preparation combination electrode material used for all-vanadium redox flow battery of the present invention's proposition can prepare the electrode material woven by carbon nano-fiber, the specific area of electrode is improved greatly, thus increases electrode reaction area.Be spun into the bismuth salt decomposes in carbonisation in nanofiber, the bismuth metal particle obtained or its compound have excellent electro catalytic activity to the right redox reaction of vanadium electricity.
2. the preparation method of the present invention's proposition, by electrostatic spinning technique, the material with superior electric catalytic activity can be spun the inside of matrix, in battery running process, can be stable be present in electrode, both improve the activity of electrode, catalyst can be avoided again the pollution of vanadium solution.
3. the electrospinning device used by the present invention is simple, and experiment condition is content with very little, and can well control the pattern, composition, structure etc. of fiber by Control release parameter etc.
4. the inventive method cheap, be easy to operation, the combination electrode material used for all-vanadium redox flow battery of high electrochemical activity can be prepared.
5. vanadium redox flow battery electrode reaction of the present invention is high in electrode material surface activity, and the electrocatalysis characteristic of electrode material is stablized.
Embodiment
In the specific embodiment of the present invention, the preparation method of bismuth-based catalysts/Carbon fiber nanoelectrode used for all-vanadium redox flow battery, comprises the following steps and process:
1) preparation of spinning solution: polyacrylonitrile or polyethylene glycol are joined in dimethyl formamide or dimethylacetylamide in certain proportion, stirs under water bath condition;
Wherein, the mean molecule quantity of polyacrylonitrile is 50000 ~ 200000, the mean molecule quantity of polyethylene glycol is 2000 ~ 10000, the mass ratio of polyacrylonitrile or polyethylene glycol and dimethyl formamide or dimethylacetylamide is 5:95 to 20:80 (being preferably 10:90 to 15:85), bath temperature is 40 ~ 80 DEG C, and polyacrylonitrile or the mixing time of polyethylene glycol in dimethyl formamide or dimethylacetylamide are 0.5 ~ 24 hour (being preferably 3 ~ 6 hours).
2) bismuth meal or bismuth salt (in the inorganic salts of bismuth-containing or organic salt one or more) are joined step 1 in proportion) described in spinning solution in, by stir or ultrasonic mode makes it be uniformly dispersed.Bismuth meal or the mixing time of bismuth salt in composite spinning liquid are 1 ~ 24 hour (being preferably 6 ~ 18 hours), and ultrasonic time is 0.5 ~ 10 hour (being preferably 2 ~ 6 hours).
Wherein, the inorganic salts of bismuth-containing or organic salt comprise bismuth oxide, bismuth chloride, bismuth nitrate, bismuth citrate; Polyacrylonitrile in the bismuth meal added or bismuth salt and solution or the mass ratio of polyethylene glycol are 1:100 to 10:1 (being preferably 1:50 to 1:1);
3) by step 2) the composite spinning liquid electrostatic spinning technique that obtains obtains nano fibrous membrane;
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 between syringe needle and transfer roller 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 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 4) electrode material of gained is directly with washed with de-ionized water or ultrasonic cleaning;
Wherein, ultrasonic time is 5 ~ 30 minutes.
6) by 5) electrode material after cleaning, dry in vacuum drying chamber or air dry oven, baking temperature is 50 ~ 100 DEG C, and the processing time is 12 ~ 48 hours, and the electrode material thickness after oven dry is at 0.01 ~ 5 millimeter.
Final electrode material is the controlled membranaceous or block materials of the thickness that is entwined by carbon nano-fiber, or the membranaceous or block materials that the thickness that is entwined of the carbon nano-fiber containing catalyst is controlled.
The present invention's experiment material used (as: polyacrylonitrile, polyvinylidene or bismuth salt 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 composite spinning liquid, the mean molecule quantity of polyacrylonitrile is 150000.
2) bismuth meal is joined in spinning solution, add the polyacrylonitrile in bismuth meal and solution mass ratio be 1:100, to stir after 12 hours, more ultrasonic 6 hours, obtain uniform composite spinning liquid.
3) by through step 2) the composite spinning liquid that obtains joins in the syringe of 20ml, pinhole diameter is 0.3 millimeter, the spacing of syringe needle and transfer roller is 12 centimetres, spinning voltage between syringe needle and transfer roller is 25kV, collecting board is the carbon paper of 200 micron thickness, and the rotating speed of transfer roller is 200 revs/min, and spinning solution flow velocity is 0.5 ml/hour, 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 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 800 DEG C, and programming rate is 10 DEG C/min, and the time is 4 hours, and inert protective atmosphere is nitrogen, and gas flow is 60 ml/min.
5) will through step 4) electrode material washed with de-ionized water after the carbonization that obtains 3 ~ 4 times, be then placed in the vacuum drying chamber of 100 DEG C, temperature retention time is 24 hours.Electrode material thickness after oven dry is at 0.3 millimeter, and the electrode material finally obtained is the block tangled by the compound-modified carbon nano-fiber of bismuth.
In the present embodiment, the specific area of the vanadium cell combination electrode material utilizing electrostatic spinning technique to prepare is 239.5m
2/ g, than the specific area (2.1m of carbon felt electrode
2/ g) high 2 orders of magnitude.Meanwhile, utilize electrostatic spinning this for the bismuthino compound material with electro catalytic activity to be spun carbon nano-fiber inner, not only increase the electro catalytic activity of electrode, and catalyst is well fixed on electrode matrix, ensure that the stability of electrode material.Be 100mA/cm in current density
2constant current charge-discharge test condition under, the energy efficiency applying the battery of this combination electrode brings up to 82.4% by 78.2% before not using.
Embodiment 2
Difference from Example 1 is:
1) mass fraction be 10% polyethylene glycol join under agitation in dimethyl formamide, bath temperature be at 40 DEG C stir within 3 hours, obtain composite spinning liquid, the mean molecule quantity of polyethylene glycol is 8000.
2) bismuth meal is joined in spinning solution, add the polyacrylonitrile in bismuth meal and solution mass ratio be 1:100, to stir after 12 hours, more ultrasonic 6 hours, obtain uniform composite spinning liquid.
3) by through step 2) the composite spinning liquid that obtains joins in the syringe of 20ml, pinhole diameter is 0.6 millimeter, distance between syringe needle and transfer roller is 15 centimetres, spinning voltage between syringe needle and transfer roller is 25kV, collecting board is the carbon paper of 200 micron thickness, and the rotating speed of transfer roller is 200 revs/min, and spinning solution flow velocity is 0.5 ml/hour, spinning temperature is 30 DEG C, and humidity is 40%RH.
4) by through step 3) nano fibrous membrane that obtains is put into pre-oxidation and carbonization in tube 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 800 DEG C, and programming rate is 10 DEG C/min, and the time is 4 hours, and inert protective atmosphere is nitrogen, and gas flow is 60 ml/min.
5) will through step 4) electrode material washed with de-ionized water after the carbonization that obtains 3 ~ 4 times, be then placed in the vacuum drying chamber of 100 DEG C, temperature retention time is 24 hours.Electrode material thickness after oven dry is at 0.3 millimeter, and the electrode material finally obtained is the block tangled by the carbon nano-fiber that bismuthino is compound-modified.
In the present embodiment, the specific area of the vanadium cell combination electrode material utilizing electrostatic spinning technique to prepare is 150.6m
2/ g, than the specific area (2.1m of carbon felt electrode
2/ g) high 2 orders of magnitude.Meanwhile, utilize electrostatic spinning this for the bismuthino compound material with electro catalytic activity to be spun carbon nano-fiber inner, not only increase the electro catalytic activity of electrode, and catalyst is well fixed on electrode matrix, ensure that the stability of electrode material.Be 100mA/cm in current density
2constant current charge-discharge test condition under, the energy efficiency applying the battery of this combination electrode brings up to 80.5% by 78.2% before not using.
Embodiment 3
1) mass fraction be 13% polyacrylonitrile join under agitation in dimethyl formamide, bath temperature be at 80 DEG C stir within 2 hours, obtain composite spinning liquid, the mean molecule quantity of polyacrylonitrile is 120000.
2) bismuth chloride is joined in spinning solution, add the polyacrylonitrile in bismuth chloride and solution mass ratio be 1:20, to stir after 10 hours, more ultrasonic 2 hours, obtain uniform composite spinning liquid.
3) by through step 2) the composite spinning liquid that obtains joins in the syringe of 40ml, pinhole diameter is 0.9 millimeter, distance between syringe needle and transfer roller is 15 centimetres, spinning voltage between syringe needle and transfer roller is 30kV, collecting board is the carbon paper of 200 micron thickness, and the rotating speed of transfer roller is 500 revs/min, and spinning solution flow velocity is 1.0 mls/hour, 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 furnace, and Pre oxidation is 300 DEG C, and programming rate is 20 DEG C/min, and temperature retention time is 4 hours, and atmosphere is air; Carburizing temperature is 900 DEG C, and programming rate is 10 DEG C/min, and the time is 4 hours, and inert protective atmosphere is nitrogen, and gas flow is 80 ml/min.
5) will through step 4) electrode material washed with de-ionized water after the carbonization that obtains 3 ~ 4 times, be then placed in the vacuum drying chamber of 80 DEG C, temperature retention time is 24 hours.Electrode material thickness after oven dry is at 0.6 millimeter, and the electrode material finally obtained is the block tangled by the compound-modified carbon nano-fiber of bismuth.
In the present embodiment, the specific area of the vanadium cell combination electrode material utilizing electrostatic spinning technique to prepare is 250.6m
2/ g, than the specific area (2.1m of carbon felt electrode
2/ g) high 2 orders of magnitude.Meanwhile, utilize electrostatic spinning this for the bismuthino compound material with electro catalytic activity to be spun carbon nano-fiber inner, not only increase the electro catalytic activity of electrode, and catalyst is well fixed on electrode matrix, ensure that the stability of electrode material.Be 100mA/cm in current density
2constant current charge-discharge test condition under, the energy efficiency applying the battery of this combination electrode brings up to 83.3% by 78.2% before not using.
Embodiment 4
1) mass fraction be 15% polyacrylonitrile join under agitation in dimethyl formamide, bath temperature be at 80 DEG C stir within 4 hours, obtain composite spinning liquid, the mean molecule quantity of polyacrylonitrile is 150000.
2) bismuth citrate is joined in spinning solution, add the polyacrylonitrile in bismuth citrate and solution mass ratio be 1:10, to stir after 18 hours, more ultrasonic 2 hours, obtain uniform composite spinning liquid.
3) by through step 2) the composite spinning liquid that obtains joins in the syringe of 25ml, pinhole diameter is 0.9 millimeter, distance between syringe needle and transfer roller is 16 centimetres, spinning voltage between syringe needle and transfer roller is 30kV, collecting board is the charcoal cloth of 200 micron thickness, and the rotating speed of transfer roller is 800 revs/min, and spinning solution flow velocity is 1.2 mls/hour, 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 furnace, and Pre oxidation is 270 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 the time is 3 hours, and inert protective atmosphere is nitrogen, and gas flow is 80 ml/min.
5) will through step 4) electrode material washed with de-ionized water after the carbonization that obtains 3 ~ 4 times, be then placed in the vacuum drying chamber of 100 DEG C, temperature retention time is 24 hours.Electrode material thickness after oven dry is at 1.0 millimeters, and the electrode material finally obtained is the block tangled by the compound-modified carbon nano-fiber of bismuth.
In the present embodiment, the specific area of the vanadium cell combination electrode material utilizing electrostatic spinning technique to prepare is 231.6m
2/ g, than the specific area (2.1m of carbon felt electrode
2/ g) high 2 orders of magnitude.Meanwhile, utilize electrostatic spinning this for the bismuthino compound material with electro catalytic activity to be spun carbon nano-fiber inner, not only increase the electro catalytic activity of electrode, and catalyst is well fixed on electrode matrix, ensure that the stability of electrode material.Be 100mA/cm in current density
2constant current charge-discharge test condition under, the energy efficiency applying the battery of this combination electrode brings up to 84.2% by 78.2% before not using.
Embodiment 5
1) mass fraction be 16% polyacrylonitrile join under agitation in dimethyl formamide, bath temperature be at 80 DEG C stir within 4 hours, obtain composite spinning liquid, the mean molecule quantity of polyacrylonitrile is 100000.
2) bismuth nitrate is joined in spinning solution, add the polyacrylonitrile in bismuth nitrate and solution mass ratio be 1:5, to stir after 18 hours, more ultrasonic 2 hours, obtain uniform composite spinning liquid.
3) by through step 2) the composite spinning liquid that obtains joins in the syringe of 40ml, pinhole diameter is 1.0 millimeters, distance between syringe needle and transfer roller is 15 centimetres, spinning voltage between syringe needle and transfer roller is 30kV, collecting board is the aluminium foil of 30 micron thickness, and the rotating speed of transfer roller is 1000 revs/min, and spinning solution flow velocity is 1.4 mls/hour, spinning temperature is 40 DEG C, and humidity is 55%RH.
4) by through step 3) nano fibrous membrane that obtains is put into pre-oxidation and carbonization in tube furnace, and Pre oxidation is 300 DEG C, and programming rate is 10 DEG C/min, and temperature retention time is 4 hours, and atmosphere is air; Carburizing temperature is 800 DEG C, and programming rate is 10 DEG C/min, and the time is 4 hours, and inert protective atmosphere is nitrogen, and gas flow is 100 ml/min.
5) will through step 4) electrode material washed with de-ionized water after the carbonization that obtains 3 ~ 4 times, be then placed in the vacuum drying chamber of 100 DEG C, temperature retention time is 48 hours.Electrode material thickness after oven dry is at 1.2 millimeters, and the electrode material finally obtained is the block tangled by the compound-modified carbon nano-fiber of bismuth.
In the present embodiment, the specific area of the vanadium cell combination electrode material utilizing electrostatic spinning technique to prepare is 212.6m
2/ g, than the specific area (2.1m of carbon felt electrode
2/ g) high 2 orders of magnitude.Meanwhile, utilize electrostatic spinning this for the bismuthino compound material with electro catalytic activity to be spun carbon nano-fiber inner, not only increase the electro catalytic activity of electrode, and catalyst is well fixed on electrode matrix, ensure that the stability of electrode material.Be 100mA/cm in current density
2constant current charge-discharge test condition under, the energy efficiency applying the battery of this combination electrode brings up to 81.2% by 78.2% before not using.
Embodiment result shows, adopts all-vanadium flow battery combination electrode material prepared by method of the present invention, and carbon fiber diameter is at Nano grade, and specific area compares traditional used electrode material to be increased greatly.Again due to by carbon nano-fiber and highly active bismuthino eelctro-catalyst compound, the electro-chemical activity of electrode will significantly improve, thus the energy efficiency of raising all-vanadium flow battery greatly.
Claims (9)
1. a preparation method for combination electrode used for all-vanadium redox flow battery, is characterized in that, comprises the following steps and process:
1) preparation of spinning solution: polyacrylonitrile or polyethylene glycol are joined in dimethyl formamide or dimethylacetylamide in certain proportion, stirs under water bath condition;
Wherein, the mean molecule quantity of polyacrylonitrile is 50000 ~ 200000, the mean molecule quantity of polyethylene glycol is 2000 ~ 10000, and the mass ratio of polyacrylonitrile or polyethylene glycol and dimethyl formamide or dimethylacetylamide is 5:95 to 20:80, and bath temperature is 40 ~ 80 DEG C;
2) bismuth meal or bismuth salt are joined 1 in proportion) described in spinning solution in, by stir or ultrasonic mode make it be uniformly dispersed;
Wherein, bismuth salt is one or more in the inorganic salts of bismuth-containing or organic salt, and the polyacrylonitrile in the bismuth meal added or bismuth salt and solution or the mass ratio of polyethylene glycol are 1:100 to 10:1;
3) by 2) the composite spinning liquid electrostatic spinning technique that obtains obtains nano fibrous membrane;
4) by 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 4) electrode material of gained is directly with washed with de-ionized water or ultrasonic cleaning;
Wherein, ultrasonic time is 5 ~ 30 minutes.
2. the preparation method of combination electrode used for all-vanadium redox flow battery according to claim 1, is characterized in that, step 1) in, polyacrylonitrile or polyethylene glycol are in the mixing time 0.5 ~ 24 hour of dimethyl formamide or dimethylacetylamide.
3. the preparation method of combination electrode used for all-vanadium redox flow battery according to claim 1, is characterized in that, step 2) in, the mixing time of bismuth salt in composite spinning liquid is 1 ~ 24 hour, and ultrasonic time is 0.5 ~ 10 hour.
4. the preparation method of combination electrode used for all-vanadium redox flow battery according to claim 1, is characterized in that, step 2) in, the inorganic salts of bismuth-containing or organic salt comprise bismuth oxide, bismuth chloride, bismuth nitrate, bismuth citrate.
5. the preparation method of combination electrode used for all-vanadium redox flow battery according to claim 1, 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 between syringe needle and transfer roller is 10 ~ 50 centimetres, spinning temperature is 20 ~ 50 DEG C, and spinning humidity is 20 ~ 70%RH.
6. the preparation method of combination electrode used for all-vanadium redox flow battery according to claim 5, 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.
7. the preparation method of combination electrode used for all-vanadium redox flow battery according to claim 1; 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.
8. the preparation method of combination electrode used for all-vanadium redox flow battery according to claim 1, it is characterized in that, step 5) cleaning after electrode material, dry in vacuum drying chamber or air dry oven, baking temperature is 50 ~ 100 DEG C, processing time is 12 ~ 48 hours, and the electrode material thickness after oven dry is at 0.01 ~ 5 millimeter.
9. the preparation method of combination electrode used for all-vanadium redox flow battery according to claim 1, it is characterized in that, final electrode material is the controlled membranaceous or block materials of the thickness that is entwined by carbon nano-fiber, or the membranaceous or block materials that the thickness that is entwined of the carbon nano-fiber containing catalyst is controlled.
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