CN109167071A - A kind of cathode for whole vanadium oxide reduction flow battery and preparation method thereof - Google Patents
A kind of cathode for whole vanadium oxide reduction flow battery and preparation method thereof Download PDFInfo
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- CN109167071A CN109167071A CN201811008817.8A CN201811008817A CN109167071A CN 109167071 A CN109167071 A CN 109167071A CN 201811008817 A CN201811008817 A CN 201811008817A CN 109167071 A CN109167071 A CN 109167071A
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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
- H01M4/8605—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
- H01M4/96—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
- 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
Abstract
The invention discloses a kind of cathode for whole vanadium oxide reduction flow battery preparation methods, it is related to vanadium cell technical field, after activating carbon fibre in advance, it will be on the carbon fibre of zinc nitrate deposition after activation, carbon fibre is placed under high temperature inert atmosphere again, the zinc oxide generated due to the zinc nitrate pyrolysis on carbon fibre, redox reaction occurs for the carbon in zinc oxide and carbon fiber, so the carbon atom on carbon fibre surface is etched, generation obtains a kind of porous, high-specific surface area cathode for whole vanadium oxide reduction flow battery.The invention also discloses a kind of cathode for whole vanadium oxide reduction flow battery, since the carbon fibre after being etched has the characteristics that porous and high-specific surface area, use the carbon fibre after being etched as cathode for whole vanadium oxide reduction flow battery, the energy efficiency and electrolyte utilization rate of battery can be improved.
Description
Technical field
The present invention relates to vanadium cell technical field more particularly to a kind of cathode for whole vanadium oxide reduction flow battery and its systems
Preparation Method.
Background technique
With the development of science and technology, electrochemical energy storage device is more and more concerned by people, wherein full vanadium oxygen
Change reduction flow battery, which possesses, to have extended cycle life, is easy other battery system institutes such as scale, quick response and addressing freedom
The advantage to hardly match, thus vanadium redox battery becomes the emphasis of field technical staff research.
In the prior art, the electrolyte in vanadium redox battery is power storage medium, is stored in outside battery
In portion's storage tank, usually using untreated carbon materials as electrode material.Electrolyte solution enters electricity by the circulatory system
Heap, in electrode surface generation redox reaction, electric discharge, battery plus-negative plate potential difference is reduced, and chemical energy is converted into electric energy, fills
When electric, battery plus-negative plate potential difference is increased, and electric energy is converted into chemical energy, to realize the storage and release of electric energy.
In the above prior art, use the carbon materials of unprocessed mistake as electrode material, due to conventional carbon material
Expect that there is the low defect of specific surface area, and chemical property is limited, cause the energy efficiency of vanadium redox battery with
And electrolyte utilization rate is all lower.
Summary of the invention
The main purpose of the present invention is to provide a kind of cathode for whole vanadium oxide reduction flow battery and preparation method thereof, purports
It is solving to use the carbon materials of unprocessed mistake as electrode material in the prior art, since conventional carbon materials have than table
The low defect of area, and chemical property is limited, leads to the energy efficiency and electrolyte benefit of vanadium redox battery
With all lower technical problem of rate.
To achieve the above object, first aspect of the embodiment of the present invention proposes a kind of cathode for whole vanadium oxide reduction flow battery system
Preparation Method, this method comprises:
Carbon fibre is taken, and activates the carbon fibre；
By the carbon fibre surface of zinc nitrate deposition after activation；
The carbon fibre for being deposited with zinc nitrate is placed under high temperature inert atmosphere and keeps the temperature default soaking time, obtains full vanadium
Redox flow batteries electrode.
Second aspect of the embodiment of the present invention provides a kind of cathode for whole vanadium oxide reduction flow battery, and the electrode passes through this
Inventive embodiments first aspect provides a kind of cathode for whole vanadium oxide reduction flow battery preparation method and is made, and has on the electrode
There are multiple holes, described hole pore size range is between 1 nanometer to 200 nanometers.
The present invention provides a kind of cathode for whole vanadium oxide reduction flow battery and preparation method thereof, by activating carbon in advance
After fiber, zinc nitrate is deposited on carbon fibre after activation, then carbon fibre is placed under high temperature inert atmosphere, due to
Zinc nitrate on carbon fibre is pyrolyzed the zinc oxide generated, and redox reaction occurs for the carbon in zinc oxide and carbon fiber, so
The carbon atom on carbon fibre surface is etched, and generation obtains a kind of porous, high-specific surface area vanadium redox battery use
Electrode.It is fine using the carbon after being etched since the carbon fibre after being etched has the characteristics that porous and high-specific surface area
Dimension is used as cathode for whole vanadium oxide reduction flow battery, and the energy efficiency and electrolyte utilization rate of battery can be improved.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those skilled in the art without creative efforts, can also basis
These attached drawings obtain other attached drawings.
Fig. 1 is that a kind of process of cathode for whole vanadium oxide reduction flow battery preparation method provided in an embodiment of the present invention is shown
It is intended to；
Fig. 2 is a kind of electrochemical property test process of vanadium redox battery provided in an embodiment of the present invention
Figure；
Fig. 3 is a kind of Flied emission scanning electron of cathode for whole vanadium oxide reduction flow battery provided in an embodiment of the present invention
Microscope figure；
Fig. 4 is a kind of another Flied emission scanning of cathode for whole vanadium oxide reduction flow battery provided in an embodiment of the present invention
Electron microscope picture；
Fig. 5 is a kind of transmission electron microscope of cathode for whole vanadium oxide reduction flow battery provided in an embodiment of the present invention
Figure；
Fig. 6 is a kind of Flied emission scanning electron of cathode for whole vanadium oxide reduction flow battery provided in an embodiment of the present invention
Microscope figure；
Fig. 7 is scheme one, scheme two and scheme three in vanadium redox battery provided in an embodiment of the present invention
The coulombic efficiency figure of middle electrode；
Fig. 8 is scheme one, scheme two and scheme three in vanadium redox battery provided in an embodiment of the present invention
The voltage efficiency figure of middle electrode；
Fig. 9 is scheme one, scheme two and scheme three in vanadium redox battery provided in an embodiment of the present invention
The energy efficiency figure of middle electrode；
Figure 10 is vanadium redox battery provided in an embodiment of the present invention in 80mA/cm2The close lower charge and discharge of electricity are bent
Line；
Figure 11 is vanadium redox battery provided in an embodiment of the present invention in 160mA/cm2The close lower charge and discharge of electricity are bent
Line chart；
Figure 12 is vanadium redox battery provided in an embodiment of the present invention in 240mA/cm2The close lower charge and discharge of electricity are bent
Line；
Figure 13 is vanadium redox battery provided in an embodiment of the present invention in 320mA/cm2The close lower charge and discharge of electricity are bent
Line.
Specific embodiment
In order to make the invention's purpose, features and advantages of the invention more obvious and easy to understand, below in conjunction with the present invention
Attached drawing in embodiment, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described reality
Applying example is only a part of the embodiment of the present invention, and not all embodiments.Based on the embodiments of the present invention, those skilled in the art
Member's every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
Referring to Fig. 1, Fig. 1 is a kind of cathode for whole vanadium oxide reduction flow battery preparation side provided in an embodiment of the present invention
The flow diagram of method, this method comprises:
S101, carbon fibre is taken, and activates carbon fibre.
Wherein, carbon fibre is high intensity, the new fiber materials of high modulus fibre of a kind of phosphorus content 95% or more.
It is to be piled up by organic fibers such as flake graphites along fiber axial direction, through obtained from carbonization and graphitization processing
Microcrystalline graphite material.
Further, when preparing electrode in the embodiment of the present invention carbon fibre used include graphite felt, carbon felt, carbon cloth,
The shape of one of carbon class material such as carbon paper and foamy carbon, carbon fibre is sheet, and thickness and area are all larger than
Zero.
Further, the purpose for activating carbon fibre is to improve the wellability of carbon fibre, so that zinc nitrate preferably sinks
On carbon fibre, activation carbon fibre method includes: product
Carbon fibre is placed in heating device, with the heating rate of 1~10 DEG C/min, by the temperature in heating device from
The temperature range of room temperature to 300~800 DEG C, and keep the temperature 0~10h.
Wherein, the high temperature furnace of the temperature-controllables such as Muffle furnace can be used in heating device.
S102, the carbon fibre surface by zinc nitrate deposition after activation.
It wherein, include: solution immersion sedimentation by the method that zinc nitrate deposits carbon fibre surface after activation, super true
Empty spray coating method and other deposition methods impregnate deposition with solution in the embodiment of the present invention and ultravacuum spray both sides
For method, the specific steps on carbon fibre surface of the description by zinc nitrate deposition after activation.
Solution impregnates sedimentation
Preset quality zinc nitrate or zinc nitrate hydrate are dissolved in deposition solvent.
Wherein, zinc nitrate or zinc nitrate hydrate used includes: the nitre such as zinc nitrate, zinc nitrate hexahydrate and nitrate trihydrate zinc
One of sour zinc hydrate.Deposition solvent used includes: deionized water, ethyl alcohol, acetone, N,N-dimethylformamide (N, N-
Dimethylformamide, DMF), one of dichloroethanes and chloroform.By preset quality zinc nitrate or zinc nitrate
Hydrate is dissolved in the solution formed after deposition solvent and is known as: zinc nitrate solution, and the concentration of zinc nitrate solution is any to saturation by zero
Concentration.
Further, the carbon fibre after activation is dipped in the deposition solvent dissolved with zinc nitrate or zinc nitrate hydrate
In, impregnate default soaking time.
Finally, taking out the carbon fibre after impregnating, and the carbon fibre after dry immersion, the carbon for being deposited with zinc nitrate is obtained
Cellulose fiber.
Wherein, since the process of the carbon fibre after dry impregnate determines the zinc nitrate and carbon that deposit on carbon fibre
The mass ratio of fiber, it is preferred that the mass ratio of the zinc nitrate gone after water and carbon fibre that deposit on carbon fibre is 0 to 20
Times.
Further, ultravacuum spray coating method hair includes:
Preset quality zinc nitrate or zinc nitrate hydrate are dissolved in deposition solvent.
Wherein, the concentration of the zinc nitrate or zinc nitrate hydrate, deposition solvent and zinc nitrate solution that are used when spraying with
Identical in above-mentioned solution immersion sedimentation, details are not described herein again.Spray equipment used preferably uses ultravacuum flush coater to protect
Quality when card spraying.
Further, carbon fibre is placed in the spraying area of spray equipment.
Further, the spout flow that spraying equipment is arranged is 0~100ml/min, opens the spray head of painting equipment, will be molten
There is the deposition solvent of zinc nitrate or zinc nitrate hydrate to be sprayed at the surface of carbon fibre.
Finally, the carbon fibre after dry spraying, obtains the carbon fibre for being deposited with zinc nitrate.
Wherein, the process of the carbon fibre after dry spraying determines the zinc nitrate and carbon deposited on carbon fibre
The mass ratio of fiber, it is preferred that the mass ratio of the zinc nitrate gone after water and carbon fibre that deposit on carbon fibre is 0 to 20
Times.
S103, the carbon fibre for being deposited with zinc nitrate is placed to keep the temperature under high temperature inert atmosphere and presets soaking time, obtained
To cathode for whole vanadium oxide reduction flow battery.Its specific steps includes:
Firstly, the carbon fibre for being deposited with zinc nitrate is placed in heating device, and it is inert atmosphere in heating device, is
Keep the inert atmosphere in heating device that can preferably be filled with inert gas into heating device.
Wherein, the high temperature furnace of the temperature-controllables such as tube furnace can be used in heating device, and argon gas, nitrogen can be used in inert gas
Gas and other inert gases.
Further, with the heating rate of 1~10 DEG C/min, by the temperature in heating device from room temperature to 900~
1100 DEG C, and keep the temperature 0~5h.
Further, the carbon fibre after heat preservation is taken out, cleans carbon fibre with the hydrochloric acid of 0.1~6mol/L.
Wherein, in heating device, under inertia high temperature atmosphere, pyrolytic reaction occurs for the zinc nitrate being deposited on carbon fibre
Zinc oxide can be generated, the chemical reaction being directed to are as follows:
Zn(NO3)2→ZnO+NO2↑+O2↑
Further, zinc oxide is reacted with the carbon atom of carbon fibre again, to reach the mesh on etching carbon fibre surface
, CO2, which is generated, due to the place of the carbon atom of zinc oxide and carbon fibre reaction, when carbon atom reacts vapors away, carbon fibre
It will form the hole of etching, hole pore size range is between 1 nanometer to 200 nanometers, to improve the ratio of carbon fibre
Surface area.The chemical reaction being directed to are as follows:
ZnO+C→Zn+CO/CO2↑
Finally, the dry carbon fibre cleaned with hydrochloric acid, obtains cathode for whole vanadium oxide reduction flow battery.
It wherein, is zinc in order to be generated in chemical reaction process and the complete oxidation of unreacted with the purpose that hydrochloric acid cleans
Zinc.
The present invention provides a kind of cathode for whole vanadium oxide reduction flow battery preparation method, by activating carbon fibre in advance
Afterwards, zinc nitrate is deposited on carbon fibre after activation, then carbon fibre is placed under high temperature inert atmosphere, due to carbon
Zinc nitrate on fiber is pyrolyzed the zinc oxide generated, and redox reaction occurs for the carbon in zinc oxide and carbon fiber, so carbon
The carbon atom of fiber surface is etched, and generation obtains a kind of porous, high-specific surface area cathode for whole vanadium oxide reduction flow battery.
Since the carbon fibre after being etched has the characteristics that porous and high-specific surface area, use the carbon fibre after being etched as
The energy efficiency and electrolyte utilization rate of battery can be improved in cathode for whole vanadium oxide reduction flow battery.
Further, a kind of cathode for whole vanadium oxide reduction flow battery provided in an embodiment of the present invention, electrode pass through upper
A kind of cathode for whole vanadium oxide reduction flow battery preparation method for stating inventive embodiments offer is made.
Specifically, the carbon fibre for being deposited with zinc nitrate is placed under high temperature inert atmosphere after preset time, obtain complete
When vanadium oxide reduction flow battery electrode, there are multiple holes on electrode, hole pore size range is received at 1 nanometer to 200
Between rice.
Further, carbon fibre used includes graphite felt, carbon felt, carbon cloth, carbon paper and foamy carbon when preparing electrode
Etc. one of carbon class material, the shape of carbon fibre is sheet, and thickness and area are all larger than zero.
Further, when zinc nitrate is deposited carbon fibre surface after activation, zinc nitrate used includes: nitric acid
One of zinc nitrates hydrates such as zinc, zinc nitrate hexahydrate and nitrate trihydrate zinc, deposition solvent used include: deionized water,
One of ethyl alcohol, acetone, DMF, dichloroethanes and chloroform.
Further, preset quality zinc nitrate or zinc nitrate hydrate are dissolved in deposition solvent, the nitric acid being formed by
The concentration of zinc solution be zero to saturation any concentration.
Further, the mass ratio of the zinc nitrate gone after water and carbon fibre that deposit on carbon fibre is 0 to 20 times.
The present invention provides a kind of cathode for whole vanadium oxide reduction flow battery, after activating carbon fibre in advance, by nitre
Sour zinc deposits on carbon fibre after activation, then carbon fibre is placed under high temperature inert atmosphere, due on carbon fibre
The zinc oxide that generates of zinc nitrate pyrolysis, redox reaction occurs for the carbon in zinc oxide and carbon fiber, so carbon fibre table
The carbon atom in face is etched, and generation obtains a kind of porous, high-specific surface area cathode for whole vanadium oxide reduction flow battery.Due to quilt
Carbon fibre after etching has the characteristics that porous and high-specific surface area, uses the carbon fibre after being etched as full vanadium oxygen
Change reduction flow battery electricity consumption pole, the energy efficiency and electrolyte utilization rate of battery can be improved.
Since during a kind of cathode for whole vanadium oxide reduction flow battery preparation method, what is deposited on carbon fibre is gone
The mass ratio of zinc nitrate and carbon fibre after water can be set to different data, be tested separately below when preparing electrode, no
In the case where the zinc nitrate and carbon fibre of homogenous quantities ratio, the chemical property of vanadium redox battery.
Referring to Fig. 2, Fig. 2 is a kind of chemical property of vanadium redox battery provided in an embodiment of the present invention
Test flow chart.
As shown in Fig. 2, being related to electrolyte when testing the electrochemical performance data of vanadium redox battery
The common steps such as configuration, the assembling of battery, the debugging of instrument, specifically include following content:
S201, positive and negative anodes electrolyte is prepared.
The analytical pure sulfuric acid amount of reordering deionized water is diluted to the diluted acid of 1~7mol/L, quantitative vanadic sulfate solid is added,
So that the electrolyte group of vanadium redox battery becomes 1~7mol/L diluted acid and adds 1~6mol/L vanadic sulfate.It is positive and negative
Pole electrolyte dosage can positive and negative anodes active material it is flux matched under the premise of, adjust concentration and dosage, freely to obtain difference
The battery of amount of capacity.
Include the following steps: specifically, preparing electrolyte
Take clean 500mL beaker, 500mL volumetric flask, magnetic stir bar, 250mL beaker, glass bar, spoon, 50mL amount
The experiment appliances such as cylinder and electronic scale, take 200mL deionized water to be placed in 500mL beaker, with 400r/ on magnetic stirring apparatus
The stirring of min revolving speed measures the concentrated sulfuric acid 84.1mL that 84.1mL mass fraction is 98% with graduated cylinder, prolongs walls of beaker and drawn with glass bar
Stream is poured slowly into beaker, and electronic scale measures tri- water vanadic sulfate of 113.0g after cooling, slowly moves into beaker, magnetic force is stirred
It mixes device revolving speed and is adjusted to 700r/min.It is transferred in volumetric flask after vanadic sulfate is completely dissolved, when solution temperature is down to room temperature,
It is settled to 500mL.
S202, assembled battery.
The electrode that the embodiment of the present invention uses is used for the positive and negative anodes of vanadium redox battery, the face of positive and negative anodes electrode
Product is 1~16cm2.Positive and negative anodes are isolated using amberplex or porous septum, use teflon gasket coordination electrode
Thickness, so that electrode final compression ratio is 50~70%, each section, which reinforce by bolt fastening structure, is assembled into full battery, examines
After having looked into air-tightness, hyperphoric good a certain amount of positive and negative anodes electrolyte.
S203, test battery.
Flow velocity of the vanadium redox battery with peristaltic pump control electrolyte in the battery, passes through new prestige battery testing
System carries out charge and discharge cycles test.Implemented by field emission scanning electron microscope and the transmission electron microscope observation present invention
The pattern of the porous cathode for whole vanadium oxide reduction flow battery of example preparation.
Wherein, above-mentioned battery two sides thickness of electrode, electrolyte volume, electrode size and electrode material can be within the above range
Unrestricted choice.
It discusses below by three kinds of schemes when preparing electrode, uses the zinc nitrate and carbon fibre of different quality ratio
In the case where, the performance of the chemical property of final vanadium redox battery
Scheme one, the zinc nitrate used are as follows: zinc nitrate hexahydrate, the carbon materials used are as follows: graphite felt, wherein by zinc nitrate
Deposition carbon fibre surface after activation, and after drying, the mass ratio of zinc nitrate hexahydrate and graphite felt is 3.5 to 1, specific behaviour
Steps are as follows for work:
S301, length and width are taken to be 4mm, with a thickness of the graphite felt two panels of 4mm, with the heating speed of 6 DEG C/min in Muffle furnace
Rate is warming up to 600 DEG C, keeps the temperature 3h, and the graphite felt after activation is immersed in configured full by configuration saturation zinc nitrate hexahydrate solution
Graphite felt quality dry in 60 DEG C of vacuum ovens after taking-up with 2h in zinc nitrate solution, constantly after debugging drying, makes six
Water zinc nitrate and graphite felt mass ratio are 3.5 to 1.
S302, by after the drying of acquisition zinc nitrate hexahydrate and graphite felt composite precursor in tube furnace under argon atmosphere,
1000 DEG C are warming up to the heating rate of 6 DEG C/min, and keeps the temperature 60min, is taken out after Temperature fall, is cleaned with the hydrochloric acid of 1mol/L
Impurity is removed, then is cleaned with deionized water to neutrality, and dry, cathode for whole vanadium oxide reduction flow battery is finally obtained.
As positive and negative anodes, Nafion-212 is diaphragm for S303, the electrode for preparing the embodiment of the present invention, poly- with a thickness of 2mm
Tetrafluoroethene is gasket, is then loaded each section grouping of battery, positive and negative anodes are all made of the VOSO of 1mol/L4And
The H of 3mol/L2SO4Amount to 25mL as electrolyte, is injected the electrolyte into battery using peristaltic pump.
S304, respectively with 80mA/cm2、160mA/cm2、240mA/cm2、320mA/cm2Current density under to battery into
The test of row charge and discharge cycles, obtains field emission scanning electron microscope figure and the library of cathode for whole vanadium oxide reduction flow battery
Human relations efficiency, voltage efficiency, energy efficiency figure.
Referring to Fig. 3, Fig. 3 is a kind of field hair of cathode for whole vanadium oxide reduction flow battery provided in an embodiment of the present invention
Scanning electron microscope diagram is penetrated, and finally measures the voltage of the vanadium redox battery under 320mA/cm2 current density
Efficiency is 81%.
Scheme two, the zinc nitrate used are as follows: zinc nitrate hexahydrate, the carbon materials used are as follows: graphite felt, wherein by zinc nitrate
Deposition carbon fibre surface after activation, and after drying, the mass ratio of zinc nitrate hexahydrate and graphite felt is 5 to 1, concrete operations
Steps are as follows:
S401, length and width are taken to be 4mm, with a thickness of the graphite felt two panels of 4mm, with the heating speed of 6 DEG C/min in Muffle furnace
Rate is warming up to 600 DEG C, keeps the temperature 3h, and the graphite felt after activation is immersed in configured full by configuration saturation zinc nitrate hexahydrate solution
Graphite felt quality dry in 60 DEG C of vacuum ovens after taking-up with 2h in zinc nitrate solution, constantly after debugging drying, makes six
Water zinc nitrate and graphite felt mass ratio are 5 to 1.
S402, by after the drying of acquisition zinc nitrate hexahydrate and graphite felt composite precursor in tube furnace under argon atmosphere,
1000 DEG C are warming up to the heating rate of 6 DEG C/min, and keeps the temperature 60min, is taken out after Temperature fall, is cleaned with the hydrochloric acid of 1mol/L
Impurity is removed, then is cleaned with deionized water to neutrality, and dry, cathode for whole vanadium oxide reduction flow battery is finally obtained.
As positive and negative anodes, Nafion-212 is diaphragm for S403, the electrode for preparing the embodiment of the present invention, poly- with a thickness of 2mm
Tetrafluoroethene is gasket, is then loaded each section grouping of battery, positive and negative anodes are all made of the VOSO of 1mol/L4And
The H of 3mol/L2SO4Amount to 25mL as electrolyte, is injected the electrolyte into battery using peristaltic pump.
S404, respectively with 80mA/cm2、160mA/cm2、240mA/cm2、320mA/cm2Current density under to battery into
The test of row charge and discharge cycles, obtains field emission scanning electron microscope figure and the library of cathode for whole vanadium oxide reduction flow battery
Human relations efficiency, voltage efficiency, energy efficiency figure.
Fig. 4 and Fig. 5 are please referred to, Fig. 4 is a kind of cathode for whole vanadium oxide reduction flow battery provided in an embodiment of the present invention
Another field emission scanning electron microscope figure, Fig. 5 be a kind of vanadium redox battery provided in an embodiment of the present invention
With the transmission electron microscope figure of electrode, and finally measure the vanadium redox battery under 320mA/cm2 current density
Voltage efficiency be 82%.
Scheme three, the zinc nitrate used are as follows: zinc nitrate hexahydrate, the carbon materials used are as follows: graphite felt, wherein by zinc nitrate
Deposition carbon fibre surface after activation, and after drying, the mass ratio of zinc nitrate hexahydrate and graphite felt is 6.5 to 1, specific behaviour
Steps are as follows for work:
S501, length and width are taken to be 4mm, with a thickness of the graphite felt two panels of 4mm, with the heating speed of 6 DEG C/min in Muffle furnace
Rate is warming up to 600 DEG C, keeps the temperature 3h, and the graphite felt after activation is immersed in configured full by configuration saturation zinc nitrate hexahydrate solution
Graphite felt quality dry in 60 DEG C of vacuum ovens after taking-up with 2h in zinc nitrate solution, constantly after debugging drying, makes six
Water zinc nitrate and graphite felt mass ratio are 6.5 to 1.
S502, by after the drying of acquisition zinc nitrate hexahydrate and graphite felt composite precursor in tube furnace under argon atmosphere,
1000 DEG C are warming up to the heating rate of 6 DEG C/min, and keeps the temperature 60min, is taken out after Temperature fall, is cleaned with the hydrochloric acid of 1mol/L
Impurity is removed, then is cleaned with deionized water to neutrality, and dry, cathode for whole vanadium oxide reduction flow battery is finally obtained.
As positive and negative anodes, Nafion-212 is diaphragm for S503, the electrode for preparing the embodiment of the present invention, poly- with a thickness of 2mm
Tetrafluoroethene is gasket, is then loaded each section grouping of battery, positive and negative anodes are all made of the VOSO of 1mol/L4And
The H of 3mol/L2SO4Amount to 25mL as electrolyte, is injected the electrolyte into battery using peristaltic pump.
S504, respectively with 80mA/cm2、160mA/cm2、240mA/cm2、320mA/cm2Current density under to battery into
The test of row charge and discharge cycles, obtains field emission scanning electron microscope figure and the library of cathode for whole vanadium oxide reduction flow battery
Human relations efficiency, voltage efficiency, energy efficiency figure.
Referring to Fig. 6, Fig. 6 is a kind of field hair of cathode for whole vanadium oxide reduction flow battery provided in an embodiment of the present invention
Scanning electron microscope diagram is penetrated, and finally measures the voltage of the vanadium redox battery under 320mA/cm2 current density
Efficiency is 80%.
Fig. 7, Fig. 8 and Fig. 9 are please referred to, Fig. 7 is side in vanadium redox battery provided in an embodiment of the present invention
The coulombic efficiency figure of electrode in case one, scheme two and scheme three, Fig. 8 are whole vanadium oxide reduction liquid provided in an embodiment of the present invention
In galvanic battery in scheme one, scheme two and scheme three electrode voltage efficiency figure, Fig. 9 be full vanadium provided in an embodiment of the present invention
In redox flow batteries in scheme one, scheme two and scheme three electrode energy efficiency figure.
Figure 10, Figure 11, Figure 12 and Figure 13 are please referred to, Figure 10 is vanadium redox provided in an embodiment of the present invention
Battery is in 80mA/cm2The close lower charging and discharging curve of electricity, Figure 11 are that vanadium redox battery provided in an embodiment of the present invention exists
160mA/cm2The close lower charging and discharging curve figure of electricity, 12 exist for vanadium redox battery provided in an embodiment of the present invention
240mA/cm2The close lower charging and discharging curve of electricity, Figure 13 are that vanadium redox battery provided in an embodiment of the present invention exists
320mA/cm2The close lower charging and discharging curve of electricity.
In association schemes one, scheme two and scheme three, the Flied emission of cathode for whole vanadium oxide reduction flow battery is scanned
The coulombic efficiency of electron microscope picture and electrode, voltage efficiency, energy efficiency figure, it can be observed that carbon fibre surface is carved
Hole out is lost, the efficiency value further according to battery under different current densities is it can be concluded that the carbon prepared in present example
Fiber electrode material has very high chemical property to show compared to original graphite felt, and voltage efficiency is in 320mA/cm2Electric current
Still there is 25% promotion under density.It is a kind of new, high-performance porous carbon material electrode.
It declares again, the application of the present invention is not limited to the above, for those of ordinary skills, Ke Yigen
It is improved or converted according to above description, all these modifications and variations all should belong to the protection model of appended claims of the present invention
It encloses.
It should be noted that for the various method embodiments described above, describing for simplicity, therefore, it is stated as a series of
Combination of actions, but those skilled in the art should understand that, the present invention is not limited by the sequence of acts described because
According to the present invention, certain steps can use other sequences or carry out simultaneously.Secondly, those skilled in the art should also know
It knows, the embodiments described in the specification are all preferred embodiments, and related actions and modules might not all be this hair
Necessary to bright.
In the above-described embodiments, it all emphasizes particularly on different fields to the description of each embodiment, there is no the portion being described in detail in some embodiment
Point, it may refer to the associated description of other embodiments.
The above are retouching to a kind of cathode for whole vanadium oxide reduction flow battery provided by the present invention and preparation method thereof
It states, for those skilled in the art, thought according to an embodiment of the present invention can in specific embodiments and applications
There is change place, to sum up, the contents of this specification are not to be construed as limiting the invention.
Claims (10)
1. a kind of cathode for whole vanadium oxide reduction flow battery preparation method, which is characterized in that the described method includes:
Carbon fibre is taken, and activates the carbon fibre；
By the carbon fibre surface of zinc nitrate deposition after activation；
The carbon fibre for being deposited with zinc nitrate is placed under high temperature inert atmosphere and keeps the temperature default soaking time, obtains full vanadium oxidation
Restore flow battery electricity consumption pole.
2. the method according to claim 1, wherein the activation carbon fibre includes:
The carbon fibre is placed in heating device, with the heating rate of 1~10 DEG C/min, by the temperature in the heating device
Degree keeps the temperature 0~10h from room temperature to 300~800 DEG C.
3. according to the method described in claim 2, it is characterized in that, described that the carbon of zinc nitrate deposition after activation is fine
Dimension table face includes:
Zinc nitrate or zinc nitrate hydrate are dissolved in deposition solvent；
The carbon fibre after activation is soaked in dissolved in the deposition solvent of zinc nitrate or zinc nitrate hydrate；
The carbon fibre after impregnating, and the carbon fibre after dry immersion are taken out, the institute for being deposited with zinc nitrate is obtained
State carbon fibre.
4. according to the method described in claim 2, it is characterized in that, described that the carbon of zinc nitrate deposition after activation is fine
Dimension table face includes:
Zinc nitrate or zinc nitrate hydrate are dissolved in deposition solvent；
The carbon fibre is placed in the spraying area of spray equipment；
The spout flow that the spraying equipment is arranged is 0~100ml/min, opens the spray head of the painting equipment, will be dissolved with nitre
The deposition solvent of sour zinc or zinc nitrate hydrate is sprayed at the surface of the carbon fibre；
The carbon fibre after dry spraying, obtains the carbon fibre for being deposited with zinc nitrate.
5. according to claim 1 to described in any item methods described in 4, which is characterized in that described to be deposited with zinc nitrate
Carbon fibre, which is placed under high temperature inert atmosphere, keeps the temperature default soaking time, obtains cathode for whole vanadium oxide reduction flow battery packet
It includes:
The carbon fibre for being deposited with zinc nitrate is placed in heating device, and is inert atmosphere in the heating device；
With the heating rate of 1~10 DEG C/min, by the temperature in the heating device from room temperature to 900~1100 DEG C, and
Keep the temperature 0~5h；
The carbon fibre after taking out heat preservation, cleans the carbon fibre with the hydrochloric acid of 0.1~6mol/L；
The dry carbon fibre cleaned with hydrochloric acid, obtains cathode for whole vanadium oxide reduction flow battery.
6. described in any item methods according to claim 3, which is characterized in that the carbon taken out after impregnating
Fiber, and the carbon fibre after dry immersion, the carbon fibre for obtaining being deposited with zinc nitrate include:
The carbon fibre after impregnating is taken out, and the carbon fibre is placed in 60 DEG C of vacuum ovens to dry, repetition tune
The carbon fibre after examination is dry, makes the mass ratio 3.5 to 1 of zinc nitrate or zinc nitrate hydrate and the carbon fibre；
Alternatively, taking out the carbon fibre after impregnating, and the carbon fibre is placed in 60 DEG C of vacuum ovens to dry, weight
The carbon fibre after polyphony examination is dry compares the mass ratio 5 of zinc nitrate or zinc nitrate hydrate and the carbon fibre
1；
Alternatively, taking out the carbon fibre after impregnating, and the carbon fibre is placed in 60 DEG C of vacuum ovens to dry, weight
The carbon fibre after polyphony examination is dry, makes the mass ratio 6.5 of zinc nitrate or zinc nitrate hydrate and the carbon fibre
Than 1.
7. described in any item methods according to claim 4, which is characterized in that the carbon after the dry spraying
Fiber, the carbon fibre for obtaining being deposited with zinc nitrate include:
The carbon fibre after taking out spraying, and the carbon fibre is placed in 60 DEG C of vacuum ovens to dry, repetition tune
The carbon fibre after examination is dry, makes the mass ratio 3.5 to 1 of zinc nitrate or zinc nitrate hydrate and the carbon fibre；
Alternatively, taking out the carbon fibre after spraying, and the carbon fibre is placed in 60 DEG C of vacuum ovens to dry, weight
The carbon fibre after polyphony examination is dry compares the mass ratio 5 of zinc nitrate or zinc nitrate hydrate and the carbon fibre
1；
Alternatively, taking out the carbon fibre after spraying, and the carbon fibre is placed in 60 DEG C of vacuum ovens to dry, weight
The carbon fibre after polyphony examination is dry, makes the mass ratio 6.5 of zinc nitrate or zinc nitrate hydrate and the carbon fibre
Than 1.
8. a kind of cathode for whole vanadium oxide reduction flow battery, which is characterized in that the electrode is any by claim 1 to 7
A kind of cathode for whole vanadium oxide reduction flow battery preparation method described in is made, and has multiple holes, institute on the electrode
Hole pore size range is stated between 1 nanometer to 200 nanometers.
9. electrode according to claim 8, which is characterized in that carbon fibre used includes graphite when preparing the electrode
One of carbon class material such as felt, carbon felt, carbon cloth, carbon paper and foamy carbon, the shape of the carbon fibre are sheet.
10. electrode according to claim 9, which is characterized in that in the carbon fibre by zinc nitrate deposition after activation
When surface, zinc nitrate used includes: one of zinc nitrates hydrates such as zinc nitrate, zinc nitrate hexahydrate and nitrate trihydrate zinc,
Deposition solvent used includes: one of deionized water, ethyl alcohol, acetone, DMF, dichloroethanes and chloroform；
Zinc nitrate or zinc nitrate hydrate are dissolved in deposition solvent, the concentration for the zinc nitrate solution being formed by is zero to saturation
Any concentration；
The mass ratio of the zinc nitrate gone after water and carbon fibre that deposit on the carbon fibre is 0 to 20 times.
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