CN105529473B - The electrode material that energy storage flow battery is modified with graphene oxide - Google Patents
The electrode material that energy storage flow battery is modified with graphene oxide 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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- 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 present invention relates to the electrode materials and preparation method thereof that energy storage flow battery is modified with graphene oxide, the electrode material is made of the graphene oxide compound of carbon materials matrix and its surface, the method is using hydro-thermal method by graphene oxide-loaded in carbon pole surface, by the electrode material of modification, its specific surface area has obtained significantly increasing, increase the contact area of electrolyte and electrode, increase the reactivity site of electrode and electrolyte, modified its oxygen-containing functional group of electrode increased dramatically simultaneously, reduce the electrochemical reaction internal resistance of vanadium redox flow battery electrode and the transmission resistance of electronics, reduce overpotential of the battery under high current density, to greatly improve the voltage efficiency and energy efficiency under all-vanadium flow battery high current density.
Description
Technical field
It prepares and its applies the present invention relates to energy storage flow battery electrode material, especially a kind of electricity used for all-vanadium redox flow battery
Pole and its application.
Background technology
Redox flow batteries (VRB) are one of extensive energy storage technology of most foreground, vanadium redox
Battery be using vanadium ion solution as the secondary cell of positive and negative electrode active material, main composition by V electrolyte, diaphragm, electrode and
The compositions such as collector.Anode electrolyte is V (V) and V (IV) sulfuric acid solution, and cathode is V (III) and V (II) sulfuric acid solution.Pass through
External pump is pumped into solution in battery pile from reservoir, electrolyte flow through graphite felt electrode be electrochemically reacted and then
Solution is transmitted back to reservoir.The active material of liquid constantly circulates, and inside battery passes through H+It is transported back and forth on diaphragm both sides
It is dynamic to realize conduction.It is secondary compared to solid due to the external storage feature of flow battery supporting electrolyte and electroactive substance
Battery system has the advantages that more excellent, and most prominent advantage is that it can detach energy capacity with power output.Power and energy
The design that the separation of amount will make all-vanadium flow battery be suitble to distinct device.In addition, in redox flow batteries, electrode is only
Reacting environment is provided for cell oxidation reduction reaction, simple operation principle makes all-vanadium flow battery service life considerably long.
All-vanadium liquid flow energy storage system is as a kind of efficient energy storage device, because it is with pollution-free, long-life, energy-efficient and maintenance
The advantages that simple, so in solar energy, wind energy storage, grid-connected, peak load regulation network, power supply system from far-off regions and uninterruptible power supply
Equal fields show wide application prospect.
The conductive height of carbon pole, mechanical strength is good, excellent corrosion resistance, and stability is good, large specific surface area etc.
Advantage, so the utilization in flow battery is very extensive, especially as the electrode of all-vanadium flow battery.But because carbon
Electrode active surface functional group type and quantity are relatively fewer, so the catalytic activity of carbon pole is low, to limit full vanadium liquid
The operating condition of galvanic battery high current charge-discharge.
In order to improve energy efficiency and power efficiency of the all-vanadium flow battery under high current density, effective ways are at present
Electrochemical catalyst is introduced on graphite felt electrode surface, redox is reduced and converts activation energy, be mainly the following method：
(1) graphite felt electrode is modified using noble metal or metal oxide, changes electrode reaction course, reduce graphite felt electrode
Reaction activity.Research shows that the graphite felt electrode of the metals such as load iridium (Ir), indium (In) is lived with good electrochemical catalysis
Property, pyrolysis reduction H2IrCl6It prepares Ir and modifies carbon felt electrode, reduce V (IV)/V (V) electricity to Charge-transfer resistance, but simultaneously
The overpotential of electrode liberation of hydrogen is reduced, thus can be only applied to the modification of vanadium cell positive electrode.Bismuth (Bi) metal has high
Overpotential of hydrogen evolution, by thermal decomposition, electro-deposition nanometer Bi metals can not only inhibit hydrogen to be precipitated in graphite felt surface, but also
V (II)/V (III) electricity is promoted to electrochemical redox reaction, but metal Bi, Ir belong to noble metal, expensive, limit
Their large-scale applications are made.Mn3O4, Nb2O5Equal metal oxides can reduce electrode reaction activation energy, improve electrode reaction
Rate reduces Chemical Kinetics, has good catalytic action to vanadium battery electrode reaction, but their electric conductivity are low, viscous
The problems such as attached unstable, is urgently to be resolved hurrily；(2) graphite felt is handled using heat treatment, acid processing and electroxidation method, increases graphite felt
Surface C-O, C=O and N functional groups, improve the electro-chemical activity of electrode, since all-vanadium flow battery is in a kind of state of flowing
Lower carry out charge and discharge, during long reaction, these chemical functional groups can gradually fall off, and cause battery capacity decaying serious.
Although carbon nanotube and carbon nano-fiber are grown in Carbon felt surface by Minjoon Park etc. simultaneously using CVD method
(see reference document：Synergistic effect of carbon nanofiber/nanotube composite
catalyst on carbon felt electrode for high-performance all-vanadium redox
flow battery[J].Nano letters,2013,13(10):4833-4839.), larger improves all-vanadium flow battery
Charging and discharging currents density, show higher energy efficiency and voltage efficiency, but this method prepares electrode process complexity, it is real
It tests hot conditions and causes a large amount of energy losses, electrode subsequent processing is cumbersome, and entire electrode production process will expend a large amount of manpower objects
Power, so the Electrode treatment process is not appropriate for all-vanadium flow battery.
Invention content
In order to overcome the shortcomings of that all-vanadium flow battery carbon pole electro-chemical activity, the present invention provide a kind of all-vanadium flow electricity
The electrode and preparation method thereof that pond is modified with graphene oxide, by the graphene oxide group of carbon materials substrate and its surface modification
At, by hydro-thermal method using graphene oxide modify carbon materials electrode, form equally distributed oxidation on carbon materials surface
Graphene nano layer improves electrode electro Chemical performance, and preparation process flow is simple, of low cost, can be applied on a large scale
The preparation of vanadium redox flow battery electrode.
In order to solve the above technical problems, present invention firstly provides a kind of electricity of graphene oxide modification used for all-vanadium redox flow battery
Pole material modifies carbon materials electrode, in the matrix using graphene oxide using carbon class material as matrix by hydro-thermal method
Surface forms graphene oxide compound, and wherein graphene oxide accounts for 1~10wt% of electrode material；The carbon class material is
The carbon materials such as carbon felt, graphite felt, carbon cloth, carbon paper.
Preferably, the graphene oxide contains hydroxyl, carboxyl, epoxy group, carbonyl, has three-dimensional structure, the hydroxyl
Molar ratio with carboxyl is 2:1-1:3, oxygen content is 20wt%-30wt% in graphene oxide, and graphene oxide composite material exists
The surface of carbon class material is distributed relatively uniform, thickness 20-2000nm.
The present invention provides a kind of preparation method of the electrode material of graphene oxide modification used for all-vanadium redox flow battery, packet simultaneously
Include following steps：
Step 1), using hummer methods, either oxygen is obtained by the reaction in graphite flake or graphite powder by the improved methods of hummers
Hydrogen peroxide is added dropwise until bubble-free in solution generates in graphite alkene solution in above-mentioned solution；
Step 2) takes graphene oxide solution obtained by step 1), and hydrochloric acid is added, is put into centrifuge tube, centrifuge washing, takes clear
Liquid is put into centrifuge tube, and high speed centrifugation is precipitated, and clear water eccentric cleaning is added and takes centrifuge tube until washing is deposited to neutrality
Middle precipitation is placed in beaker, be added deionized water, ultrasonic disperse to get various concentration graphene oxide solution；
Step 3) takes graphene oxide solution obtained by step 2), is put into polytetrafluoroethylene (PTFE) autoclave, and carbon is added
The ratio of material, carbon materials and graphene oxide is 15-50cm2：0.01-0.1g, hydro-thermal reaction are cooled to room temperature, and are obtained
Target electrode.
Preferably, in step 1) hummer methods or the improved methods of hummers, KMnO4Mass ratio with graphene is
1-10：1, dense H3PO4With dense H2SO4Volume ratio be 0-1：10, it is optionally added into sodium nitrate, potassium peroxydisulfate.
Preferably, it is 10~50ml that concentration of hydrochloric acid, which is 0.1~3mol/L volumes, in step 2), centrifugation time be 15min~
300min, rotating speed are 2000~5000r/min, and centrifuge washing is three times.
Preferably, the centrifugation time that clear water eccentric cleaning is added in step 2) is 30min~540min, rotating speed is 6000~
10000r/min, until the pH value in washing solution is 6~7.
Preferably, 30~120min of ultrasonic disperse in step 2), the concentration of gained graphene oxide solution is respectively 0.5,
1、1.5、2、2.5、3、3.5、4、4.5、5、5.5、6、6.5g/L。
Preferably, in step 3), 10~40ml of graphene oxide solution is put into 100ml polytetrafluoroethylene (PTFE) autoclaves
In, it is 15~50cm to be put into one piece of area2Graphite felt, when the reaction time is 2~24,150~200 DEG C of hydrothermal temperature.
The present invention further provides application of the above-mentioned electrode material in all-vanadium liquid flow energy storage battery, the current densities of battery
For 100-250mA/cm2, current efficiency 95-98%, voltage efficiency 80-97%.
Further, energy efficiency 80-90%.
From the foregoing, it will be observed that the technology path of the present invention is：By potassium permanganate, the concentrated sulfuric acid and concentrated phosphoric acid mixing, it is optionally added into
Sodium nitrate, potassium peroxydisulfate obtain graphene oxide mixed solution after reacting a period of time, are obtained through overpickling and washing
Purer graphene oxide solution, the graphene oxide that obtained graphene oxide solution is diluted to various concentration are molten
Liquid is added to together with carbon materials in polytetrafluoroethylene (PTFE) autoclave, at a certain temperature, hydro-thermal reaction for a period of time,
Obtain the electrode material of graphene oxide modification.
Common electrode is prepared and modification technique route in compared with the existing technology：Carbon is prepared using the method for high annealing
Crude granule is dried for standby using pickling, the impurity of washing carbon particle, is glued the carbon particle of preparation using nafion solution
On graphite felt fibres surface, a few hours are dried in the UV lamp, and obtaining the graphite felt electrode of carbon particle modification, (see reference text
It offers：Park M,Ryu J,Kim Y,et al.Corn protein-derived nitrogen-doped carbon
materials with oxygen-rich functional groups:a highly efficient
electrocatalyst for all-vanadium redox flow batteries[J].Energy&Environmental
Science,2014,7(11):3727-3735.)。
Compared with the prior art, the method processing oxidation stone using high annealing is omitted in preparation process in the present invention
The preparation process of black alkene, this experiment directly uses hydro-thermal method, and in graphite felt, the reaction time is short by graphene oxide-loaded, is omitted
The processing procedure of presoma and time, reaction condition is mild, reduces energy consumption, not will produce toxic, pernicious gas in production process,
Greatly save equipment and fund input.
By regulating and controlling the preparation process and hydrothermal reaction condition of graphene oxide, the present invention obtains having elevated oxygen level
Graphene oxide has abundant oxygen-containing functional group, the electricity with stannic oxide/graphene nano layer is prepared on carbon materials
Pole material.In all-vanadium flow battery, there is excellent electric property.By controlling oxygen content and official in graphene oxide
The ratio of hydroxyl and carboxyl can be rolled into a ball, electrode of the invention has very excellent current efficiency, voltage efficiency and energy efficiency, tool
Have broad application prospects.
Description of the drawings
Fig. 1 is the graphite felt electrode that the embodiment of the present invention 1 is modified and blank graphite felt electrode in 150mA/cm2Electric current is close
The lower charging and discharging curve figure of degree, it can be seen from the figure that the present invention has very using the graphite felt electrode of graphene oxide modification
Excellent chemical property.
Fig. 2 is blank group graphite felt figure compared with the graphite felt electrode that the graphene oxide of embodiment 1 is modified, and shows to aoxidize
Graphene is successfully supported on graphite felt fibres surface, and is distributed very uniform.
Fig. 3 be embodiment 1 graphene oxide modification graphite felt XSP collection of illustrative plates in oxygen and carbon content ratio, the bright oxygen of the chart
Carbon ratios level off to 1:1, it is modified electrode surface and contains a large amount of oxygen-containing functional groups.
Fig. 4 is that the cyclic voltammogram of 2g/L graphene modified graphite felts modifies graphite felt with by hydro-thermal method graphene oxide
It is compared, the graphite felt electrode electrochemistry comprehensive performance of the bright graphene oxide modification of the chart is higher than the graphite of graphene modified
Felt electrode.
Specific implementation mode
Below by example, the invention will be further described.Unless otherwise noted, the raw material employed in the present invention is equal
It is conventional purchase gained, used test method is test method commonly used in the art.
Embodiment 1
Purity 99.9999% graphite powder 0.3g, potassium permanganate 2g, concentrated sulfuric acid 36ml, concentrated phosphoric acid 4ml are taken, round bottom burning is put into
Bottle, three is sufficiently mixed uniformly, round-bottomed flask is placed in magnetic agitation pot, oil bath, and setting temperature is 45 DEG C, the reaction time
It is 24 hours, prepared graphene oxide is placed in ice water, ensures that the temperature of ice-water bath is 1 DEG C, into graphene oxide
33% hydrogen peroxide is added, until bubble-free generates in solution, step solution is taken to be put into 50ml centrifuge tubes, 30ml, 2mol/ is added
L hydrochloric acid solutions, centrifuge 15min, rotating speed 2000r/min, and washing three times, takes clear liquid that deionized water, centrifuge washing time is added
For 15min, rotating speed 6000r/min, until pH value of solution is 6, obtain graphene oxide precipitation, containing hydroxyl, carboxyl, epoxy group,
Carbonyl, with three-dimensional structure, the molar ratio of hydroxyl and carboxyl is 2:1, oxygen content is 20wt% in graphene oxide.
It takes graphene oxide to precipitate, a certain amount of water, ultrasonic disperse 30min, by the graphene oxide solution of high concentration is added
It is diluted to 2g/L, above-mentioned solution 15ml is taken to be put into polytetrafluoroethylene (PTFE) autoclave, addition area is 15cm2Graphite felt,
Reaction time is 5 hours, and reaction temperature is 150 DEG C, is cooled to room temperature, and graphene oxide is evenly distributed on the surface of graphite felt,
Thickness is 30nm, obtains the electrode that can be used for all-vanadium flow battery, by prepared electrode assembling battery, carries out charge and discharge electrical measurement
Examination：In the battery of assembling, current density 150mA/cm2When, gained current efficiency is 98%, voltage efficiency 81%, energy
Amount efficiency is 79%.
Embodiment 2
Take purity 99.9999% graphite powder 1.5g, potassium permanganate 10g, sodium nitrate 1g, concentrated sulfuric acid 180ml, concentrated phosphoric acid
20ml is put into round-bottomed flask, and three is sufficiently mixed uniformly, round-bottomed flask is placed in magnetic agitation pot, oil bath, and temperature is arranged
It is 50 DEG C, the reaction time is 30 hours, and prepared graphene oxide is placed in ice water, ensures that the temperature of ice-water bath is 3 DEG C,
33% hydrogen peroxide is added into graphene oxide, until bubble-free generates in solution, step solution is taken to be put into 50ml centrifuge tubes,
30ml is added, 2mol/L hydrochloric acid solutions centrifuge 15min, rotating speed 3000r/min, and washing three times, takes clear liquid that deionization is added
Water, the centrifuge washing time is 30min, rotating speed 7000r/min, until pH value of solution is 6, obtains graphene oxide precipitation, contains hydroxyl
Base, carboxyl, epoxy group, carbonyl, with three-dimensional structure, the molar ratio of hydroxyl and carboxyl is 1:1, oxygen content in graphene oxide
For 25wt%.
It takes graphene oxide to precipitate, a certain amount of deionized water, ultrasonic disperse 45min, by the graphite oxide of high concentration is added
Alkene solution is diluted to 1g/L, and above-mentioned solution 15ml is taken to be put into polytetrafluoroethylene (PTFE) autoclave, and addition area is 30cm2Carbon
Felt, reaction time are 6 hours, and reaction temperature is 160 DEG C, is cooled to room temperature, and graphene oxide is equal in the distribution of the surface of graphite felt
Even, thickness 50nm will obtain the electrode that can be used for all-vanadium flow battery, by prepared electrode assembling battery, carry out charge and discharge
Electrical testing：In the battery of assembling, current density 100mA/cm2When, gained current efficiency is 96.2%, and voltage efficiency is
86%, energy efficiency 82.73%.
Embodiment 3
Take purity 99.9999% graphite powder 1.5g, potassium permanganate 15g, potassium peroxydisulfate 1g, concentrated sulfuric acid 180ml, concentrated phosphoric acid
20ml is put into round-bottomed flask, and three is sufficiently mixed uniformly, round-bottomed flask is placed in magnetic agitation pot, oil bath, and temperature is arranged
It is 55 DEG C, the reaction time is 26 hours, and prepared graphene oxide is placed in ice water, ensures that the temperature of ice-water bath is 5 DEG C,
33% hydrogen peroxide is added into graphene oxide, until bubble-free generates in solution, step solution is taken to be put into 50ml centrifuge tubes,
30ml is added, 2mol/L hydrochloric acid solutions centrifuge 45min, rotating speed 4000r/min, and washing three times, takes clear liquid that deionization is added
Water, the centrifuge washing time is 30min, rotating speed 8000r/min, until pH value of solution is 7, obtains graphene oxide precipitation, contains hydroxyl
Base, carboxyl, epoxy group, carbonyl, with three-dimensional structure, the molar ratio of hydroxyl and carboxyl is 1:2, oxygen content in graphene oxide
For 28wt%.
It takes graphene oxide to precipitate, a certain amount of deionized water, ultrasonic disperse 65min, by the graphite oxide of high concentration is added
Alkene solution is diluted to 2g/L, and above-mentioned solution 15ml is taken to be put into polytetrafluoroethylene (PTFE) autoclave, and addition area is 40cm2Stone
Black felt, reaction time are 10 hours, and reaction temperature is 170 DEG C, is cooled to room temperature, and graphene oxide is distributed on the surface of graphite felt
Uniformly, thickness 100nm will obtain the electrode that can be used for all-vanadium flow battery, and prepared electrode assembling battery is filled
Discharge test：In the battery of assembling, current density 100mA/cm2When, gained current efficiency is 97%, and voltage efficiency is
87%, energy efficiency 83%.
Implement real 4
Purity 99.9999% graphite powder 4.5g, concentrated sulfuric acid 540ml, concentrated phosphoric acid 60ml, potassium peroxydisulfate 2g is taken to be put into round bottom
Three is sufficiently mixed uniformly, round-bottomed flask is placed in magnetic agitation pot, oil bath by flask, and setting temperature is 65 DEG C, when reaction
Between be 30 hours, prepared graphene oxide is placed in ice water, ensure ice-water bath temperature be 5 DEG C, to graphene oxide
33% hydrogen peroxide of middle addition takes step solution to be put into 50ml centrifuge tubes until bubble-free generates in solution, and 30ml is added,
2mol/L hydrochloric acid solutions, centrifuge 45min, rotating speed 5000r/min, and washing three times, takes clear liquid that deionized water, centrifuge washing is added
Time is that 15min, rotating speed 9000r/min contain hydroxyl, carboxyl, epoxy until pH value of solution obtains graphene oxide precipitation for 7
Base, carbonyl, with three-dimensional structure, the molar ratio of hydroxyl and carboxyl is 1:3, oxygen content is 30wt% in graphene oxide.
Graphene oxide precipitates, and a certain amount of water is added, ultrasonic disperse 75min is dilute by the graphene oxide solution of high concentration
2g/L is released, above-mentioned solution 15ml is taken to be put into polytetrafluoroethylene (PTFE) autoclave, the reaction time is 10 hours, and reaction temperature is
It 165 DEG C, is cooled to room temperature, graphene oxide is evenly distributed on the surface of graphite felt, thickness 100nm, will obtain can be used for complete
Prepared electrode assembling battery is carried out charge-discharge test by the electrode of vanadium flow battery：In the battery of assembling, electric current is close
Degree is 180mA/cm2When, gained current efficiency is 97%, voltage efficiency 80.4%, energy efficiency 77.1%.
Embodiment 5：
Purity 99.9999% graphite powder 0.3g, potassium permanganate 2.5g, concentrated sulfuric acid 36ml, concentrated phosphoric acid 4ml is taken to be put into round bottom
Three is sufficiently mixed uniformly, round-bottomed flask is placed in magnetic agitation pot, oil bath by flask, and setting temperature is 45 DEG C, when reaction
Between be 24 hours, prepared graphene oxide is placed in ice water, ensure ice-water bath temperature be 1 DEG C, to graphene oxide
33% hydrogen peroxide of middle addition takes step solution to be put into 50ml centrifuge tubes until bubble-free generates in solution, and 30ml is added,
2mol/L hydrochloric acid solutions, centrifuge 15min, rotating speed 2000r/min, and washing three times, takes clear liquid that deionized water, centrifuge washing is added
Time is 15min, rotating speed 6000r/min, until pH value of solution is 6, obtains graphene oxide precipitation, contains hydroxyl, carboxyl, epoxy
Base, carbonyl, with three-dimensional structure, the molar ratio of hydroxyl and carboxyl is 1:2, oxygen content is 20wt% in graphene oxide.
It takes graphene oxide to precipitate, a certain amount of water, ultrasonic disperse 30min, by the graphene oxide solution of high concentration is added
It is diluted to 2g/L, above-mentioned solution 15ml is taken to be put into polytetrafluoroethylene (PTFE) autoclave, addition area is 15cm2Graphite felt,
Reaction time is 5 hours, and reaction temperature is 150 DEG C, is cooled to room temperature, and graphene oxide is evenly distributed on the surface of graphite felt,
Thickness is 30nm, obtains the electrode that can be used for all-vanadium flow battery, by prepared electrode assembling battery, carries out charge and discharge electrical measurement
Examination：In the battery of assembling, current density 150mA/cm2When, gained current efficiency is 96%, voltage efficiency 80%, energy
Amount efficiency is 76.8%.
Embodiment 6
Other conditions are same as Example 2, the difference is that only in the preparation process of graphene oxide and are added without nitric acid
Sodium.In the battery of assembling, current density 100mA/cm2When, gained current efficiency is 95.8%, voltage efficiency 85%,
Energy efficiency is 79.5%.
Embodiment 7
Other conditions are same as Example 3, the difference is that only in the preparation process of graphene oxide and are added without over cure
Sour potassium.In the battery of assembling, current density 100mA/cm2When, gained current efficiency is 96%, voltage efficiency 87%,
Energy efficiency is 79%.
Comparative example 1
Grapheme material is taken, a certain amount of ethyl alcohol is added, solution is diluted to 2g/L by ultrasonic disperse 75min, takes above-mentioned solution
15ml is put into polytetrafluoroethylene (PTFE) autoclave, and addition area is 15cm2Graphite felt, the reaction time be 10 hours, reaction
Temperature is 165 DEG C, is cooled to room temperature, graphene is evenly distributed on the surface of graphite felt, will obtain can be used for all-vanadium flow battery
Electrode, prepared electrode is subjected to cyclic voltammetry, the electrode is equal compared to the electrode positive and negative anodes of graphene oxide modification
It shows larger peak voltage difference and sees Fig. 4.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
Cannot the limitation to the scope of the claims of the present invention therefore be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (1)
1. a kind of preparation method of electrode for all-vanadium flow battery, includes the following steps：
Take 99.9999% graphite powder of purity 1.5 g, potassium permanganate 15g, potassium peroxydisulfate 1g, 180 ml of the concentrated sulfuric acid, concentrated phosphoric acid 20
Ml is put into round-bottomed flask, is sufficiently mixed uniformly, round-bottomed flask is placed in magnetic agitation pot, oil bath, and setting temperature is
55 DEG C, the reaction time is 26 hours, and the round-bottomed flask is placed in ice water, ensures that the temperature of ice-water bath is 5 DEG C, to the round bottom
33% hydrogen peroxide is added in flask, until bubble-free generates in solution, step solution is taken to be put into 50 ml centrifuge tubes, is added 30
Ml, 2 mol/L hydrochloric acid solutions centrifuge 45 min, and rotating speed is 4000 r/min, and washing three times, takes clear liquid to be put into centrifuge tube, from
The heart washs, and wash time is 30 min, 8000 r/min of rotating speed, and clear water eccentric cleaning is added, until pH value of solution is 7, obtains oxygen
Graphite alkene precipitates, and the graphene oxide contains hydroxyl, carboxyl, epoxy group and carbonyl, has three-dimensional structure, hydroxyl and carboxyl
Molar ratio be 1:2, oxygen content is 28wt% in graphene oxide;
It takes graphene oxide to precipitate, is added a certain amount of deionized water, ultrasonic disperse 65 min is molten by the graphene oxide of high concentration
Liquid is diluted to 2 g/L, and 15 ml of above-mentioned solution is taken to be put into polytetrafluoroethylene (PTFE) autoclave, and addition area is 40cm2Graphite
Felt, reaction time are 10 hours, and reaction temperature is 170 DEG C, is cooled to room temperature, and graphene oxide is equal in the distribution of the surface of graphite felt
Even, thickness 100nm obtains the electrode for all-vanadium flow battery, by prepared electrode assembling battery, carries out charge and discharge electrical measurement
Examination：In the battery of assembling, current density is 100 mA/cm2When, gained current efficiency is 97%, voltage efficiency 87%, energy
Efficiency is 83%.
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