CN106299394A - A kind of high-activity carbon fibre felt electrode material and its preparation method and application - Google Patents
A kind of high-activity carbon fibre felt electrode material and its preparation method and application Download PDFInfo
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- CN106299394A CN106299394A CN201610836567.1A CN201610836567A CN106299394A CN 106299394 A CN106299394 A CN 106299394A CN 201610836567 A CN201610836567 A CN 201610836567A CN 106299394 A CN106299394 A CN 106299394A
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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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- 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 high-activity carbon fibre felt electrode material and its preparation method and application.Its preparation method is as follows: 1) will put into after carbon fiber felt cutting in the container filling acetone soln, carries out ultrasonic vibration, removes the greasy dirt on carbon fiber felt surface, repeatedly washes, dry for standby after taking-up；2) put in high concentration potassium hydroxide aqueous solution, soak 2～3 hours under room temperature, be vacuum dried after taking-up；3) gained sample is inserted in tube furnace, and be passed through protective gas, rise to target temperature with constant rate of speed, be incubated 2～4 hours, then naturally cool to room temperature；4), after taking out sample, use acid solution to carry out pickling, repeatedly wash with deionized water afterwards, then dry；5) gained sample is carried out second reaming process: repeat step 2)～4), prepare high-activity carbon fibre felt electrode material.The present invention achieves the porous of carbon fiber surface with a kind of relatively simple easy method, can be used as all-vanadium flow battery positive electrode.
Description
Technical field
The present invention relates to extensive energy-storage battery technical field, more particularly relate to a kind of high-activity carbon fibre felt electrode material
Material and its preparation method and application.
Background technology
Along with the development of global economy society, the mankind present ever-increasing trend to the demand of electric power.And conventional fossil
The energy generation mode finiteness due to resource and the severe contamination to environment will be difficult to the needs meeting Future Society to electric power.
Therefore, national governments are just continuing to increase the investment R&D intensity to the regenerative resource such as wind energy and solar energy, and scientific and technological circle also start
The upsurge of the tackling of key scientific and technical problems of renewable energy utilization technology.Various countries have formulated Renewable Energy Development planning one after another, such as beautiful
Energy information administration of state speculates, the electricity supply to the year two thousand thirty U.S. about 40% will come from renewable energy power generation.2009,
The Chinese government promises to undertake to the world in " New Energy Sources In China industry development planning ", regenerative resource consumption will be made to account for the year two thousand twenty complete
The 15% of portion's energy-consuming.But, being affected by randomness variablees such as season, weather, day and night temperatures, wind energy, solar energy etc. can
Renewable source of energy generation produces randomness fluctuation and has discontinuous, unstable feature.If by straight for these low-grade electric energy
Connect grid-connected, it will bring impact harm to electrical network, cause the unstability of supply of electric power.This brings great for its large-scale application
Obstacle, causes large area " to abandon electricity ", the phenomenon of the wasting of resources such as " useless electricity ".Data according to incompletely statistics, only 2012, institute of China
The wind power resources of waste is more than 20TWh.
The effective scheme solving this problem is to have introduced regular, smooth work between " renewable energy power generation " and " electrical network "
Energy storage technology as intermediary, to change the supply of electric power pattern of tradition " i.e. send out and i.e. use ".First low-grade electric energy is deposited
Storage is got up, and carries out grid-connected output again after integrating in the way of smooth, stable.In many energy storage technologies, all-vanadium liquid flow energy storage
Battery (Vanadium Flow Battery, VFB) is because having following plurality of advantages: 1) energy efficiency is high, run safety and stability,
Have extended cycle life；2) freely, power and capacity are separate, system flexible design in addressing；3) pollution-free, electrolyte is the most again
Raw, safeguard that simple and operation cost is low etc. it is considered to be it is random to be used for solving the renewable energy system such as solar energy, wind energy
Property and the most promising technology of intermittent unstable state defect problem, have in renewable energy power generation and intelligent grid construction
Great demand.In addition, this technology is at electrical network " peak load shifting ", uninterrupted emergency power supply, electric motorcar charging station, communication base
Stand and military field all has important potential using value.In the energy storage technology development plan that the U.S. formulates for 2012,
All-vanadium liquid flow energy storage battery ranks the first place of the technology of first developing.Technique early than 1985 by Australia's newly south Weir
The MarriaKacos professor of scholar university and partner thereof propose, and they use the vanadium ion VO of different valence state2+/VO2 +, V2+/V3+
Respectively as positive and negative electrode active substance, largely avoid the cross-contamination of both positive and negative polarity electrolyte solution.This technology is
Having several demonstrative projects to run in different geographical, its core technology is mainly by Japan, the U.S., Australia, Canada and Europe
Zhou Deng developed country is grasped.China catches up from behind, and also begins to carry out every research of technique the most actively from the nineties in last century
Carrying out demonstrating running, there are the Research Centers such as Dalian Chemiclophysics Inst., Chinese Academy of Sciences, Tsing-Hua University, Central South University in main research unit
School and Dalian Raycom energy storage, Beijing Pu Nengdeng enterprise.But, commercialization popularization and application to be realized, all-vanadium liquid flow energy storage technology
It is urgently to be resolved hurrily that battery there is also series of problems.Improve the charging and discharging currents density of all-vanadium flow electric current, reduce battery module
Size, and then to reduce manufacturing cost be the highly important research direction in this field in recent years.
Electrode material is one of critical material in liquid flow energy storage battery, be also determine cell power density important because of
Element.The main electrode material of VFB is carbon fiber felt or graphite felt at present.The major advantage of this electrode material is porosity
Height, conduct electricity very well, acid corrosion-resistant performance excellent, but its specific surface area is less and for VO2+/VO2 +The electricity of oxidation-reduction pair
Pole reactivity and reversibility are poor, and one of become the principal element of restriction cell power density raising.Fine in order to improve carbon
The performance of dimension material, generally need to carry out surface process or modification to it, and conventional method mainly includes surface oxidation and metal bag
Cover.The method of carbon fiber surface oxidation specifically includes that high-temperature air oxidation, hot sulfuric acid treatment, ozone oxidation, plasma are carved
Erosion, electrochemical oxidation etc., can improve the quantity of the oxygen-containing functional group such as hydroxyl, carboxyl of fiber surface, can improve electrode material with
The wellability of electrolyte and electrode reaction activity.But oxidation processes is easily reduced mechanical performance and the electric conductivity of carbon fiber,
And easily cause electrode material decline of overpotential for oxygen evolution in charging process.Surface coating is to have in electrode surface deposition
The metal of catalysis activity or metal oxide particle, to improve electro-chemical activity and the kinetics reversibility of electrode reaction.But it is golden
Belong to material highly acid, strong oxidizing property electrolyte system longtime running in stability problem be difficult to solve, and gold used
Belonging to great majority is noble metal or its alloy such as Ir, Pt, Ru etc., and high cost is also the obstacle of its large-scale application.Therefore, exploitation one
Kind of specific surface area is big, catalysis activity is high, stable cycle performance and cheap electrode material are still important grinding in this field
Study carefully problem.
In recent years, activated carbon fiber (Activated carbon fiber, ACF) causes people and pays close attention to emerging greatly
Interest, it is to develop a new generation's threadiness activated carbon with Industry of Carbon Fiber development.Comparing traditional carbon fibres material, ACF has
Higher specific surface area (900～2500m2g-1), there is abundant microcellular structure and appropriate surface functional group such as-OH ,-
COOH ,-C=O and lactone group etc., additionally, it also has adsorption-desorption kinetics faster to the active substance flowing through its inside
Speed.Thus it has purposes widely in fields such as waste water process, air cleaning, catalyst carrier and electrode materials.Deng
Et al. by ACF be used as microorganism fuel cell cathode material, the power making battery in the case of the unsupported any catalyst of ACF is close
Degree has reached 315mWm-2, hence it is evident that higher than traditional carbon fiber paper cathode material (124mWm having loaded Pt catalyst-2).So
And, active carbon fibre fabric-active carbon fiber felt (Activated carbon fiber felt, ACFF) is used as VFB electrode material
Material yet there are no all reports.
Summary of the invention
It is an object of the invention to provide a kind of high-activity carbon fibre felt electrode material and its preparation method and application, it is intended to
Solve common carbon fibers and knit felt for VO2+/VO2 +The problem that the electro catalytic activity of oxidation-reduction pair is low.
The present invention is achieved in that the preparation method of a kind of high-activity carbon fibre felt electrode material, it is characterised in that institute
The method of stating comprises the following steps:
1) will put into after carbon fiber felt cutting in the container filling acetone soln, carry out ultrasonic vibration, remove carbon fiber felt
The greasy dirt on surface, is washed with deionized after taking-up repeatedly, dry for standby；
2) carbon fiber felt is put in high concentration potassium hydroxide aqueous solution, soak 2～3 hours under room temperature, carry out after taking-up
Vacuum drying；
3) sample obtained after vacuum drying is inserted in tube furnace, and be passed through protective gas, rise to mesh with constant rate of speed
Mark temperature, is incubated 2～4 hours under this temperature conditions, then naturally cools to room temperature；
4), after taking out sample, use acid solution to carry out pickling, repeatedly wash with deionized water afterwards, then dry；
5) gained sample is carried out second reaming process: repeat step 2)～4), prepare high-activity carbon fibre felt electrode material
Material.
Preferably, step 2) described in the concentration of potassium hydroxide aqueous solution for for 6～12mol/L.
Preferably, step 3) described in protective gas be one or more gaseous mixtures in nitrogen, helium, argon
Body；Described constant rate of speed is 5～10 DEG C/min；Described target temperature is 600～800 DEG C.
Preferably, step 4) described in acid solution be 0.5～2.0mol/L hydrochloric acid, sulphuric acid and nitric acid in one or two
Plant solution mixed above.
Present invention also offers the high-activity carbon fibre felt electrode material prepared that a kind of above-mentioned preparation method prepares.
Present invention also offers the prepared high-activity carbon fibre felt electrode material of a kind of above-mentioned preparation method at vanadium liquid stream
Application in battery.
Relative to prior art, there is advantages that
The present invention achieves the porous of carbon fiber surface with a kind of relatively simple easy method, can be used as full vanadium
Flow battery positive electrode, on the one hand improves the specific surface area active that place occurs as electrode reaction；The most favourable
Active substance in electrolyte solution is in the absorption of electrode surface, thus significantly improves the electro catalytic activity of electrode material,
VO can be reduced simultaneously2+/VO2+The charge transfer impedance of oxidation-reduction pair electrode reaction and consequent polarization overpotential,
Significantly improve the reversibility of electrode reaction.High-activity carbon fibre felt electrode material prepared by the present invention can be used for assembling full vanadium liquid
Galvanic battery, is greatly improved energy conversion efficiency and the charging and discharging currents density of battery, and then the power density of raising battery, complete
While becoming identical energy storage task, volume and the manufacturing cost of battery module can be reduced.May advantageously facilitate all-vanadium flow electricity
The commercialization in pond.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
In having technology to describe, the required accompanying drawing used is briefly described, it should be apparent that, the accompanying drawing in describing below is only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, it is also possible to
Other accompanying drawing is obtained according to these accompanying drawings.
The preparation method flow process signal of a kind of high-activity carbon fibre felt electrode material that Fig. 1 provides for the embodiment of the present invention
Figure；
Fig. 2 is the microscopic appearance figure of high-activity carbon fibre felt electrode material prepared in embodiments of the invention 1；
Fig. 3 be high-activity carbon fibre felt electrode material (a) prepared in embodiments of the invention 1 with untreated commonly
Carbon fiber felt electrode material (b) contact angle comparing result in aqueous；
Fig. 4 is high-activity carbon fibre felt electrode material prepared in embodiments of the invention 1 and untreated common carbon
Fibre felt electrode material is at 0.05mol/L VO2++0.05mol/L VO2 ++3mol/L H2SO4Circulation volt in electrolyte solution
Peace curve.
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Describe, it is clear that described embodiment is only a part of embodiment of the present invention rather than whole embodiments wholely.Based on
Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under not making creative work premise
Embodiment, broadly falls into the scope of protection of the invention.
The preparation side of a kind of high-activity carbon fibre felt electrode material that the embodiment of the present invention that what Fig. 1 was exemplary show provides
Method schematic flow sheet, this preparation method can be used for preparation high-activity carbon fibre felt electrode material of application in vanadium flow battery.
As it is shown in figure 1, the preparation method of a kind of high-activity carbon fibre felt electrode material of embodiment of the present invention offer, including
Following steps:
1) will put into after carbon fiber felt cutting in the container filling acetone soln, carry out ultrasonic vibration, remove carbon fiber felt
The greasy dirt on surface, is washed with deionized after taking-up repeatedly, dry for standby；
2) carbon fiber felt is put in high concentration potassium hydroxide aqueous solution, soak 2～3 hours under room temperature, carry out after taking-up
Vacuum drying；
3) sample obtained after vacuum drying is inserted in tube furnace, and be passed through protective gas, rise to mesh with constant rate of speed
Mark temperature, is incubated 2～4 hours under this temperature conditions, then naturally cools to room temperature；
4), after taking out sample, use acid solution to carry out pickling, repeatedly wash with deionized water afterwards, then dry；
5) gained sample is carried out second reaming process: repeat step 2)～4), prepare high-activity carbon fibre felt electrode material
Material.
In embodiments of the present invention, step 2) described in the concentration of potassium hydroxide aqueous solution for for 6～12mol/L.
In embodiments of the present invention, step 3) described in protective gas be in nitrogen, helium, argon one or both with
Upper mixed gas；Described constant rate of speed is 5～10 DEG C/min；Described target temperature is 600～800 DEG C.
In embodiments of the present invention, step 4) described in acid solution be 0.5～2.0mol/L hydrochloric acid, sulphuric acid and nitric acid in
One or more mixed solutions.
The embodiment of the present invention prepares a kind of high-activity carbon fibre felt electrode material by above-mentioned preparation method, has height
The feature that specific surface area, surface pore structure are flourishing, catalysis activity is high and cheap.
The embodiment of the present invention additionally provides the prepared high-activity carbon fibre felt electrode material of a kind of above-mentioned preparation method at vanadium
Application in flow battery.In actual application, the high-activity carbon fibre felt electrode material that can the present invention be prepared is used as full vanadium liquid
The electrode material of galvanic battery, can be by collector plate, the high-activity carbon fibre felt electrode material of the present invention and battery diaphragm with pressure filter
Mode assemble all-vanadium flow battery.
The present invention achieves the porous of carbon fiber surface with a kind of relatively simple easy method, can be used as full vanadium
Flow battery positive electrode, on the one hand improves the specific surface area active that place occurs as electrode reaction；The most favourable
Active substance in electrolyte solution is in the absorption of electrode surface, thus significantly improves the electro catalytic activity of electrode material,
VO can be reduced simultaneously2+/VO2+The charge transfer impedance of oxidation-reduction pair electrode reaction and consequent polarization overpotential,
Significantly improve the reversibility of electrode reaction.High-activity carbon fibre felt electrode material prepared by the present invention can be used for assembling full vanadium liquid
Galvanic battery, is greatly improved energy conversion efficiency and the charging and discharging currents density of battery, and then the power density of raising battery, complete
While becoming identical energy storage task, volume and the manufacturing cost of battery module can be reduced.May advantageously facilitate all-vanadium flow electricity
The commercialization in pond.
Further describe with specific embodiment and comparative example below.
Embodiment 1
In the present embodiment, when preparation is for the high-activity carbon fibre felt electrode material of all-vanadium flow battery, use such as
Lower step:
1) carbon fiber felt is cut into 30mm × 30mm × 5mm size, puts in the beaker filling acetone soln, and will burn
Cup is placed in megasonic tank and carries out shaking 30 minutes, to remove the greasy dirt on carbon fiber felt surface.Deionization is repeatedly used after taking-up
Water washs, and puts into 60 DEG C of drying for standby in baking oven.
2) configure the potassium hydroxide aqueous solution of 6mol/L, the carbon fiber felt after cutting is put in this solution, soak under room temperature
Steep 3 hours, after taking-up, put into 60 DEG C dry 12 hours in vacuum drying oven.
3) place a sample in tube furnace, and in stove, be passed through nitrogen protect as protective gas, by furnace temperature first with 5 DEG C/
Min constant rate of speed rises to 800 DEG C, is then incubated 2 hours under this temperature conditions, then naturally cools to room temperature.
4) hydrochloric acid solution using 0.5mol/L carries out pickling, to remove out the potassium hydroxide of remained on surface to the sample taken out
Impurity, washes repeatedly with deionized water afterwards, and puts in baking oven 60 DEG C and be dried.
5) sample is carried out second reaming process: repeat step 2)～4), prepare active carbon fiber felt, in case assembled battery
Use.
The high-activity carbon fibre felt electrode material prepared is carried out morphology characterization: use field emission scanning electron microscope
Observing its microscopic appearance, result is as shown in Figure 2.As in figure 2 it is shown, the surface of electrode material is uniform loose structure, aperture chi
Very little it is in micro-nano rank.This structure will make electrode material have higher specific surface area, thus is easy to electrode active material
Transmission and absorption.Fig. 3 is high-activity carbon fibre felt electrode material (a) prepared in the present embodiment and untreated common carbon
Fibre felt electrode material (b) contact angle in aqueous.Found by contrast, untreated common carbon fibers felt contact angle
Being 124 °, much larger than 90 °, show above water droplet common carbon fibers felt electrode material nonwetting, hydrophobicity is relatively strong, and the present embodiment
High-activity carbon fibre felt electrode material water droplet prepared by is sprawled completely on its surface, and contact angle is 0 °, and surfacing processes
Hydrophilic by hydrophobic change front and back, good hydrophilic is one of requirement of vanadium redox flow battery electrode material.
The high-activity carbon fibre felt electrode material prepared is carried out Electrochemical Characterization: first construct by with prepared
High-activity carbon fibre felt electrode material be working electrode, with large area graphite cake for electrode, with saturated calomel electrode for ginseng
Three-electrode system electrolyzer than electrode composition；Then electrolyte solution: 0.05mol/LVO is prepared2++0.05mol/LVO2 ++
3mol/L H2SO4, be circulated voltammetric scan wherein thus obtain prepared high-activity carbon fibre felt electrode material for
VO2+/VO2 +The cyclic voltammetry curve of oxidation-reduction pair, as shown in Figure 4.By oxidation and peak point current big of reduction process
Little and the potential difference of ratio, oxidation and reduction peak and oxidation and reduction peak current, with the variation relation of sweep speed, can be seen
Going out, high-activity carbon fibre felt electrode material is for VO2+/VO2 +Oxidation-reduction pair has good electro catalytic activity.Oxidation is also
Parent peak current value is apparently higher than untreated common carbon fibers felt.
Additionally, in the present embodiment, by high-activity carbon fibre felt electrode materials application in assembling all-vanadium flow battery.Battery
Assemble in the way of pressure filter according to the order of end plate-collector plate-electrode/membrane/electrode-collector plate-end plate.Wherein, barrier film
Use perfluoro sulfonic acid membrane.By this battery at 100mA/cm2Electric current density under carry out constant current charge-discharge test, result such as Fig. 4 institute
Show.Result shows, this battery is at 100mA/cm2Electric current density under can complete charge and discharge process well, the energy of battery
Conversion efficiency is up to 83.5%.
Comparative example 1
Comparing with embodiment 1, the untreated common carbon fibers felt using same size is that electrode material assembles entirely
Vanadium flow battery, its assembling mode is identical with embodiment 1, and same at 100mA/cm2Electric current density under carry out constant current
Charge-discharge test.Result shows, this battery is at 100mA/cm2Electric current density under battery energy conversion efficiency be only
79.4%.
Embodiment 2
In the present embodiment, when preparation is for the high-activity carbon fibre felt electrode material of all-vanadium flow battery, use such as
Lower step:
1) carbon fiber felt is cut into institute 50mm × 50mm × 5mm size, puts in the beaker filling acetone soln, and will
Beaker is placed in megasonic tank and carries out shaking 30 minutes, to remove the greasy dirt on carbon fiber felt surface.Repeatedly spend after taking-up from
Sub-water washs, and puts into 60 DEG C of drying for standby in baking oven.
2) aqueous solution of the potassium hydroxide of configuration 8mol/L.Carbon fiber felt is put in this solution and soaks 3 hours under room temperature,
60 DEG C dry 12 hours in vacuum drying oven are put into after taking-up.
3) place a sample in tube furnace, and in stove, be passed through nitrogen as protective gas protection.By furnace temperature n first with 8 DEG C/
Min constant rate of speed rises to 700 DEG C, is then incubated 2 hours under this temperature conditions, then naturally cools to room temperature.
4) sulfuric acid solution using 1mol/L carries out pickling to the sample taken out, miscellaneous to remove out the potassium hydroxide of remained on surface
Matter.Repeatedly wash with deionized water afterwards, and put in baking oven 60 DEG C and be dried.
5) sample is carried out second reaming process: repeat step 2)～4), prepare active carbon fiber felt, in case assembled battery
Use.
The high-activity carbon fibre felt electrode material prepared is carried out contact angle and chemical property in pattern, aqueous solution
Characterizing, test condition is with embodiment 1.Result shows: the surface of high-activity carbon fibre felt electrode material prepared by the present embodiment in
Loose structure, aperture size is in micro-nano rank；Aqueous solution contact angle is 0 °, and hydrophilic is good；For VO2+/VO2 +Oxidation
Reduction electricity is to having good electro catalytic activity.
By high-activity carbon fibre felt electrode materials application in assembling all-vanadium flow battery.Battery assembling mode is with embodiment 1.
By this battery at 120mA/cm2Electric current density under carry out constant current charge-discharge test, result is as shown in Figure 3.Result shows, this electricity
Pond is at 120mA/cm2Electric current density under can complete charge and discharge process well, the energy conversion efficiency of battery is up to
80.9%.
Comparative example 2
Comparing with embodiment 2, the untreated common carbon fibers felt using same size is that electrode material assembles entirely
Vanadium flow battery, its assembling mode is identical with embodiment 1, and same at 120mA/cm2Electric current density under carry out constant current
Charge-discharge test.Result shows, this battery is at 120mA/cm2Electric current density under battery energy conversion efficiency be only
75.2%.
Embodiment 3
In the present embodiment, when preparation is for the high-activity carbon fibre felt electrode material of all-vanadium flow battery, use such as
Lower step:
1) carbon fiber felt is cut into institute 30mm × 30mm × 5mm size, puts in the beaker filling acetone soln, and will
Beaker is placed in megasonic tank and carries out shaking 30 minutes, to remove the greasy dirt on carbon fiber felt surface.Repeatedly spend after taking-up from
Sub-water washs, and puts into 60 DEG C of drying for standby in baking oven.
2) aqueous solution of the potassium hydroxide of configuration 10mol/L.Carbon fiber felt is put in this solution to soak 2 under room temperature little
Time, put into 60 DEG C dry 12 hours in vacuum drying oven after taking-up.
3) place a sample in tube furnace, and in stove, be passed through nitrogen as protective gas protection.By furnace temperature first with 10 DEG C/
Min constant rate of speed rises to 750 DEG C, is then incubated 2 hours under this temperature conditions, then naturally cools to room temperature.
4) salpeter solution using 2mol/L carries out pickling to the sample taken out, miscellaneous to remove out the potassium hydroxide of remained on surface
Matter.Repeatedly wash with deionized water afterwards, and put in baking oven 60 DEG C and be dried.
5) sample is carried out second reaming process: repeat step 2)～4), prepare active carbon fiber felt, in case assembled battery
Use.
The high-activity carbon fibre felt electrode material prepared is carried out contact angle and chemical property in pattern, aqueous solution
Characterizing, test condition is with embodiment 1.Result shows: the surface of high-activity carbon fibre felt electrode material prepared by the present embodiment in
Loose structure, aperture size is in micro-nano rank；Aqueous solution contact angle is 0 °, and hydrophilic is good；For VO2+/VO2 +Oxidation
Reduction electricity is to having good electro catalytic activity.
By high-activity carbon fibre felt electrode materials application in assembling all-vanadium flow battery.Battery assembling mode is with embodiment 1.
By this battery at 100mA/cm2Electric current density under carry out constant current charge-discharge test, result is as shown in Figure 3.Result shows, this electricity
Pond is at 100mA/cm2Electric current density under can complete charge and discharge process well, the energy conversion efficiency of battery is up to
84.5%.
Comparative example 3
Comparing with embodiment 3, the untreated common carbon fibers felt using same size is that electrode material assembles entirely
Vanadium flow battery, its assembling mode is identical with embodiment 1, and same at 100mA/cm2Electric current density under carry out constant current
Charge-discharge test.Result shows, this battery is at 100mA/cm2Electric current density under battery energy conversion efficiency be only
79.4%.
Embodiment 4
In the present embodiment, when preparation is for the high-activity carbon fibre felt electrode material of all-vanadium flow battery, use such as
Lower step:
1) carbon fiber felt is cut into institute 50mm × 50mm × 5mm size, puts in the beaker filling acetone soln, and will
Beaker is placed in megasonic tank and carries out shaking 30 minutes, to remove the greasy dirt on carbon fiber felt surface.Repeatedly spend after taking-up from
Sub-water washs, and puts into 60 DEG C of drying for standby in baking oven.
2) aqueous solution of the potassium hydroxide of configuration 12mol/L.Carbon fiber felt is put in this solution to soak 2 under room temperature little
Time, put into 60 DEG C dry 12 hours in vacuum drying oven after taking-up.
3) place a sample in tube furnace, and in stove, be passed through nitrogen as protective gas protection.By furnace temperature first with 10 DEG C/
Min constant rate of speed rises to 600 DEG C, is then incubated 2 hours under this temperature conditions, then naturally cools to room temperature.
4) hydrochloric acid solution using 1.5mol/L carries out pickling, to remove out the potassium hydroxide of remained on surface to the sample taken out
Impurity.Repeatedly wash with deionized water afterwards, and put in baking oven 60 DEG C and be dried.
5) sample is carried out second reaming process: repeat step 2)～4), prepare active carbon fiber felt, in case assembled battery
Use.
The high-activity carbon fibre felt electrode material prepared is carried out contact angle and chemical property in pattern, aqueous solution
Characterizing, test condition is with embodiment 1.Result shows: the surface of high-activity carbon fibre felt electrode material prepared by the present embodiment in
Loose structure, aperture size is in micro-nano rank；Aqueous solution contact angle is 0 °, and hydrophilic is good；For VO2+/VO2 +Oxidation
Reduction electricity is to having good electro catalytic activity.
By high-activity carbon fibre felt electrode materials application in assembling all-vanadium flow battery.Battery assembling mode is with embodiment 1.
By this battery at 120mA/cm2Electric current density under carry out constant current charge-discharge test, result is as shown in Figure 3.Result shows, this electricity
Pond is at 120mA/cm2Electric current density under can complete charge and discharge process well, the energy conversion efficiency of battery is up to
81.8%.
Comparative example 4
Comparing with embodiment 4, the untreated common carbon fibers felt using same size is that electrode material assembles entirely
Vanadium flow battery, its assembling mode is identical with embodiment 1, and same at 120mA/cm2Electric current density under carry out constant current
Charge-discharge test.Result shows, this battery is at 120mA/cm2Electric current density under battery energy conversion efficiency be only
75.4%.
Although preferred embodiments of the present invention have been described, but those skilled in the art once know basic creation
Property concept, then can make other change and amendment to these embodiments.So, claims are intended to be construed to include excellent
Select embodiment and fall into all changes and the amendment of the scope of the invention.
Obviously, those skilled in the art can carry out various change and the modification essence without deviating from the present invention to the present invention
God and scope.So, if these amendments of the present invention and modification belong to the scope of the claims in the present invention and equivalent technologies thereof
Within, then the present invention is also intended to comprise these change and modification.
Claims (6)
1. the preparation method of a high-activity carbon fibre felt electrode material, it is characterised in that said method comprising the steps of:
1) will put into after carbon fiber felt cutting in the container filling acetone soln, carry out ultrasonic vibration, remove carbon fiber felt surface
Greasy dirt, be repeatedly washed with deionized after taking-up, dry for standby；
2) carbon fiber felt is put in high concentration potassium hydroxide aqueous solution, soak 2～3 hours under room temperature, after taking-up, carry out vacuum
It is dried；
3) sample obtained after vacuum drying is inserted in tube furnace, and be passed through protective gas, rise to target temperature with constant rate of speed
Degree, is incubated 2～4 hours under this temperature conditions, then naturally cools to room temperature；
4), after taking out sample, use acid solution to carry out pickling, repeatedly wash with deionized water afterwards, then dry；
5) gained sample is carried out second reaming process: repeat step 2)～4), prepare high-activity carbon fibre felt electrode material.
2. the method for claim 1, it is characterised in that step 2) described in the concentration of potassium hydroxide aqueous solution be 6～
12mol/L。
3. the method for claim 1, it is characterised in that step 3) described in protective gas be in nitrogen, helium, argon
One or more mixed gas；Described constant rate of speed is 5～10 DEG C/min；Described target temperature is 600～800 DEG C.
4. the method for claim 1, it is characterised in that step 4) described in acid solution be 0.5～2.0mol/L salt
One or more mixed solutions in acid, sulphuric acid and nitric acid.
5. the high-activity carbon fibre felt electrode material that the preparation method as according to any one of claim 1-4 prepares.
6. the high-activity carbon fibre felt electrode material that the preparation method as according to any one of claim 1-4 prepares is at vanadium
Application in flow battery.
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| CN107910535A (en) * | 2017-11-22 | 2018-04-13 | 哈尔滨工业大学 | A kind of preparation method of the high carrying capacity sulfur electrode of fibre reinforced |
| CN109167071A (en) * | 2018-08-31 | 2019-01-08 | 深圳大学 | A kind of cathode for whole vanadium oxide reduction flow battery and preparation method thereof |
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| CN112993273A (en) * | 2019-12-12 | 2021-06-18 | 中国科学院大连化学物理研究所 | Self-supporting air electrode and preparation and application thereof |
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| CN111772269B (en) * | 2020-07-13 | 2022-06-14 | 东北大学秦皇岛分校 | Recyclable medical mask based on flexible super-electric structure and preparation method thereof |
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