CN107863536A - Multiple dimensioned porous electrode applied to flow battery and its preparation method and application - Google Patents
Multiple dimensioned porous electrode applied to flow battery and its preparation method and application Download PDFInfo
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- CN107863536A CN107863536A CN201710960189.2A CN201710960189A CN107863536A CN 107863536 A CN107863536 A CN 107863536A CN 201710960189 A CN201710960189 A CN 201710960189A CN 107863536 A CN107863536 A CN 107863536A
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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
- H01M4/861—Porous electrodes with a gradient in the porosity
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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
- H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
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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 a kind of multiple dimensioned porous electrode applied to flow battery and its preparation method and application, multiple dimensioned porous electrode includes porous electrode skeleton that is carbon fiber lapped, bonding or be knitted to form, the surface distributed of the carbon fiber has second hole, and three-level hole is distributed with the inner surface of the second hole.Above-mentioned multiple dimensioned porous electrode can be applied to all-vanadium flow battery, during applied to all-vanadium flow battery, the current efficiency of battery can be made to reach more than 98%, energy efficiency reaches 89%, and running current density reaches 200mAcm‑2More than, effective run time was more than 500 hours.
Description
Technical field
The present invention relates to flow battery technology field, more particularly to a kind of multiple dimensioned porous electricity applied to flow battery
Pole and its preparation method and application.
Background technology
The energy is the basis of human survival, is the power of social development, the rational exploitation and utilization of the energy is received much concern.Pass
A large amount of uses of system fossil energy bring the problems such as environmental pollution, climate change.Greatly develop with wind energy and solar energy
Regenerative resource for representative be realize energy resource supply clean, the effective way of sustainability.But between regenerative resource has
The features such as having a rest property, fluctuation, larger impact is often caused to power network, turn into the bottleneck for limiting its large-scale application.Development
The power storage system of power network level is the effective way for solving this problem.In existing extensive electricity storage technology, flow battery because
Its scalability is good, and security is good, long lifespan, and the life-span in complete period is low, has vast potential for future development.
In flow battery, active material is typically dissolved in liquid electrolyte in the form of an ion.Both positive and negative polarity electrolyte stores up
In the presence of in the fluid reservoir of outside, when battery operation, both positive and negative polarity electrolyte is pumped to both positive and negative polarity and electrochemical reaction occurs respectively
To store or discharge electric energy.By different activities material classification, existing flow battery mainly includes all-vanadium flow battery, siderochrome liquid
Galvanic battery, zinc-bromine flow battery, hydrogen bromine flow battery etc..Existing electrode of liquid flow cell is typically using carbon felt, graphite felt, carbon
Paper, carbon cloth etc. are based on carbon fiber lapped porous electrode material.For plane electrode, such porous electrode can improve
Specific surface area and electrochemical catalysis activity, while have that stability is good, permeability is high, low cost and other advantages.Based on existing electrode
Flow battery, such as all-vanadium flow battery, (the 40-80mA cm under relatively low running current density-2), charge-discharge energy efficiency
Up to 70-80%.But existing flow battery is because running current density is low, power output is low, cause that pile materials are more, cost is held high
It is expensive, it is difficult to promote.
Development high-specific surface area, high activity electrode pair improve flow battery running current density and power density to closing weight
Will, this will significantly reduce the cost of energy-storage system, promote its commercialization process.In electrode of liquid flow cell design, electricity need to be taken into account
Extremely activity and electrode mass transfer characteristic, but specific surface area often mutually restricts with electrode permeability, it is difficult to improve simultaneously.Ordinary circumstance
Under, the specific surface area of electrode can be improved by reducing carbon fiber diameter, but can greatly reduce the permeability of electrode simultaneously, cause electricity
Solution liquid stream dynamic resistance and pump work dramatically increase, and deteriorate battery performance.
Therefore, it is necessary to prior art is improved.
The content of the invention
Based on this, it is an object of the invention to provide a kind of multiple dimensioned porous electrode applied to flow battery.
Specific technical scheme is as follows：
A kind of multiple dimensioned porous electrode applied to flow battery, including it is carbon fiber lapped, bond or be knitted to form more
Pore electrod skeleton, the surface distributed of the carbon fiber have second hole, and three-level hole is distributed with the inner surface of the second hole.
In wherein some embodiments, a diameter of 2 μm -20 μm of the carbon fiber, length is 10 μm of -10mm.
In wherein some embodiments, a diameter of 50nm-500nm of the second hole, hole depth 50nm-500nm, Kong Jian
Away from for 50nm-500nm.
In wherein some embodiments, a diameter of 5nm-10nm in the three-level hole, hole depth 10nm-30nm, pitch of holes
For 5nm-10nm.
It is a further object of the present invention to provide the preparation method of the above-mentioned multiple dimensioned porous electrode applied to flow battery.
The preparation method of the above-mentioned multiple dimensioned porous electrode applied to flow battery, comprises the following steps：
(1) by initial carbon materials immersion nickel salt, molysite or cobalt salt solution, (solvent can be water, ethanol, acetone or isopropyl
Alcohol) in and carry out supersound process 5-60min, the mass fraction of nickel salt, molysite or cobalt salt is 3-30% in solution；Processing after
60-120 DEG C of drying；
(2) carbon materials that step (1) obtains is heat-treated, atmosphere is inert gas and oxidizing gas gaseous mixture
Body, the volume fraction of oxidizing gas is 2-50%, and heating rate is 2-10 DEG C/min, and heat treatment temperature is 500-900 DEG C, heat
Processing time is 1-3h, and natural cooling drops to room temperature after heat treatment；
(3) carbon materials for obtaining step (2) is cleaned repeatedly in dust technology, places into aqueous slkali or alkali metal salt is molten
Impregnated in liquid；The mass fraction of alkali or alkali metal salt is 5-70% in solution, impregnates and ultrasonic 5-60min, taking-up are dried；
(4) carbon materials that step (3) obtains is heat-treated in inert gas atmosphere, heating rate be 2-10 DEG C/
Min, heat treatment temperature are 600-900 DEG C, and heat treatment time 1-3h, natural cooling drops to room temperature after heat treatment；Use successively again
Distilled water, dust technology cleaning, drying, produce the multiple dimensioned porous electrode for being applied to flow battery.
In wherein some embodiments, the initial carbon materials is selected from carbon felt, graphite felt, carbon paper or carbon cloth, and thickness is
0.1-3mm。
In wherein some embodiments, the nickel salt is selected from nickel chloride, nickel acetate, nickel formate, nickel sulfate or nickel nitrate；Institute
State molysite and be selected from iron chloride, ferric acetate, ferric formate, ferric sulfate or ferric nitrate；The cobalt salt is selected from cobalt chloride, cobalt acetate, formic acid
Cobalt, cobaltous sulfate or cobalt nitrate.
In wherein some embodiments, the oxidizing gas is one kind or several in vapor, oxygen or carbon dioxide
Kind；The inert gas is nitrogen, helium or argon gas.
In wherein some embodiments, the aqueous slkali is lithium hydroxide, sodium hydroxide or potassium hydroxide solution, the alkali
Metal salt solution is lithium carbonate, lithium sulfate, lithium nitrate, lithium formate, lithium acetate, sodium carbonate, sodium sulphate, sodium nitrate, sodium formate, vinegar
Sour sodium, potassium carbonate, potassium sulfate, potassium nitrate, potassium formate or liquor kalii acetici.
It is a further object of the present invention to provide a kind of flow battery.
A kind of flow battery, including the above-mentioned multiple dimensioned porous electrode applied to flow battery.
In wherein some embodiments, the flow battery is selected from all-vanadium flow battery, siderochrome flow battery, ferrovanadium liquid stream
Battery, zinc-bromine flow battery, vanadium bromine flow battery or vanadium cerium flow battery.
The principle and advantage of the present invention is as follows：
The invention aims to solve porous electrode permeability in flow battery mutually to make with porous electrode specific surface area
About, the problem of being difficult to improve simultaneously.
The present invention breaches electrode structural designs and preparation technology in traditional flow battery, by using iron-cobalt-nickel metal oxygen
Compound catalytic oxidation and alkali metal ion oxidation reaction are realized multiple dimensioned more in the method for carbon fiber surface pore-creating twice
The preparation of pore electrod.The present invention is anti-by pore-creating twice before and after on different scale on the premise of electrode permeability is not influenceed
Electrode specific surface area and electrode catalyst activity should be drastically increased；By the formed second hole of the reaction of pore-creating twice and three-level
Hole yardstick is different, and mutually without influence, the multiplication factor of electrode area is first time, second of independent pore-creating after pore-creating twice in succession
The product of electrode area multiplication factor afterwards.
Multiple dimensioned porous electrode prepared by the present invention has the advantages that high-specific surface area, high catalytic activity, high permeability.
Preparation technology of the present invention is simple, and production cost is low, easily operated, is adapted to large-scale production.
Multiple dimensioned porous electrode prepared by the present invention can be applied to all-vanadium flow battery, siderochrome flow battery, ferrovanadium liquid
Galvanic battery, zinc-bromine flow battery, vanadium bromine flow battery or vanadium cerium flow battery.During applied to all-vanadium flow battery, battery can be made
Current efficiency reach more than 98%, energy efficiency reaches 89%, and running current density reaches 200mA cm-2More than, effectively transport
The row time was more than 500 hours.
Brief description of the drawings
Fig. 1 is multiple dimensioned porous electrode structure schematic diagram；
Fig. 2 is the stereoscan photograph of multiple dimensioned porous electrode prepared by embodiment 1；
Fig. 3 is the all-vanadium flow battery based on the electrode of embodiment 1 in 200-500mA cm-2It is permanent under different running current density
Flow charging and discharging curve；
Fig. 4 is the all-vanadium flow battery based on the electrode of embodiment 1 in 200-500mA cm-2It is permanent under different running current density
Flow the efficiency and electrolyte utilization rate of discharge and recharge；
Fig. 5 is the all-vanadium flow battery based on the electrode of embodiment 1 in 400mA cm-2Cyclicity under the conditions of constant current charge-discharge
Energy.
Embodiment
For the ease of understanding the present invention, the present invention will be described more fully below.But the present invention can be with perhaps
More different form is realized, however it is not limited to embodiment described herein.On the contrary, the purpose for providing these embodiments is to make
Understanding more thorough and comprehensive to the disclosure.
Unless otherwise defined, all of technologies and scientific terms used here by the article is with belonging to technical field of the invention
The implication that technical staff is generally understood that is identical.Term used in the description of the invention herein is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases
The arbitrary and all combination of the Listed Items of pass.
Embodiment 1
A kind of multiple dimensioned porous electrode (structural representation is as shown in Figure 1) applied to flow battery of the embodiment of the present invention,
Second hole, the inner surface point of the second hole is distributed with the porous electrode skeleton formed including carbon fiber, the carbon fiber surface
It is furnished with three-level hole.Carbon fiber diameter is 8 μm, length 9mm；Second hole a diameter of 300-500nm, hole depth 50-100nm, hole
Spacing is 50-100nm；Three-level bore dia is 5-10nm, hole depth 10-30nm, pitch of holes be 5-10mm (stereoscan photograph,
Scanning electron microscope (SEM) photograph is as shown in Figure 2).
The above-mentioned multiple dimensioned porous electrode preparation method applied to flow battery, comprise the following steps：
Carbon cloth is used as original material, original material is placed in the acetone soln containing nickel nitrate (mass fraction 15%)
In, dipping and ultrasonic 30min, take out in 60 DEG C of drying.The material of acquisition is put into tube furnace to be heat-treated, atmosphere is steamed for water
The mixed gas of gas and nitrogen, vapor volume fraction are 3%, and heating rate is 5 DEG C/min, and heat treatment temperature is 850 DEG C, heat
Processing time is 1.5h.It is heat-treated and natural cooling is down to after room temperature and cleaned repeatedly with dust technology, is put into mass fraction as 60%
Potassium hydroxide aqueous solution in dipping and ultrasonic 20min, take out drying after be put into the tube furnace containing nitrogen atmosphere carry out heat
Processing, heating rate are 5 DEG C/min, and heat treatment temperature is 800 DEG C, heat treatment time 1.5h, and natural cooling drops after heat treatment
To room temperature.Take out and obtain target electrode with distilled water, the clean drying of dust technology successively.
Embodiment 2
A kind of assembling of all-vanadium flow battery of the embodiment of the present invention.
Multiple dimensioned porous electrode assembling all-vanadium flow battery prepared by Application Example 1, using aluminum end plate, gold-plated
Copper collector plate, have the graphite cake in interdigitation flow field, teflon gasket andNR-211 barrier films, and by end plate,
After collector plate, graphite cake, electrode, pad, barrier film, pad, electrode, graphite cake, collector plate, end plate stack successively, pass through bolt
Nut fastens and is assembled into battery.Constant current charge-discharge test is carried out to the all-vanadium flow battery of assembling, in 200mAcm-2Electric current is close
Under degree, energy efficiency 89.8%.And traditional carbon cloth electrode is assembled into all-vanadium flow battery under the same conditions,
200mA·cm-2Under current density, energy efficiency is only 73.4%.
All-vanadium flow battery based on the electrode of embodiment 1 is in 200-500mAcm-2Constant current charge and discharge under different running current density
Electric curve is as shown in Figure 3；
All-vanadium flow battery based on the electrode of embodiment 1 is in 200-500mAcm-2Constant current charge and discharge under different running current density
The efficiency and electrolyte utilization rate of electricity are as shown in Figure 4；
All-vanadium flow battery based on the electrode of embodiment 1 is in 400mA cm-2Cycle performance under the conditions of constant current charge-discharge is such as
Shown in Fig. 5.
Embodiment 3
A kind of multiple dimensioned porous electrode applied to flow battery of the embodiment of the present invention, including the porous electricity that carbon fiber is formed
Second hole is distributed with pole skeleton, the carbon fiber surface, and three-level hole is distributed with the inner surface of the second hole.Carbon fiber diameter is
9 μm, length 5mm；Second hole a diameter of 400-600nm, hole depth 80-110nm, pitch of holes 70-110nm；Three-level hole is straight
Footpath is 5-10nm, hole depth 10-30nm, pitch of holes 5-10mm.
Preparation method, comprise the following steps：
Carbon felt is used as original material, original material is placed in the aqueous solution containing iron chloride (mass fraction 25%)
In, dipping and ultrasonic 20min, take out in 80 DEG C of drying.The material of acquisition is put into tube furnace to be heat-treated, atmosphere is dioxy
Change the mixed gas of carbon and nitrogen, carbon dioxide volume fraction is 20%, and heating rate is 5 DEG C/min, heat treatment temperature 900
DEG C, heat treatment time 2h.It is heat-treated and natural cooling is down to after room temperature and cleaned repeatedly with dust technology, being put into mass fraction is
Dipping and ultrasonic 30min in 50% sodium hydrate aqueous solution, are put into the tube furnace containing nitrogen atmosphere after taking out drying
Row heat treatment, heating rate be 5 DEG C/min, and heat treatment temperature is 850 DEG C, heat treatment time 1.5h, naturally cold after heat treatment
But room temperature is dropped to.Take out and obtain target electrode with distilled water, the clean drying of dust technology successively.
Embodiment 4
A kind of assembling of all-vanadium flow battery of the embodiment of the present invention.
Multiple dimensioned porous electrode assembling all-vanadium flow battery prepared by Application Example 3, using aluminum end plate, gold-plated
Copper collector plate, have the graphite cake in interdigitation flow field, teflon gasket andNR-211 barrier films, and by end plate,
After collector plate, graphite cake, electrode, pad, barrier film, pad, electrode, graphite cake, collector plate, end plate stack successively, pass through bolt
Nut fastens and is assembled into battery.Constant current charge-discharge test is carried out to the all-vanadium flow battery of assembling, in 300mAcm-2Electric current is close
Under degree, energy efficiency 86.1%.
Embodiment 5
A kind of multiple dimensioned porous electrode applied to flow battery of the embodiment of the present invention, including the porous electricity that carbon fiber is formed
Second hole is distributed with pole skeleton, the carbon fiber surface, and three-level hole is distributed with the inner surface of the second hole.Carbon fiber diameter is
10 μm, length 3mm；Second hole a diameter of 200-300nm, hole depth 70-120nm, pitch of holes 60-100nm；Three-level hole is straight
Footpath is 5-10nm, hole depth 10-30nm, pitch of holes 5-10mm.
Preparation method, comprise the following steps：
Carbon paper is used as original material, original material is placed in the aqueous solution containing cobalt acetate (mass fraction 10%)
In, dipping and ultrasonic 20min, take out in 50 DEG C of drying.The material of acquisition is put into tube furnace to be heat-treated, atmosphere is steamed for water
The mixed gas of gas and nitrogen, vapor volume fraction are 5%, and heating rate is 5 DEG C/min, and heat treatment temperature is 800 DEG C, heat
Processing time is 1.5h.It is heat-treated and natural cooling is down to after room temperature and cleaned repeatedly with dust technology, is put into mass fraction as 70%
Potassium hydroxide aqueous solution in dipping and ultrasonic 30min, take out drying after be put into the tube furnace containing nitrogen atmosphere carry out heat
Processing, heating rate are 5 DEG C/min, and heat treatment temperature is 800 DEG C, heat treatment time 1.5h, and natural cooling drops after heat treatment
To room temperature.Take out and obtain target electrode with distilled water, the clean drying of dust technology successively.
Embodiment 6
A kind of assembling of all-vanadium flow battery of the embodiment of the present invention.
Multiple dimensioned porous electrode assembling all-vanadium flow battery prepared by Application Example 5, using aluminum end plate, gold-plated
Copper collector plate, have the graphite cake in interdigitation flow field, teflon gasket andNR-211 barrier films, and by end plate,
After collector plate, graphite cake, electrode, pad, barrier film, pad, electrode, graphite cake, collector plate, end plate stack successively, pass through bolt
Nut fastens and is assembled into battery.Constant current charge-discharge test is carried out to the all-vanadium flow battery of assembling, in 400mAcm-2Electric current is close
Under degree, energy efficiency 82.3%.
Embodiment 7
A kind of multiple dimensioned porous electrode applied to flow battery of the embodiment of the present invention, including the porous electricity that carbon fiber is formed
Pole skeleton, second hole and three-level hole.Carbon fiber diameter is 13 μm, length 5mm；The a diameter of 200-400nm of second hole, hole depth are
90-150nm, pitch of holes 80-130nm；Three-level bore dia is 5-10nm, hole depth 10-30nm, pitch of holes 5-10mm.
Preparation method, comprise the following steps：
Carbon paper is used as original material, original material is placed in the acetone soln containing cobalt acetate (mass fraction 20%)
In, dipping and ultrasonic 20min, take out in 70 DEG C of drying.The material of acquisition is put into tube furnace to be heat-treated, atmosphere is steamed for water
The mixed gas of gas and nitrogen, vapor volume fraction are 5%, and heating rate is 5 DEG C/min, and heat treatment temperature is 800 DEG C, heat
Processing time is 1.5h.It is heat-treated and natural cooling is down to after room temperature and cleaned repeatedly with dust technology, is put into mass fraction as 70%
Sodium hydrate aqueous solution in dipping and ultrasonic 30min, take out drying after be put into the tube furnace containing nitrogen atmosphere carry out heat
Processing, heating rate are 5 DEG C/min, and heat treatment temperature is 850 DEG C, and heat treatment time 2h, natural cooling drops to after heat treatment
Room temperature.Take out and obtain target electrode with distilled water, the clean drying of dust technology successively.
Embodiment 8
A kind of assembling of all-vanadium flow battery of the embodiment of the present invention.
Multiple dimensioned porous electrode assembling all-vanadium flow battery prepared by Application Example 7, using aluminum end plate, gold-plated
Copper collector plate, have the graphite cake in interdigitation flow field, teflon gasket andNR-211 barrier films, and by end plate,
After collector plate, graphite cake, electrode, pad, barrier film, pad, electrode, graphite cake, collector plate, end plate stack successively, pass through bolt
Nut fastens and is assembled into battery.Constant current charge-discharge test is carried out to the all-vanadium flow battery of assembling, in 500mAcm-2Electric current is close
Under degree, energy efficiency 78.2%.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope that this specification is recorded all is considered to be.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more specific and detailed, but simultaneously
Can not therefore it be construed as limiting the scope of the patent.It should be pointed out that come for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (11)
1. a kind of multiple dimensioned porous electrode applied to flow battery, it is characterised in that including carbon fiber lapped, bonding or braiding
The porous electrode skeleton of formation, the surface distributed of the carbon fiber have second hole, and three-level is distributed with the inner surface of the second hole
Hole.
2. the multiple dimensioned porous electrode according to claim 1 applied to flow battery, it is characterised in that the carbon fiber
A diameter of 2 μm -20 μm, length is 10 μm of -10mm.
3. the multiple dimensioned porous electrode according to claim 1 applied to flow battery, it is characterised in that the second hole
A diameter of 50nm-500nm, hole depth 50nm-500nm, pitch of holes 50nm-500nm.
4. the multiple dimensioned porous electrode according to claim 1 applied to flow battery, it is characterised in that the three-level hole
A diameter of 5nm-10nm, hole depth 10nm-30nm, pitch of holes 5nm-10nm.
5. the preparation method of the multiple dimensioned porous electrode applied to flow battery described in claim any one of 1-4, its feature
It is, comprises the following steps：
(1) initial carbon materials is immersed in nickel salt, molysite or cobalt salt solution and carries out supersound process 5-60min, nickel in solution
The mass fraction of salt, molysite or cobalt salt is 3-30%；Processing is after 60-120 DEG C of drying；
(2) carbon materials that step (1) obtains being heat-treated, atmosphere is inert gas and oxidizing gas mixed gas,
The volume fraction of oxidizing gas is 2-50%, and heating rate is 2-10 DEG C/min, and heat treatment temperature is 500-900 DEG C, at heat
The reason time is 1-3h, and natural cooling drops to room temperature after heat treatment；
(3) carbon materials for obtaining step (2) is cleaned repeatedly in dust technology, is placed into aqueous slkali or alkali metal salt soln
Dipping；The mass fraction of alkali or alkali metal salt is 5-70% in solution, impregnates and ultrasonic 5-60min, taking-up are dried；
(4) carbon materials that step (3) obtains is heat-treated in inert gas atmosphere, heating rate is 2-10 DEG C/min, heat
Treatment temperature is 600-900 DEG C, and heat treatment time 1-3h, natural cooling drops to room temperature after heat treatment；Again successively with distilled water,
Dust technology cleaning, drying, produce the multiple dimensioned porous electrode for being applied to flow battery.
6. preparation method according to claim 5, it is characterised in that the initial carbon materials be selected from carbon felt, graphite felt,
Carbon paper or carbon cloth, thickness 0.1-3mm.
7. preparation method according to claim 5, it is characterised in that the nickel salt is selected from nickel chloride, nickel acetate, formic acid
Nickel, nickel sulfate or nickel nitrate；The molysite is selected from iron chloride, ferric acetate, ferric formate, ferric sulfate or ferric nitrate；The cobalt salt choosing
From cobalt chloride, cobalt acetate, cobaltous formate, cobaltous sulfate or cobalt nitrate.
8. preparation method according to claim 5, it is characterised in that the oxidizing gas is vapor, oxygen or two
One or more in carbonoxide；The inert gas is nitrogen, helium or argon gas.
9. preparation method according to claim 5, it is characterised in that the aqueous slkali be lithium hydroxide, sodium hydroxide or
Potassium hydroxide solution, the alkali metal salt soln are lithium carbonate, lithium sulfate, lithium nitrate, lithium formate, lithium acetate, sodium carbonate, sulfuric acid
Sodium, sodium nitrate, sodium formate, sodium acetate, potassium carbonate, potassium sulfate, potassium nitrate, potassium formate or liquor kalii acetici.
10. a kind of flow battery, it is characterised in that including being applied to the more of flow battery described in claim any one of 1-4
Yardstick porous electrode.
11. flow battery according to claim 10, it is characterised in that the flow battery be selected from all-vanadium flow battery,
Siderochrome flow battery, ferrovanadium flow battery, zinc-bromine flow battery, vanadium bromine flow battery or vanadium cerium flow battery.
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| CN117525447A (en) * | 2024-01-05 | 2024-02-06 | 天津泰然储能科技有限公司 | Three-stage gradient porous electrode for all-vanadium redox flow battery and preparation method thereof |
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