CN105742658B - The preparation method of electrode material for all-vanadium flow battery - Google Patents
The preparation method of electrode material for all-vanadium flow battery Download PDFInfo
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- CN105742658B CN105742658B CN201610159140.2A CN201610159140A CN105742658B CN 105742658 B CN105742658 B CN 105742658B CN 201610159140 A CN201610159140 A CN 201610159140A CN 105742658 B CN105742658 B CN 105742658B
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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
- 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 preparation method of electrode of liquid flow cell material, the more particularly to preparation method of electrode material for all-vanadium flow battery.The implementation process of the method is：Carbon class material is immersed in certain density nitrogenous class raw material, a kind of presoma of target electrode is obtained through ultrasound, dried process, then the above-mentioned presoma of high temperature cabonization, obtains final product target electrode.So obtain significantly being lifted by the nitrogen-containing functional group on its surface of electrode material of modification, its electro-chemical activity and electric conductivity are obtained for raising, reduce the reaction internal resistance of electrode used for all-vanadium redox flow battery, the reactivity site of electrode and electrolyte is increased simultaneously, so as to drastically increase the voltage efficiency and energy efficiency of all-vanadium flow battery.Electrode production process of the invention is simple, raw material is easy to get, with low cost, and stable performance can be produced in enormous quantities.
Description
Technical field
The present invention relates to the preparation method of electrode of liquid flow cell material, more particularly to electrode material for all-vanadium flow battery
Preparation method.
Background technology
Flow battery because its system design flexibly, power output and capacity are relatively independent, long service life, can high current fill
Electric discharge, and overall performance stabilization.Flow battery particularly all-vanadium flow battery is considered as to solve the interval such as solar energy and wind energy
Property, a kind of effective ways of transient output resource.
Since the vanadium redox batteries that begin one's study such as M.Skyllas-kazacos in 1985, all-vanadium flow
Battery has obtained huge development, and it uses VO2 +/VO2+And V2+/V3+Oxidation-reduction pair is in sulfuric acid solution respectively as positive and negative
Pole, shows open-circuit voltage wide and can the electrochemical properties such as deep discharge.Typical material used by all-vanadium flow battery is
Some carbon class materials：Including carbon felt, carbon cloth and graphite felt etc..Such material has operating voltage window wide, specific surface area
Greatly, good stability and the advantages of reasonable prices.However, there is low and poor anti-of electro-chemical activity in above-mentioned carbon class material
The problems such as answering power invertibity.
In order to improve the electro-chemical activity of above-mentioned material, it is modified has done substantial amounts of research both at home and abroad.Including：At heat
Reason, acid treatment and the method such as noble metal decorated.Heat treatment operation process is numerous and diverse, and oxidizing process is difficult to control, and over oxidation can drop
The service life and stability of low electrode material.It is more long that acid treatment mainly uses the concentrated sulfuric acid, concentrated nitric acid to carry out electrode material
The treatment of time, the energy efficiency of all-vanadium flow battery has obtained significantly being lifted, but produces a large amount of spent acid after treatment, to ring
Cause greatly pollution in border.It is noble metal decorated because of its needs sintering and complex process, it is relatively costly, it is difficult to extensive to prepare.
Graphite phase carbon nitride because having the electronic structure of excellent chemical stability and uniqueness, in recent years, as being free of
The catalyst and catalyst carrier of metal are widely studied.In photochemical catalyzing, hydrogen reduction, as green energy-storing material and
Hard mould agent is used for H2And CO2The aspect such as storage all achieve impressive progress.
The content of the invention
The invention aims to solve the active low and poor reaction that above-mentioned vanadium redox flow battery electrode material is present
A kind of reversible sex chromosome mosaicism of power, it is proposed that method of modifying of vanadium redox flow battery electrode, its technology for preparing electrode is simple, low cost
It is honest and clean, industrial mass manufacture can be carried out.
To achieve these goals, the technical solution adopted by the present invention is：A kind of electrode material for all-vanadium flow battery
Preparation method, it comprises the following steps：
（1）Ultrasonically treated 5 ~ 40min is carried out in the solution that carbon class material is immersed nitrogenous class raw material；
（2）Will be through step（1）The carbon class material for the treatment of is put and is dried in an oven, and drying temperature is 80 ~ 120 DEG C, is dried
8 ~ 16h of time, obtains the presoma of target electrode；
（3）By step（2) presoma of gained target electrode is placed in tube furnace or Muffle furnace and is carbonized in, and carburizing temperature is
450 ~ 600 DEG C, 3 ~ 8 DEG C/min of heating rate, temperature is incubated 1 ~ 6h after being raised to carburizing temperature, that is, obtain graphite phase carbon nitride modification
Target electrode material used for all-vanadium redox flow battery.
In such scheme, described nitrogenous class raw material is the materials such as urea, melamine or cyanamide, and preferably urea is molten
Liquid.
In such scheme, the carbon class material is carbon felt, carbon cloth, carbon paper or graphite felt etc., preferably graphite felt.
In such scheme, the solution concentration of the nitrogenous class raw material is 0.001 ~ 1g/ml.
In such scheme, the solvent of the solution of the nitrogenous class raw material is deionized water.
In such scheme, step（1）Described in the preferred 15min of sonication treatment time.
In such scheme, step（2）Described in drying temperature be preferably 100 DEG C.
In such scheme, step（3）Described in carburizing temperature is preferably 550 DEG C in tube furnace or in Muffle furnace.
In such scheme, step（3）Described in soaking time is preferably 1h in tube furnace or in Muffle furnace.
The present invention passes through high temperature cabonization by graphite phase carbon nitride growth in situ in target electrode surface, because graphite-phase is nitrogenized
Carbon contains abundant quaternary N structure, and quaternary nitrogen is more stable in sour environment, and because the electronegativity of nitrogen is easily to vanadium
Ion is adsorbed, and forms a kind of nitrogen-vanadium transition state, facilitates the transmission of ion and the transfer of electric charge, so as to improve full vanadium liquid
The electro-chemical activity of galvanic battery electrode material, improves the voltage efficiency and energy efficiency of all-vanadium flow battery.
The invention has the advantages that：
（1）Electrode material prepared by the present invention, because the modification of graphite phase carbon nitride increased the nitrogenous official of electrode surface
Can roll into a ball, introduce more reaction active sites, improve electro catalytic activity and reaction power invertibity.
（2）Electrode material prepared by the present invention improves carbon class material due to the increase of electrode surface nitrogen-containing functional group
（Carbon felt, carbon cloth, carbon paper or graphite felt etc.）Hydrophily, and the electric conductivity of electrode material is increased, so as to improve full vanadium
The energy efficiency and voltage efficiency of flow battery.
（3）Present invention process process is simple, and raw material is easy to get, and the reaction time is short, flexible and convenient operation, it is easy to scale metaplasia
Produce.
Brief description of the drawings
Fig. 1 is the graphite felt electrode that the present invention is modified and blank graphite felt electrode in 100 mA/cm2Filled under current density
Discharge curve, it can be seen that the present invention utilizes the graphite felt electrode of graphite phase carbon nitride modification with very excellent
Chemical property.
Fig. 2 is the graphite felt electrode that the present invention is modified and blank graphite felt electrode in 150 mA/cm2Filled under current density
Discharge curve, it can be seen that the electrode prepared by the present invention shows under high current density relative to blank felt
Good chemical property.
Fig. 3 is that the graphite felt ESEM that blank group graphite felt is modified with the graphite phase carbon nitride that the present invention is made compares
Figure, shows that graphite oxide phase carbon nitride is successfully supported on graphite felt fibres surface.
Specific embodiment
Below by the instantiation Examples detail present invention.
Embodiment one：
Take 4g melamines to be dissolved in 50ml deionized waters, the stirring and dissolving in beaker, by the graphite felt electricity of certain area
Pole is placed in solution, is totally submerged it.Then, beaker is put into Ultrasound Instrument carries out ultrasonically treated, and ultrasonic time is
10min, makes melamine solution be dispersed in graphite felt electrode.Then, graphite felt electrode is taken out, is placed on evaporating dish
On, drying in an oven, drying temperature is 80 DEG C, and drying time is 14h, obtains target electrode presoma.Then, by the target
Electrode precursor is carbonized in being put into tube furnace, and heating rate is 4 DEG C/min, treats that temperature rises to 550 DEG C, is incubated 3h, obtains final product full vanadium
The electrode material of flow battery.In order to test the chemical property of the electrode, the electrode assembling battery is carried out into charge and discharge electrical measurement
Examination, in 50mA/cm2Under current density, the voltage efficiency of all-vanadium flow battery is 89.7%, and energy efficiency is 88.3%.
Embodiment two：
Take 6g urea to be dissolved in 50ml deionized waters, the stirring and dissolving in beaker puts the graphite felt electrode of certain area
In solution, it is totally submerged it.Then, beaker is put into Ultrasound Instrument carries out ultrasonically treated, and ultrasonic time is 15min, is made
Urea liquid is dispersed in graphite felt electrode.Then, graphite felt electrode is taken out, is placed on evaporating dish, done in an oven
Dry, drying temperature is 100 DEG C, and drying time is 12h, obtains target electrode presoma.Then, the target electrode presoma is put
Enter carbonization in tube furnace, heating rate is 5 DEG C/min, treat that temperature rises to 550 DEG C, be incubated 2h, obtain final product used for all-vanadium redox flow battery
Electrode material.In order to test the chemical property of the electrode, the electrode assembling battery is carried out into charge-discharge test, in 100mA/
cm2Under current density, the voltage efficiency of all-vanadium flow battery is 80.2%, and energy efficiency is 78.3%.
Embodiment three：
Take 10g urea to be dissolved in 50ml deionized waters, be placed in for the carbon felt electrode of certain area by the stirring and dissolving in beaker
In solution, it is totally submerged it.Then, beaker is put into Ultrasound Instrument carries out ultrasonically treated, and ultrasonic time is 15min, makes urine
Plain solution is dispersed in carbon felt electrode.Then, carbon felt electrode is taken out, is placed on evaporating dish, dried in an oven, dried
Temperature is 120 DEG C, and drying time is 10h, obtains target electrode presoma.Then, the target electrode presoma is put into tubular type
It is carbonized in stove, heating rate is 6 DEG C/min, treats that temperature rises to 550 DEG C, be incubated 1h, obtains final product electrode material used for all-vanadium redox flow battery
Material.In order to test the chemical property of the electrode, the electrode assembling battery is carried out into charge-discharge test, in 120mA/cm2Electric current
Under density, the voltage efficiency of all-vanadium flow battery is 75.1%, and energy efficiency is 74.2%.
Embodiment four：
Take 10g melamines to be dissolved in 50ml deionized waters, the stirring and dissolving in beaker, by the carbon felt electrode of certain area
It is placed in solution, is totally submerged it.Then, beaker is put into Ultrasound Instrument carries out ultrasonically treated, and ultrasonic time is 20min,
Urea liquid is set to be dispersed in carbon felt electrode.Then, carbon felt electrode is taken out, is placed on evaporating dish, dried in an oven,
Drying temperature is 120 DEG C, and drying time is 10h, obtains target electrode presoma.Then, the target electrode presoma is put into
It is carbonized in tube furnace, heating rate is 4 DEG C/min, treats that temperature rises to 500 DEG C, be incubated 2h, obtains final product electricity used for all-vanadium redox flow battery
Pole material.In order to test the chemical property of the electrode, the electrode assembling battery is carried out into charge-discharge test, in 150mA/cm2
Under current density, the voltage efficiency of all-vanadium flow battery is 66.8%, and energy efficiency is 65.6%.
Claims (7)
1. a kind of preparation method of electrode material for all-vanadium flow battery, it is characterised in that comprise the following steps：
(1) ultrasonically treated 5~40min is carried out in the solution that carbon class material is immersed nitrogenous class raw material, wherein, described is nitrogenous
Class raw material is urea, melamine or cyanamide, and the solvent of the solution of the nitrogenous class raw material is deionized water；
(2) the carbon class material processed through step (1) is put and dries in an oven, drying temperature is 80~120 DEG C, drying time
8~16h, obtains the presoma of target electrode；
(3) it is carbonized in the presoma of gained target electrode in step (2) being placed in into tube furnace or Muffle furnace, carburizing temperature is 450
~600 DEG C, 3~8 DEG C/min of heating rate, temperature is incubated 1~6h after being raised to carburizing temperature, that is, obtain graphite phase carbon nitride modification
Target electrode material used for all-vanadium redox flow battery.
2. the preparation method of electrode material for all-vanadium flow battery as claimed in claim 1, it is characterised in that：The carbon class
Material is carbon felt, carbon cloth, carbon paper or graphite felt.
3. the preparation method of electrode material for all-vanadium flow battery as claimed in claim 1, it is characterised in that：The nitrogenous class
The solution concentration of raw material is 0.001~1g/ml.
4. the preparation method of electrode material for all-vanadium flow battery as claimed in claim 1, it is characterised in that：In step (1)
The sonication treatment time is 15min.
5. the preparation method of electrode material for all-vanadium flow battery as claimed in claim 1, it is characterised in that：In step (2)
The drying temperature is 100 DEG C.
6. the preparation method of electrode material for all-vanadium flow battery as claimed in claim 1, it is characterised in that：In step (3)
The carburizing temperature in tube furnace or in Muffle furnace is 550 DEG C.
7. the preparation method of electrode material for all-vanadium flow battery as claimed in claim 1, it is characterised in that：In step (3)
The soaking time in tube furnace or in Muffle furnace is 1h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106548978B (en) * | 2016-11-22 | 2018-12-18 | 京东方科技集团股份有限公司 | A kind of production method of functional graphic, array substrate and display device |
| CN106532068A (en) * | 2016-12-10 | 2017-03-22 | 南京理工大学 | Modified graphite felt electrode used for microbial fuel cell |
| CN108539211B (en) * | 2017-03-03 | 2021-06-25 | 湖南农业大学 | Preparation method of fluoride salt modified multifunctional electrode material for vanadium battery |
| CN110197905B (en) * | 2018-02-27 | 2021-03-30 | 湖南省银峰新能源有限公司 | Modified carbon material and graphene-like nanosheet-modified redox flow battery electrode prepared from same |
| CN110194453B (en) * | 2018-02-27 | 2021-08-03 | 湖南省银峰新能源有限公司 | Modified carbon material and nitrogen-rich liquid flow battery electrode prepared from same |
| CN108598498B (en) * | 2018-05-08 | 2020-09-29 | 沈阳建筑大学 | Graphite felt electrode modified by nitrogen-doped reduced graphene oxide and preparation method thereof |
| CN108840403A (en) * | 2018-05-31 | 2018-11-20 | 长江大学 | A kind of graphite felt cathode material preparation method and modified graphite felt cathode Fenton reactor |
| CN109830698B (en) * | 2019-02-18 | 2022-02-08 | 湖南农业大学 | Preparation method of electrode with hollow fold structure |
| CN109904468B (en) * | 2019-02-18 | 2022-03-29 | 湖南农业大学 | Preparation method of bacteria modified carbon electrode |
| CN109809375B (en) * | 2019-03-28 | 2021-11-05 | 四川大学 | Three-dimensional structure electrode and preparation method thereof |
| CN110620244A (en) * | 2019-09-24 | 2019-12-27 | 福州大学 | Glucose hydrothermal carbon and nitrogen co-doped graphite felt electrode and preparation method and application thereof |
| CN111463445B (en) * | 2020-03-26 | 2022-05-06 | 上海电气集团股份有限公司 | Modified carbon material, all-vanadium redox flow battery, and preparation method and application thereof |
| CN113809338B (en) * | 2021-09-22 | 2023-09-08 | 贵州志喜科技有限公司 | Preparation method of electrode material for all-vanadium redox flow battery |
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| CN102487142A (en) * | 2010-12-01 | 2012-06-06 | 大连融科储能技术发展有限公司 | Electrode for flow energy storage battery |
| CN104409739A (en) * | 2014-11-14 | 2015-03-11 | 天津大学 | Preparation method of nitrogen doped graphite felt used for direct flow methanol fuel cell cathode |
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