CN109216718A - Vanadium cell electrode and vanadium cell - Google Patents
Vanadium cell electrode and vanadium cell Download PDFInfo
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- CN109216718A CN109216718A CN201811063112.6A CN201811063112A CN109216718A CN 109216718 A CN109216718 A CN 109216718A CN 201811063112 A CN201811063112 A CN 201811063112A CN 109216718 A CN109216718 A CN 109216718A
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- vanadium cell
- cell electrode
- vanadium
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- hydrogen peroxide
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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
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- Sustainable Energy (AREA)
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- Fuel Cell (AREA)
Abstract
The invention discloses a kind of vanadium cell electrode and vanadium cells, belong to redox flow batteries technical field.The present invention prepares cost of material height, preparation process complexity for existing vanadium cell electrode; the relatively low problem of performance; white blanket is immersed in hydrogen peroxide; after taking out washing, drying; it under inert gas shielding, is carbonized in advance at 170~280 DEG C, then heats to 800~1000 DEG C of progress carburizing reagents; carburizing reagent finishes, then is passed through inert gas and CO2Mixed gas, activated to get vanadium cell electrode；Then it is assembled to obtain vanadium cell.The present invention is low using price, reproducible white blanket is as raw material, and cheap, can effectively reduce vanadium cell reduces cost, and is greatly improved vanadium cell performance.
Description
Technical field
The invention belongs to redox flow batteries technical fields, and in particular to a kind of vanadium cell electrode and vanadium cell.
Background technique
Vanadium cell is a kind of energy storage battery system novel, pollution-free, with long service life.Vanadium cell till now,
In industrial applications early period, influencing on vanadium cell for electrode as wherein critical component is very big.Wider vanadium is applied at present
Battery extremely carbon material electrical pole, but the series of electrode electro-chemical activity is poor.And carbon nanotube, graphene etc. is used to make
Standby combination electrode, but at high cost is that it is difficult to overcome the problems, such as.Therefore, acquisition electro-chemical activity is high, stability is good, price is low
Honest and clean electrode material is the direction of vanadium cell electrode material development.
Existing carbon class electrode is substantially such as asphaltic base, gluing base or PAN carbon fiber felt and uses petroleum material system
It is standby, material have it is non-renewable, compare the type material fiber element be it is a kind of it is inexhaustible, nexhaustible can be again
Production-goods source, therefore prepare vanadium battery electrode using reproducible natural material, price and it is environmental-friendly on have biggish hair
Open up space.The existing research for preparing carbon fiber using cellulose etc. on a small quantity at present, such as patent bacteria cellulose fibre base nanometer
The preparation method (CN103184586A) of carbon fiber, a kind of flaxen fiber conversion carbon fiber to reach the preparation method of defect mending
(CN103173894A), but the performance of its carbon fiber is relatively low.
Summary of the invention
Prepare that cost of material is high, preparation process is multiple the technical problem to be solved by the present invention is to existing vanadium cell electrode
Miscellaneous, performance is relatively low.
The technical proposal adopted by the invention to solve the above technical problems is that provide a kind of vanadium cell electrode, by with
Lower section method is prepared:
A, white blanket is immersed in hydrogen peroxide, after taking out washing, drying, the white blanket that obtains that treated；
B, under inert gas shielding, by treated, white blanket is carbonized in advance at 170~280 DEG C, then heats to 800
~1000 DEG C of progress carburizing reagents；
C, carburizing reagent finishes, and maintains temperature, is passed through inert gas and CO2Mixed gas, activated, activated
Finish to get vanadium cell electrode.
Wherein, in vanadium cell electrode described above, in step A, the mass concentration of the hydrogen peroxide is 2~10%.
Preferably, in vanadium cell electrode described above, in step A, the mass concentration of the hydrogen peroxide is 4~7%.
Wherein, in vanadium cell electrode described above, in step A, it is 50 that white blanket, which is immersed in the temperature in hydrogen peroxide,
~70 DEG C, the time is 2~4h.
Wherein, in vanadium cell electrode described above, in step A, the temperature of the drying is 70~90 DEG C.
Wherein, in vanadium cell electrode described above, in step B, the time of the pre- carbonization is 100~140min.
Wherein, in vanadium cell electrode described above, in step B, 800~1000 DEG C are warming up to 5~10 DEG C/min
2~4h of carburizing reagent.
Wherein, in vanadium cell electrode described above, in step C, inert gas and CO in the mixed gas2Body
Product is than being 8~4:1.
Wherein, in vanadium cell electrode described above, in step C, the time of the activation is 1~2h.
Wherein, in vanadium cell electrode described above, in step B and step C, the inert gas is N2, Ar or He.
On the basis of vanadium cell electrode described above is made, the present invention also provides one kind to contain above-mentioned vanadium
The vanadium cell of electrode for cell.
Beneficial effects of the present invention:
White blanket is carbonized and is activated by the present invention, and vanadium cell electrode is prepared, to substitute existing carbon
Plain class electrode, is applied on vanadium cell, is greatly improved vanadium cell performance；Low using price, reproducible white blanket
As raw material, price is compared and uses asphaltic base, gluing base or PAN carbon fiber felt etc., cheap, can effectively reduce vanadium
Battery reduces cost；Production procedure is shorter, simple process, and nonwoven is made into the process of reactivation processing of fine and later period；It is carbonized and living
Change process does not need that organic reagent is added, and is activated and uses nontoxic CO2, environmentally friendly, no poisonous and harmful substance
Generation and residual.
Specific embodiment
Specifically, vanadium cell electrode, is prepared by following methods:
A, white blanket is immersed in hydrogen peroxide, after taking out washing, drying, the white blanket that obtains that treated；
B, under inert gas shielding, by treated, white blanket is carbonized in advance at 170~280 DEG C, then heats to 800
~1000 DEG C of progress carburizing reagents；
C, carburizing reagent finishes, and maintains temperature, is passed through inert gas and CO2Mixed gas, activated, activated
Finish to get vanadium cell electrode.
The white blanket that the present invention uses can be used commercially available white blanket (felt being directly prepared by 100% cotton), in step A
White blanket is first immersed in the hydrogen peroxide that concentration is 2~10%, in 50~70 DEG C of 2~4h of immersion treatment, to remove white blanket table
Face impurity；The excessive concentration of hydrogen peroxide may oxidized porous carbon material, it is therefore preferred that selecting mass concentration for 4~7%
Hydrogen peroxide.When washing, the hydrogen peroxide in white blanket should be cleaned up as far as possible using distilled water, then be dried at 70~90 DEG C.
In order to keep the carbonization effect of subsequent blanket more preferable, at the same after menarche carbonization to the structure of blanket in later period pyrocarbon
It can be played a certain protective role in change, therefore first in 170~280 DEG C of 100~140min of pre- carbonization in step B.
In order to preferably be carbonized and reduce the destruction for tying purchase in carbonisation to it, in step B, after pre- carbonization, with 5
~10 DEG C/min is warming up to 800~1000 DEG C of 2~4h of carburizing reagent.
After carburizing reagent, maintenance system temperature, the inert gas and CO being passed through2Volume ratio be 8~4:1 mixing
Gas, 1~2h of priming reaction: CO in this step2Activation is played, inert gas plays protection and adjusts CO2Concentration, control are drawn
The effect of the active group amount entered, inert gas and CO during priming reaction2Fiber surface is etched, is formed in fiber surface small
Hole, while making part CO2It is grafted on fiber surface, reinforcing fiber activity.
In step B and step C of the present invention, inert gas commonly used in the art, such as N is can be used in inert gas2, Ar or He etc..
On the basis of above-mentioned vanadium cell electrode, by the conventional vanadium cell preparation method of this field, using the present invention
Vanadium cell a kind of vanadium cell is prepared with electrode, compared with the conventional vanadium cell of this field, battery performance has very big
Promotion.
Below by embodiment, invention is further described in detail, but does not therefore limit the scope of the present invention
Among the embodiment described range.
Embodiment 1
White blanket is immersed in the hydrogen peroxide that concentration is 4%, after being handled 4 hours at being 50 DEG C in temperature, is taken out with steaming
After distilled water is rinsed well, it is put at baking oven is 70 DEG C in temperature and dries, be then placed in vacuum tube furnace, be passed through high-purity Ar, in temperature
Pre- carbonization 140 minutes is carried out at 170 DEG C of degree, then 800 DEG C of carburizing reagents 4 hours are warming up to for 5 DEG C/min with heating rate, then
It is passed through Ar and CO2Volume ratio is that the mixed gas of 8:1 is cooled to room temperature after reaction 4 hours to get vanadium cell electrode.
Above-mentioned white blanket (is changed to electrode assembled battery activation method identical as use by PAN using above-mentioned vanadium cell
Carbon fiber felt) the battery of PAN carbon fiber felt assembling compare, after circulation 200 times, the average coulombic efficiency of battery is high
2.8%, average voltage efficiencies are high by 1.9%, and average energy efficiency is high by 0.53%.
Embodiment 2
White blanket is immersed in the hydrogen peroxide that concentration is 5%, after being handled 3 hours at being 60 DEG C in temperature, is taken out with steaming
After distilled water is rinsed well, it is put at baking oven is 80 DEG C in temperature and dries, be then placed in vacuum tube furnace, be passed through high-purity Ar, in temperature
Pre- carbonization 120 minutes is carried out at 200 DEG C of degree, then is warming up at 900 DEG C and is reacted 3 hours for 7 DEG C/min with heating rate, is then led to
Enter Ar and CO2Volume ratio is that the mixed gas of 6:1 is cooled to room temperature after reaction 3 hours to get vanadium cell electrode.
The battery assembled using the PAN carbon fiber felt of above-mentioned vanadium cell electrode assembled battery activation method identical as use
It compares, after circulation 200 times, the average coulombic efficiency of battery is high by 3.1%, and average voltage efficiencies are high by 2.1%, average energy effect
Rate is high by 0.65%.
Embodiment 3
White blanket is immersed in the hydrogen peroxide that concentration is 7%, after being handled 2 hours at being 70 DEG C in temperature, is taken out with steaming
After distilled water is rinsed well, it is put at baking oven is 90 DEG C in temperature and dries, be then placed in vacuum tube furnace, be passed through high-purity Ar, in temperature
It carries out pre- carbonization 100 minutes at 280 DEG C of degree, then is after 10 DEG C/min is warming up to and react 2 hours at 1000 DEG C with heating rate, it is logical
Enter Ar and CO2Volume ratio is that the mixed gas of 4:1 is cooled to room temperature after reaction 1 hour to get vanadium cell electrode.
The battery assembled using the PAN carbon fiber felt of above-mentioned vanadium cell electrode assembled battery activation method identical as use
It compares, after circulation 200 times, the average coulombic efficiency of battery is high by 1.5%, and average voltage efficiencies are high by 0.7%, average energy effect
Rate is high by 0.1%.
Claims (10)
1. vanadium cell electrode, it is characterised in that: be prepared by following methods:
A, white blanket is immersed in hydrogen peroxide, after taking out washing, drying, the white blanket that obtains that treated；
B, under inert gas shielding, will treated that white blanket is carbonized in advance at 170~280 DEG C, then heat to 800~
1000 DEG C of progress carburizing reagents；
C, carburizing reagent finishes, and maintains temperature, is passed through inert gas and CO2Mixed gas, activated, activation finish to get
Vanadium cell electrode.
2. vanadium cell electrode according to claim 1, it is characterised in that: in step A, the mass concentration of the hydrogen peroxide
It is 2~10%.
3. vanadium cell electrode according to claim 2, it is characterised in that: in step A, the mass concentration of the hydrogen peroxide
It is 4~7%.
4. vanadium cell electrode according to claim 1, it is characterised in that: in step A, white blanket is immersed in hydrogen peroxide
Temperature be 50~70 DEG C, the time be 2~4h.
5. vanadium cell electrode according to claim 1, it is characterised in that: in step A, the temperature of the drying is 70~
90℃。
6. vanadium cell electrode according to claim 1, it is characterised in that: in step B, the time of the pre- carbonization is
100~140min.
7. vanadium cell electrode according to claim 1, it is characterised in that: in step B, be warming up to 5~10 DEG C/min
800~1000 DEG C of 2~4h of carburizing reagent.
8. vanadium cell electrode according to claim 1, it is characterised in that: in step C, indifferent gas in the mixed gas
Body and CO2Volume ratio be 8~4:1.
9. described in any item vanadium cell electrodes according to claim 1~8, it is characterised in that: in step C, the activation
Time is 1~2h.
10. vanadium cell, it is characterised in that: contain vanadium cell electrode according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811063112.6A CN109216718A (en) | 2018-09-12 | 2018-09-12 | Vanadium cell electrode and vanadium cell |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811063112.6A CN109216718A (en) | 2018-09-12 | 2018-09-12 | Vanadium cell electrode and vanadium cell |
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| CN109216718A true CN109216718A (en) | 2019-01-15 |
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| CN201811063112.6A Pending CN109216718A (en) | 2018-09-12 | 2018-09-12 | Vanadium cell electrode and vanadium cell |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112233910A (en) * | 2020-10-19 | 2021-01-15 | 成都先进金属材料产业技术研究院有限公司 | Preparation method of nano vanadium dioxide/natural porous carbon electrode material |
Citations (4)
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|---|---|---|---|---|
| CN103441288A (en) * | 2013-09-16 | 2013-12-11 | 大连理工高邮研究院有限公司 | Method for producing carbon felt electrode material for flow battery |
| CN104118873A (en) * | 2014-08-13 | 2014-10-29 | 济南圣泉集团股份有限公司 | Method for preparing active porous graphene |
| CN105518814A (en) * | 2013-09-20 | 2016-04-20 | 爱恩株式会社 | Activated carbon for use in electrode of power-storage device, and method for producing same |
| CN107665777A (en) * | 2016-07-30 | 2018-02-06 | 北京化工大学 | A kind of preparation method of biomass-based active carbon electrode material |
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2018
- 2018-09-12 CN CN201811063112.6A patent/CN109216718A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103441288A (en) * | 2013-09-16 | 2013-12-11 | 大连理工高邮研究院有限公司 | Method for producing carbon felt electrode material for flow battery |
| CN105518814A (en) * | 2013-09-20 | 2016-04-20 | 爱恩株式会社 | Activated carbon for use in electrode of power-storage device, and method for producing same |
| CN104118873A (en) * | 2014-08-13 | 2014-10-29 | 济南圣泉集团股份有限公司 | Method for preparing active porous graphene |
| CN107665777A (en) * | 2016-07-30 | 2018-02-06 | 北京化工大学 | A kind of preparation method of biomass-based active carbon electrode material |
Non-Patent Citations (1)
| Title |
|---|
| Z.H.ZHANG等: ""A highly active biomass-derived electrode for all vanadium redox flow batteries"", 《ELECTROCHIMICA ACTA》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112233910A (en) * | 2020-10-19 | 2021-01-15 | 成都先进金属材料产业技术研究院有限公司 | Preparation method of nano vanadium dioxide/natural porous carbon electrode material |
| CN112233910B (en) * | 2020-10-19 | 2022-11-01 | 成都先进金属材料产业技术研究院股份有限公司 | Preparation method of nano vanadium dioxide/natural porous carbon electrode material |
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Application publication date: 20190115 |
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