CN106972186A - It is used for all-vanadium redox flow battery that there is catalysis to be combined membrane preparation method to positive and negative electrode - Google Patents
It is used for all-vanadium redox flow battery that there is catalysis to be combined membrane preparation method to positive and negative electrode Download PDFInfo
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- CN106972186A CN106972186A CN201610022065.5A CN201610022065A CN106972186A CN 106972186 A CN106972186 A CN 106972186A CN 201610022065 A CN201610022065 A CN 201610022065A CN 106972186 A CN106972186 A CN 106972186A
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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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- 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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Abstract
Amberplex field is used the present invention relates to vanadium redox battery (VRB), specially a kind of preparation method of the composite membrane to positive and negative electrode with catalysis used for all-vanadium redox flow battery.The problem of barrier film of most of all-vanadium flow batteries is present be：The demand of some aspects of battery can only be met, it is difficult to obtain the proton-conductive films of high comprehensive performance, such as：Hinder the equilibrium problem between vanadium and electrical conductivity performance.The metal salt with obvious catalysis will be reacted using substep the tape casting to positive and negative electrode to be incorporated into barrier film both sides, is assigned barrier film catalysis, is prepared the composite membrane with catalysis.Composite diaphragm prepared by the present invention has good resistance vanadium performance, mechanical performance and good single VRB battery performances, can be applied to vanadium redox battery field.
Description
Technical field
Amberplex field is used the present invention relates to vanadium redox battery (VRB), is specially one kind
The preparation method of the composite membrane to positive and negative electrode with catalysis used for all-vanadium redox flow battery.
Background technology
The new energy such as exploitation wind energy, solar energy are the important channels for solving energy resources shortage, represent the energy not
Come the direction developed.But time and region dependence are limited by, off-grid wind energy, solar power generation must be used
Energy-storage system, is otherwise difficult round-the-clock utilize；And direct grid-connected must also be adjusted using energy-storage system to power network
Peak and frequency modulation, otherwise can carry out larger impact to grid power and frequency band.Therefore, efficient, large-scale energy
Measuring memory technology just turns into the key core of its development and application.
Vanadium cell (vanadium oxide reduction flow battery/Vanadiumredox flow battery) is to be based on VO2+/VO2 +
With V2+/V3+Electricity to liquid flow energy storage battery technology, energy stores are in electrolyte.Compared with traditional battery,
Vanadium cell can high current fast charging and discharging, self-discharge rate it is low, realize the massive store of energy, be to meet intelligence
Power network and wind energy, solar power generation are to the preferable stored energy form of extensive energy storage demand, the vanadium money of China's abundant
Source advantage also provides condition for development vanadium cell energy storage technology.
Barrier film (PEM) is one of critical material and significant components of vanadium cell, is both electrolyte ion
The passage of transmission, plays a part of separating both positive and negative polarity, prevents battery short circuit again.Therefore, barrier film is largely
On decide coulombic efficiency, energy efficiency and the cycle life of vanadium cell.A kind of good PEM should
Possess good chemical stability, resistance to electrochemical oxidation, low vanadium ion permeability and low cost.Study people
Member has carried out substantial amounts of research work on VRB barrier films, obtains many beneficial achievements.But, there is also
Some problems.The demand of some aspects of battery can only be met, it is difficult to obtain the proton-conductive films of high comprehensive performance.
Therefore, how to prepare high performance vanadium battery diaphragm material has turned into the pass that restriction vanadium cell engineering and technology develop
One of key bottleneck.
The content of the invention
It is an object of the invention to provide a kind of composite membrane to positive and negative electrode with catalysis used for all-vanadium redox flow battery
Preparation method, the metal salt for having obvious catalysis to electrode reaction is incorporated into barrier film, ensure every
While film macroion selective penetrated property, barrier film catalysis is assigned, the composite membrane with catalysis is prepared.
The composite membrane both good conductivities, and ion-selective permeability is good, while improving barrier film intensity again, are applicable to complete
Vanadium oxide reduction flow battery (VRB).
Technical scheme：
One kind is used for all-vanadium redox flow battery, and there is catalysis to be combined membrane preparation method, including following step to positive and negative electrode
Rapid and process conditions：
(1) metal salt to positive and negative electrode with catalysis is dissolved in respective solvent respectively, stirring and dissolving,
It is made into the metal salt solution that mass percent is 1~10%；
(2) perfluorinated sulfonic resin is dissolved in high boiling organic solvent, dissolved by heating in a kettle., be made into matter
The perfluor sulfoacid resin solution that percentage is 3~25% is measured, it is 170 DEG C~260 DEG C to dissolve by heating temperature conditionss；
(3) it is the perfluor sulfoacid resin solution of gained in step (2) is ultrasonically treated, remove bubble and impurity；
(4) solution casting method is used, by the perfluor sulfoacid resin solution casting of step (3) on a glass,
In 60~140 DEG C of different temperatures, 0.5~3h different times solvent volatilization film forming；When solvent is not completely dried,
The metal salt solution of positive pole in step (1) is cast on film and continues drying；
(5) film for preparing step (4) is placed on a glass in turn, then by negative pole in step (1)
Metal salt solution, which is cast on film, continues drying, standby.
It is described it is used for all-vanadium redox flow battery there is catalysis to be combined membrane preparation method to positive and negative electrode, higher boiling has
Machine solvent is dimethyl sulfoxide (DMSO), N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE
Or dichloromethane.
It is described it is used for all-vanadium redox flow battery there is catalysis to be combined membrane preparation method to positive and negative electrode, metal salt is
Bismuth nitrate, bismuth chloride or phosphoric acid tungsten.
Described used for all-vanadium redox flow battery there is catalysis to be combined membrane preparation method, step (1) to positive and negative electrode
In solvent be N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, sulfuric acid or acetone.
Described used for all-vanadium redox flow battery there is catalysis to be combined membrane preparation method, step (2) to positive and negative electrode
In, perfluor sulfoacid resin solution preferred mass fraction is 5%~15%.
Described used for all-vanadium redox flow battery there is catalysis to be combined membrane preparation method, step (3) to positive and negative electrode
In, perfluor sulfoacid resin solution ultrasonic time is 0.5~4 hour.
Described used for all-vanadium redox flow battery there is catalysis to be combined membrane preparation method, step (4) to positive and negative electrode
Or in step (5), film drying temperature is 80~140 DEG C, the time is 1~4h.
Advantages of the present invention and have the beneficial effect that：
1st, at present, the problem of barrier film of most of all-vanadium flow batteries is present is：The some aspects of battery can only be met
Demand, it is difficult to obtain the proton-conductive films of high comprehensive performance, such as：Hinder flat between vanadium and electrical conductivity performance
Weighing apparatus problem.The metal salt with obvious catalysis will be reacted using substep the tape casting to positive and negative electrode to be incorporated into
In barrier film both sides, barrier film catalysis is assigned, the composite membrane with catalysis is prepared.Prepared by the present invention answers
Closing barrier film has good resistance vanadium performance, mechanical performance and good single VRB battery performances.
2nd, the present invention combines barrier film and the scientific and reasonable design of electrode catalyst progress, and building has catalytic activity
Composite membrane, effectively play the electrode catalyst function of catalyst, formed in battery charge and discharge process efficiently, it is steady
Fixed electrode catalyst reaction interface, is conducive to the science of catalyst, safely, effectively uses, the composite membrane has
Good ion-selective permeability and long-acting positive and negative electrode catalytic activity, are stored up to improving vanadium cell performance, reduction
Energy system cost has very important meaning.
Brief description of the drawings
Fig. 1 is composite membrane surface sweeping Electronic Speculum test (a, surface topography, b, Cross Section Morphology).
Fig. 2 is Nafion212, composite membrane vanadium ion penetration testing curve.
Fig. 3 (a)-Fig. 3 (b) is that Nafion212, composite membrane vanadium single cell energy efficiency curve and discharge and recharge are bent
Line；Wherein, Fig. 3 (a) energy efficient curves；Fig. 3 (b) charging and discharging curves.
Embodiment
Below, technical scheme is described in further detail by embodiment and accompanying drawing.
Embodiment 1
In the present embodiment, comprise the following steps that：
1st, 0.2g bismuth nitrates are dissolved in 10mL DMFs (DMF), stirring and dissolving, for bearing
Pole side catalysis layer；0.15g phosphoric acid tungsten is dissolved in 10mL DMFs (DMF), stirred
Dissolving, for side of the positive electrode catalysis layer.
2nd, 4g perfluorinated sulfonic resins are dissolved in DMF (DMF), added in autoclave
Heat of solution, is made into the perfluor sulfoacid resin solution that mass percent is 6%, and it is 220 DEG C to dissolve by heating temperature conditionss.
3rd, by the ultrasonically treated 1h of solution of gained in step (2), bubble and impurity are removed.
4th, using solution casting method, the perfluor sulfoacid resin solution 50mL of step (3) is cast in into glass plate
On, 2h volatilization film forming is dried at a temperature of 120 DEG C, the thickness of perfluorinated sulfonic resin film is 45 μm, by step
(1) metal salt solution of positive pole, which is cast on gained film, in continues drying.
5th, the gained film for preparing step (4) is placed on a glass in turn, then by negative pole in step (1)
Metal salt solution be cast to gained film on continue drying, it is standby.
In the present embodiment, the composite film thickness of acquisition is 60 μm, and each interracial contact is good in composite membrane, nothing point
Cut phenomenon.
The correlated performance data of the present embodiment is as follows：
As shown in figure 1, be can be seen that from the SEM photograph of composite membrane by morphology analysis catalyst in film
Surface, inside are evenly distributed.As shown in Fig. 2 using Nafion212, composite membrane be amberplex in 1.5mol/L
VO2+The comparison of middle infiltration, it can be seen that VO2+Concentration through amberplex is continuous with the extension of time
Increase, but composite membrane is lower than Nafion212 membranous permeation rate.In addition, being surveyed by Fig. 3 (a) for VRB monocells
Examination, obtains the energy efficiency of composite membrane apparently higher than Nafion212 films, can be seen that with reference to Fig. 3 (b)
Under same current density, the discharge voltage of the VRB monocells by amberplex of composite membrane compares Nafion212
The height of film, charging voltage is relatively low.Therefore, catalysis composite membrane can significantly improve battery performance.
Embodiment 2
Difference from Example 1 is：
1st, 0.4g bismuth nitrates are dissolved in 10mL DMFs (DMF), stirring and dissolving is used for
Negative side catalysis layer；0.3g phosphoric acid tungsten is dissolved in 10mL DMFs (DMF), stirred
Dissolving, for side of the positive electrode catalysis layer.
2nd, remaining step is same as Example 1.
In the present embodiment, the composite film thickness of acquisition is 70 μm, and each interracial contact is fine in composite membrane, still
The uniformity and flatness on film surface are not fine.
Embodiment 3
Difference from Example 1 is：
1st, 0.1g bismuth nitrates are dissolved in 10mL DMFs (DMF), stirring and dissolving, for bearing
Pole side catalysis layer；0.75g phosphoric acid tungsten is dissolved in 10mL DMFs (DMF), stirred
Dissolving, for side of the positive electrode catalysis layer.
2nd, remaining step is same as Example 1.
In the present embodiment, the composite film thickness of acquisition is 55 μm, and each interracial contact is good in composite membrane, nothing point
Cut phenomenon.
The correlated performance data of the present embodiment is as follows：
Composite membrane is measured at room temperature in vanadium redox battery, charge-discharge test coulombic efficiency and energy
Efficiency is below data about 2% or so in example 1.It is that Catalytic Layer is relatively thin to analyze reason, the catalytic effect played
It is weaker.
Test result indicates that：The present invention will have substantially catalysis work(using substep the tape casting to positive and negative electrode reaction
The metal salt of energy is incorporated into barrier film both sides, prepares the composite membrane with catalysis.Prepared by the present invention compound
Membrane conductivity can meet vanadium cell use requirement, at the same have good resistance vanadium performance, electric conductivity and
The advantages of good battery performance, it can be widely used in vanadium redox battery field.
Claims (7)
1. one kind is used for all-vanadium redox flow battery there is catalysis to be combined membrane preparation method to positive and negative electrode, its feature exists
In comprising the following steps and process conditions：
(1) metal salt to positive and negative electrode with catalysis is dissolved in respective solvent respectively, stirring and dissolving,
It is made into the metal salt solution that mass percent is 1~10%；
(2) perfluorinated sulfonic resin is dissolved in high boiling organic solvent, dissolved by heating in a kettle., be made into matter
The perfluor sulfoacid resin solution that percentage is 3~25% is measured, it is 170 DEG C~260 DEG C to dissolve by heating temperature conditionss；
(3) it is the perfluor sulfoacid resin solution of gained in step (2) is ultrasonically treated, remove bubble and impurity；
(4) solution casting method is used, by the perfluor sulfoacid resin solution casting of step (3) on a glass,
In 60~140 DEG C of different temperatures, 0.5~3h different times solvent volatilization film forming；When solvent is not completely dried,
The metal salt solution of positive pole in step (1) is cast on film and continues drying；
(5) film for preparing step (4) is placed on a glass in turn, then by negative pole in step (1)
Metal salt solution, which is cast on film, continues drying, standby.
2. there is catalysis composite membrane system to positive and negative electrode according to used for all-vanadium redox flow battery described in claim 1
Preparation Method, it is characterised in that high boiling organic solvent is dimethyl sulfoxide (DMSO), DMF, N, N-
Dimethyl acetamide, 1-METHYLPYRROLIDONE or dichloromethane.
3. there is catalysis composite membrane system to positive and negative electrode according to used for all-vanadium redox flow battery described in claim 1
Preparation Method, it is characterised in that metal salt is bismuth nitrate, bismuth chloride or phosphoric acid tungsten.
4. there is catalysis composite membrane system to positive and negative electrode according to used for all-vanadium redox flow battery described in claim 1
Preparation Method, it is characterised in that the solvent in step (1) is DMF, N, N- dimethyl second
Acid amides, sulfuric acid or acetone.
5. there is catalysis composite membrane system to positive and negative electrode according to used for all-vanadium redox flow battery described in claim 1
Preparation Method, it is characterised in that in step (2), perfluor sulfoacid resin solution preferred mass fraction is 5%~15%.
6. there is catalysis composite membrane system to positive and negative electrode according to used for all-vanadium redox flow battery described in claim 1
Preparation Method, it is characterised in that in step (3), perfluor sulfoacid resin solution ultrasonic time is 0.5~4 hour.
7. there is catalysis composite membrane system to positive and negative electrode according to used for all-vanadium redox flow battery described in claim 1
Preparation Method, it is characterised in that in step (4) or step (5), film drying temperature is 80~140 DEG C,
Time is 1~4h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610022065.5A CN106972186B (en) | 2016-01-14 | 2016-01-14 | Preparation method of composite membrane with catalytic function on positive electrode and negative electrode for all-vanadium redox flow battery |
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| CN201610022065.5A CN106972186B (en) | 2016-01-14 | 2016-01-14 | Preparation method of composite membrane with catalytic function on positive electrode and negative electrode for all-vanadium redox flow battery |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114204087A (en) * | 2021-12-03 | 2022-03-18 | 武汉氢能与燃料电池产业技术研究院有限公司 | High-density composite proton exchange membrane for low-temperature fuel cell and preparation method thereof |
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| CN103682386A (en) * | 2012-08-30 | 2014-03-26 | 中国科学院大连化学物理研究所 | Battery structure for flow energy storage batteries and all-vanadium flow energy storage battery |
| CN104218248A (en) * | 2013-05-31 | 2014-12-17 | 中国科学院大连化学物理研究所 | Difunctional negative electrode and its application as all-vanadium redox energy storage battery negative electrode |
| CN104282923A (en) * | 2014-10-09 | 2015-01-14 | 中国科学院金属研究所 | Anode/enhanced/cathode amphoteric composite membrane for all-vanadium redox flow battery and preparation method of composite membrane |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103682386A (en) * | 2012-08-30 | 2014-03-26 | 中国科学院大连化学物理研究所 | Battery structure for flow energy storage batteries and all-vanadium flow energy storage battery |
| CN104218248A (en) * | 2013-05-31 | 2014-12-17 | 中国科学院大连化学物理研究所 | Difunctional negative electrode and its application as all-vanadium redox energy storage battery negative electrode |
| CN104282923A (en) * | 2014-10-09 | 2015-01-14 | 中国科学院金属研究所 | Anode/enhanced/cathode amphoteric composite membrane for all-vanadium redox flow battery and preparation method of composite membrane |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114204087A (en) * | 2021-12-03 | 2022-03-18 | 武汉氢能与燃料电池产业技术研究院有限公司 | High-density composite proton exchange membrane for low-temperature fuel cell and preparation method thereof |
| CN114204087B (en) * | 2021-12-03 | 2023-05-12 | 武汉氢能与燃料电池产业技术研究院有限公司 | High-density composite proton exchange membrane for low-temperature fuel cell and preparation method thereof |
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