CN105655621B - Zinc cerium base ionic liquid flow battery - Google Patents
Zinc cerium base ionic liquid flow battery Download PDFInfo
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- CN105655621B CN105655621B CN201610178691.3A CN201610178691A CN105655621B CN 105655621 B CN105655621 B CN 105655621B CN 201610178691 A CN201610178691 A CN 201610178691A CN 105655621 B CN105655621 B CN 105655621B
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- ionic liquid
- zinc
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- cerium
- base ionic
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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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Abstract
The present invention relates to a kind of new zinc cerium base ionic liquid flow battery, belong to electrochemical field, can be widely applied to the extensive energy storage of new energy.The present invention obtains the active material of high concentration due to preparing both positive and negative polarity electrolyte from the very strong ionic liquid of dissolving power.For the zinc-base ionic liquid of negative pole, the mol ratio of presoma zinc fluoride and presoma ionic liquid is (1 3):1.For the cerium base ionic liquid of positive pole, the mol ratio of presoma cerous fluoride and presoma ionic liquid is (1 3):1.The energy density of the present invention can reach more than 3 times of existing aqueous medium zinc cerium flow battery energy density.
Description
Technical field
The present invention relates to a kind of new zinc cerium base ionic liquid flow battery, belong to electrochemical field, can answer extensively
Extensive energy storage for new energy.
Background technology
The a variety of stern challenges of 21st century facing mankind, such as climate warming, desertification of land, lack of energy.The world
National governments pay much attention to the utilization of new energy.Energy storage technology is the key technology of utilization of new energy resources.Existing electric power storage
Energy technology has power station of drawing water, compressed air, superconducting magnetic and battery etc..Flow battery is a kind of new Large Copacity redox
Electrochemical energy storage device.Different from conventional batteries, the active material of flow battery is dissolved in electrolyte not on electrode
In, be electrolyte constituent.The electrode of flow battery is electrochemicaUy inert material, only provides place for electrode reaction, and
It is not involved in into the electrode reaction of stream.Thus, the power and capacity of flow battery can be with independent designs.Its power depends on electricity
Pole and the size of pile, capacity then depend on the amount and concentration of electrolyte.
Currently, the research of zinc cerium flow battery is only limitted to aqueous medium system,
Negative reaction is：
Positive pole reacts：
The concentration of the aqueous medium system electrolyte liquid active material is about 2.0mol/L, anode electrolyte active material
Concentration is about 1mol/L.If being converted into the mol ratio of solute and solvent, electrolyte liquid is 1:28, anode electrolyte 1:
56.For energy density, so low active material concentration can not meet to be actually needed.
The content of the invention
It is an object of the invention to provide a kind of high-energy-density zinc cerium base ionic liquid flow battery, overcomes existing liquid stream electricity
The weak point in pond, widen the utilization scope of zinc cerium resource.
The present invention is to improve to form on the basis of existing flow battery.The present invention is mainly by negative pole, electrolyte liquid, just
The pile that the multiple batteries monomer of pole, anode electrolyte and amberplex (barrier film) composition is unified into, electrolyte liquid is placed in negative
In the fluid reservoir of pole, the conveying of electrolyte liquid is carried out by pump, anode electrolyte is placed in positive pole fluid reservoir, is carried out just by pump
The conveying of pole electrolyte.Anode chamber in pile is linked to be back with electrolysis fluid catheter with negative pole fluid reservoir, electrolyte liquid delivery pump
Road, electrolyte liquid circulate in the loop.Cathode chamber in pile is by being electrolysed fluid catheter and positive pole fluid reservoir, positive pole
Electrolyte delivery pump is linked to be loop, and anode electrolyte circulates in the loop.The key of the present invention is the negative electricity
Solution liquid is zinc-base ionic liquid, and anode electrolyte is cerium base ionic liquid.
The zinc-base ionic liquid of the electrolyte liquid, 1- methyl, 3- propyl imidazole trifluoro second are dissolved in from zinc fluoride
Zinc-base ionic liquid is made into hydrochlorate, its structural formula is as follows：
N=1-3, zinc-base ionic liquid are single substances, are not mixtures, and it is both solvent and active material；
The cerium base ionic liquid of the anode electrolyte, 1- methyl, 3- propyl imidazole trifluoros are dissolved in from cerous fluoride
Cerium base ionic liquid is made into acetate, its structural formula is as follows：
N=1-3, cerium base ionic liquid is single substance, is not mixture, and it is both solvent and active material.
Containing the sodium fluoride that mass percent is 0.5% -10% in both positive and negative polarity electrolyte.
The zinc cerium base ionic liquid flow battery of the present invention is using zinc-base ionic liquid as negative electrode active material, cerium base ion
Liquid is positive active material, and its electrode reaction is as follows：
Negative reaction：
Positive pole reacts：
Its operation principle is to realize energy using the redox reaction between different valence state zinc cerium base ionic liquid
Conversion, positive and negative electrode active material are the cerium zinc-base ionic liquid of liquid, and redox reaction occurs on inert electrode.Charge and discharge
When electric, positive and negative electrode electrolyte circulates in respective loop.During charging, zinc-base ionic liquid is reduced into zinc, trivalent cerium base
Ionic liquid is oxidized to quadrivalent cerium base ionic liquid；During electric discharge, zinc is oxidized to zinc-base ionic liquid, and quadrivalent cerium base ionic liquid is also
It is former into trivalent cerium base ionic liquid.The positive and negative electrode standard electric potential difference of battery cell is 2.60V.
The zinc cerium base ionic liquid flow battery of the present invention, due to positive and negative to prepare from the very strong ionic liquid of dissolving power
Pole electrolyte, thus obtain the active material of high concentration.For the zinc-base ionic liquid of negative pole, presoma zinc fluoride with
The mol ratio of presoma ionic liquid is (1-3):1.For the cerium base ionic liquid of positive pole, presoma cerous fluoride is with before
The mol ratio for driving body ionic liquid is (1-3):1.Big, the zinc cerium of molecular weight and volume ratio hydrone in view of ionic liquid
The concentration of base ionic liquid active material is about more than 3 times of aqueous medium zinc cerium flow battery active material concentration；It is, this
It is close that the energy density for the zinc cerium base ionic liquid flow battery that invention provides can reach existing aqueous medium zinc cerium flow battery energy
More than 3 times of degree.
Brief description of the drawings
Fig. 1 is the structural representation of the zinc cerium base ionic liquid flow battery monomer of the present invention.
Embodiment
(arrow flows to for electrolyte in figure) as shown in Figure 1, the present invention is mainly by negative pole, electrolyte liquid, positive pole, positive pole
The pile that the multiple batteries monomer of electrolyte and amberplex (barrier film) composition is unified into, electrolyte liquid are placed in negative pole fluid reservoir
In, the conveying of electrolyte liquid is carried out by pump, anode electrolyte is placed in positive pole fluid reservoir, and anode electrolyte is carried out by pump
Conveying.Anode chamber in pile is linked to be loop, negative electricity with electrolysis fluid catheter with negative pole fluid reservoir, electrolyte liquid delivery pump
Solution liquid circulates in the loop.Cathode chamber in pile is defeated by being electrolysed fluid catheter and positive pole fluid reservoir, anode electrolyte
Pump is sent to be linked to be loop, anode electrolyte circulates in the loop.The electrolyte liquid is zinc-base ionic liquid, and positive pole is electric
Solution liquid is cerium base ionic liquid.
The zinc-base ionic liquid of the electrolyte liquid, presoma 1- methyl, 3- third are dissolved in from presoma zinc fluoride
Obtained in base imidazoles trifluoroacetic acid ionic liquid.
The cerium base ionic liquid of the anode electrolyte, presoma 1- methyl, 3- are dissolved in from presoma cerous fluoride
Obtained in propyl imidazole trifluoroacetic acid ionic liquid.
The inert materials such as carbon felt, graphite felt, graphite cake, graphite paper or carbon cloth can be selected in the positive and negative electrode of battery cell.Ion
Battery cell is divided into cathode chamber and anode chamber two parts by exchange membrane, and positive pole is in cathode chamber, and negative pole is in anode chamber.It is described
Amberplex selects anion-exchange membrane.
For the present invention in charge and discharge process, both positive and negative polarity electrolyte is constantly pumped into battery by both positive and negative polarity electrolyte delivery pump respectively
In monomer, the flowing of electrolyte accelerates the material transmittance process in electrode interface, advantageously reduces the electrification in electrode reaction
And concentration polarization.The rated power of battery depends on the size of pile, and amount of capacity depends on electrolyte.
During discharge and recharge of the present invention, the negative, positive pole electrolyte in negative, positive pole fluid reservoir under the promotion of electrolyte delivery pump,
By being electrolysed fluid catheter into electrode reaction is carried out in negative, positive pole room, then flow back to again in negative, positive pole fluid reservoir.
NaF content is mass percentage content in embodiment.
Embodiment 1：
Anion-exchange membrane separates the positive and negative pole room of battery；Positive and negative electrode is done with carbon felt, the apparent area of the two is
20cm2.Electrolyte liquid is 100 grams of 1- methyl, and 3- propyl imidazole zinc fluorine trifluoroacetic acid ionic liquid (n=1)+5%NaF is molten
Liquid, anode electrolyte are 200 grams of 1- methyl, 3- propyl imidazole cerium fluorine trifluoroacetic acid ionic liquid (n=1)+5%NaF solution.
Charging and discharging currents are 200mA, electrolyte flow rate 5mL/min.The energy density of battery is 123Wh/L, is aqueous medium zinc cerium liquid
3.15 times of galvanic battery energy density (39Wh/L).
Embodiment 2：
Anion-exchange membrane separates the positive and negative pole room of battery；Positive and negative electrode is done with carbon felt, the apparent area of the two is
20cm2.Electrolyte liquid is 100 grams of 1- methyl, 3- propyl imidazole zinc fluorine trifluoroacetic acid ionic liquid (n=2)+0.5%NaF
Solution, anode electrolyte are 200 grams of 1- methyl, and 3- propyl imidazole cerium fluorine trifluoroacetic acid ionic liquid (n=2)+10%NaF is molten
Liquid.Charging and discharging currents are 200mA, electrolyte flow rate 5mL/min.The energy density of battery is 185Wh/L, is aqueous medium zinc cerium
4.74 times of flow battery energy density (39Wh/L).
Embodiment 3：
Anion-exchange membrane separates the positive and negative pole room of battery；Positive and negative electrode is done with carbon felt, the apparent area of the two is
20cm2.Electrolyte liquid is 100 grams of 1- methyl, 3- propyl imidazole zinc fluorine trifluoroacetic acid ionic liquid (n=3)+10%NaF
Solution, anode electrolyte are 200 grams of 1- methyl, and 3- propyl imidazole cerium fluorine trifluoroacetic acid ionic liquid (n=3)+5%NaF is molten
Liquid.Charging and discharging currents are 200mA, electrolyte flow rate 5mL/min.The energy density of battery is 249Wh/L, is aqueous medium zinc cerium
6.38 times of flow battery energy density (39Wh/L).
Claims (6)
1. a kind of zinc cerium base ionic liquid flow battery, including both positive and negative polarity and both positive and negative polarity electrolyte, it is characterized in that：Described negative pole
Electrolyte is zinc-base ionic liquid, and anode electrolyte is cerium base ionic liquid；
The zinc-base ionic liquid of described electrolyte liquid, 1- methyl, 3- propyl imidazole trifluoroacetic acids are dissolved in from zinc fluoride
Zinc-base ionic liquid is made into salt, its structural formula is as follows：
Wherein：N=1-3, zinc-base ionic liquid are single substances, are not mixtures, and it is both solvent and active material；
The cerium base ionic liquid of described anode electrolyte, 1- methyl, 3- propyl imidazole trifluoro second are dissolved in from cerous fluoride
Cerium base ionic liquid is made into hydrochlorate, its structural formula is as follows：
Wherein：N=1-3, cerium base ionic liquid is single substance, is not mixture, and it is both solvent and active material；
Containing the sodium fluoride that mass percent is 0.5% -10% in both positive and negative polarity electrolyte.
2. a kind of zinc cerium base ionic liquid flow battery according to claim 1, it is characterized in that：Both positive and negative polarity reaction is as follows：
Negative reaction：
Positive pole reacts：
3. a kind of zinc cerium base ionic liquid flow battery according to claim 1, it is characterized in that：Described electrolyte liquid
Zinc-base ionic liquid, be dissolved in presoma 1- methyl, 3- propyl imidazole trifluoroacetate ionic liquids from presoma zinc fluoride
Obtained in body, the mol ratio of presoma zinc fluoride and presoma ionic liquid is (1-3):1；
The cerium base ionic liquid of the anode electrolyte, presoma 1- methyl, 3- propyl group are dissolved in from presoma cerous fluoride
Obtained in imidazoles trifluoroacetic acid ionic liquid, the mol ratio of presoma cerous fluoride and presoma ionic liquid is (1-3):1.
4. a kind of zinc cerium base ionic liquid flow battery according to claim 1, it is characterized in that：Cell it is positive and negative
The quasi- electrical potential difference of pole marks is 2.60V.
5. a kind of zinc cerium base ionic liquid flow battery according to claim 1, it is characterized in that：Both positive and negative polarity from carbon felt,
One kind in graphite felt, graphite cake, graphite paper or carbon cloth inert material.
6. a kind of zinc cerium base ionic liquid flow battery according to claim 1, it is characterized in that：Positive and negative electrode is done with carbon felt,
The apparent area of the two is 20cm2；Electrolyte liquid is 100 grams of 1- methyl, 3- propyl imidazole zinc fluorine trifluoroacetic acid salt ions
Liquid and the NaF solution that mass percent is 10%；Anode electrolyte is 200 grams of 1- methyl, 3- propyl imidazole cerium fluorine trifluoro second
Hydrochlorate ionic liquid and the NaF solution that mass percent is 5%；Charging and discharging currents are 200mA, electrolyte flow rate 5mL/min,
The energy density of battery is 249Wh/L, is 6.38 times of aqueous medium zinc cerium flow battery energy density；
Wherein：1- methyl, the n=3 of 3- propyl imidazole zinc fluorine trifluoroacetic acid ionic liquids；1- methyl, 3- propyl imidazole cerium fluorine
The n=3 of trifluoroacetic acid ionic liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610178691.3A CN105655621B (en) | 2016-03-26 | 2016-03-26 | Zinc cerium base ionic liquid flow battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610178691.3A CN105655621B (en) | 2016-03-26 | 2016-03-26 | Zinc cerium base ionic liquid flow battery |
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| Publication Number | Publication Date |
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| CN105655621A CN105655621A (en) | 2016-06-08 |
| CN105655621B true CN105655621B (en) | 2017-12-15 |
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| EP2355223B1 (en) * | 2010-01-29 | 2019-04-17 | Samsung Electronics Co., Ltd. | Redox flow battery including an organic electrolyte soution |
| CN102760577A (en) * | 2011-04-27 | 2012-10-31 | 海洋王照明科技股份有限公司 | Double-electric layer capacitor electrolyte and double-electric layer capacitor using same |
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