CN105591142B - A kind of flow battery negative pole zinc-base il electrolyte and preparation method thereof - Google Patents
A kind of flow battery negative pole zinc-base il electrolyte and preparation method thereof Download PDFInfo
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- CN105591142B CN105591142B CN201610179436.0A CN201610179436A CN105591142B CN 105591142 B CN105591142 B CN 105591142B CN 201610179436 A CN201610179436 A CN 201610179436A CN 105591142 B CN105591142 B CN 105591142B
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- zinc
- electrolyte
- flow battery
- methyl
- fluoride
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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
-
- 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 extensive energy storage flow battery technology, particularly a kind of flow battery negative pole zinc-base il electrolyte and preparation method thereof belongs to electrochemical energy storage field.The key of the present invention is that zinc-base ionic liquid is both solvent and active material, and the mol ratio of Zn-ef ficiency and the zinc-base ionic liquid as solvent is (1 3):1.This mol ratio (1 considerably beyond Zn-ef ficiency and aqueous solvent in aqueous medium zinc electrolyte：28).Thus non-aqueous media flow battery system using zinc-base ionic liquid as electrolyte liquid is intended to more much bigger than the energy density of corresponding aqueous medium system, and typically the former is more than 3 times of the latter.
Description
Technical field
The present invention relates to extensive energy storage flow battery technology, particularly a kind of flow battery negative pole zinc-base ionic liquid
Electrolyte and preparation method thereof, belongs to electrochemical energy storage field.
Background technology
Flow battery is a kind of electro-chemical systems of the extensive energy storage of energy.It has the battery knot different from conventional batteries
Structure, its active material is not on electrode, but in the electrolytic solution；This design feature is similar with fuel cell, but manufactures
Cost is less than fuel cell, and production technology is relatively easy compared with lead-acid battery and fuel cell.Flow battery can deep discharge, energy
Efficiency high, power are up to MW class, and application field is very wide, can be as emergency standby power, and grid-connected power generation system is matched somebody with somebody
Energy storage device, and peak load regulation network etc. are covered, there is the sexual valence more than lithium ion battery and Ni-MH battery in extensive energy storage field
Compare advantage.Aqueous medium zinc load flow battery, due to active material, the limitation of solubility causes its energy density in aqueous solvent
It is difficult to further lifting；Energy density is general in below 50Wh/L, it is impossible to meet people growing to energy-storage battery high energy
The demand of metric density.
The content of the invention
It is an object of the invention to provide a kind of flow battery negative pole zinc-base il electrolyte and preparation method thereof.
Technical scheme：
A kind of flow battery negative pole zinc-base il electrolyte, by 1- methyl, 3- propyl imidazole zinc fluorine trifluoroacetic acids
Salt and sodium fluoride composition, the weight/mass percentage composition of sodium fluoride in the electrolytic solution is 0.5% -10%；
Described 1- methyl, 3- propyl imidazole zinc fluorine trifluoroacetates are both solvent and active material, and its structural formula is such as
Under：
Wherein n=1-3.
A kind of flow battery negative pole preparation method of zinc-base il electrolyte, comprises the following steps：
A, zinc fluoride is put into beaker, be placed in 40-60 DEG C of baking oven 6-18 hours；
B, zinc fluoride obtained by step A is ground to 500-1000 mesh, be placed in 40-60 DEG C of baking oven 2-6 hours；
C, zinc fluoride obtained by step B is added in 1- methyl, 3- propyl imidazole trifluoroacetates, zinc fluoride and 1- first
Base, the mol ratio of 3- propyl imidazole trifluoroacetates is (1-3):1；The sodium fluoride of 500-1000 mesh is added simultaneously, is stirred continuously
2-5 hours, required electrolyte is produced, wherein sodium fluoride accounts for 0.5-the 10% of electrolyte gross mass.
The present invention uses zinc fluoride and 1- methyl, 3- propyl imidazole trifluoroacetic acids reactant salt generation 1- methyl, 3- propyl group miaows
Azoles zinc fluorine trifluoroacetate.The composition of electrolyte is 1- methyl, 3- propyl imidazoles zinc fluorine trifluoroacetate and sodium fluoride.Sodium fluoride
Weight/mass percentage composition in the electrolytic solution is 0.5-10%.
The present invention electrolyte can respectively with non-aqueous media iron-based ionic liquid, vanadium base ionic liquid, bromo ionic liquid
Body and cerium base ionic liquid arrange in pairs or groups to form zinc iron-based ionic liquid flow battery system, almagrerite base ionic liquid flow battery body
System, zinc bromo ionic liquid flow battery system and zinc cerium base ionic liquid flow battery system.
The key of the present invention is that zinc-base ionic liquid is both solvent and active material, and Zn-ef ficiency is with being used as solvent
Zinc-base ionic liquid mol ratio be (1-3):1.This is considerably beyond Zn-ef ficiency in aqueous medium zinc electrolyte and aqueous solvent
Mol ratio (1：28).Thus the non-aqueous media flow battery system using zinc-base ionic liquid as electrolyte liquid is intended to than corresponding
The energy density of aqueous medium system is much bigger, it is general the former be more than 3 times of the latter.Sodium fluoride is conducive to strengthening inside battery
Ion conductivity.
Brief description of the drawings
Fig. 1 is the monomer battery structure schematic diagram using the zinc-base il electrolyte of the present invention as electrolyte liquid.
Embodiment
Below by specific embodiment, the invention will be further described, but should not be understood as limitation of the invention,
According to present disclosure, the modification of other diversified forms is made, realized technology is replaced and belongs to the scope of the present invention.It is real
Apply NaF in example content be weight/mass percentage composition, embodiment 4,5,6,7 be using the present invention zinc-base il electrolyte as
The performance parameter of the cell of electrolyte liquid.
Embodiment 1：
Prepare 100 grams of 1- methyl, 3- propyl imidazole zinc fluorine trifluoroacetic acid ionic liquid (n=1)+0.5%NaF electrolysis
Liquid.
32.74 grams of zinc fluorides are weighed first, are placed in 250mL beakers, are placed in 60 DEG C of baking ovens 6 hours；Then will fluorination
Zinc is ground to 1000 mesh, is placed in 60 DEG C of baking ovens 2 hours；Finally weigh 66.76 grams of 1- methyl, 3- propyl imidazole trifluoroacetates
Ionic liquid, is moved into beaker；The zinc fluoride of above-mentioned drying is added into beaker, fully reaction；Plus 0.50 gram of 1000 mesh fluorination
Sodium, is stirred 2 hours；The electrolyte of preparation needed for producing.
Embodiment 2：
Prepare 100 grams of 1- methyl, 3- propyl imidazole zinc fluorine trifluoroacetic acid ionic liquid (n=2)+5%NaF electrolyte.
47.04 grams of zinc fluorides are weighed first, are placed in 250mL beakers, are placed in 40 DEG C of baking ovens 18 hours；Then will fluorination
Zinc is ground to 500 mesh, is placed in 40 DEG C of baking ovens 6 hours；Finally weigh 47.96 grams of 1- methyl, 3- propyl imidazole trifluoroacetates
Ionic liquid, is moved into beaker；The zinc fluoride of above-mentioned drying is added into beaker, fully reaction；Plus 5 gram of 500 mesh sodium fluoride, stir
Mix 5 hours；The electrolyte of preparation needed for producing.
Embodiment 3：
Prepare 100 grams of 1- methyl, 3- propyl imidazole zinc fluorine trifluoroacetic acid ionic liquid (n=3)+10%NaF electrolyte.
53.58 grams of zinc fluorides are weighed first, are placed in 250mL beakers, are placed in 50 DEG C of baking ovens 12 hours；Then will fluorination
Zinc is ground to 800 mesh, is placed in 50 DEG C of baking ovens 4 hours；Finally weigh 36.42 grams of 1- methyl, 3- propyl imidazole trifluoroacetates
Ionic liquid, is moved into beaker；The zinc fluoride of above-mentioned drying is added into beaker, fully reaction；Plus 10 gram of 800 mesh sodium fluoride,
Stirring 3 hours；The electrolyte of preparation needed for producing.
Embodiment 4：
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 is 200 grams of 1- methyl, 3- propyl imidazole iron fluorine trifluoroacetic acid ionic liquid (n=1)+5%NaF solution.
Charging and discharging currents are 200mA, and electrolyte flow rate is 5mL/min.The energy density of battery is 106Wh/L, is aqueous medium zinc-iron liquid
3.03 times of galvanic battery energy density (35Wh/L).
Embodiment 5：
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 is 200 grams of 1- methyl, and 3- propyl imidazole vanadium fluorine trifluoroacetic acid ionic liquid (n=3)+5%NaF is molten
Liquid.Charging and discharging currents are 200mA, and electrolyte flow rate is 5mL/min.The energy density of battery is 251Wh/L, is aqueous medium almagrerite
6.12 times of flow battery energy density (41Wh/L).
Embodiment 6：
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 is 200 grams of 1- methyl, and 3- propyl imidazole aluminium bromine trifluoroacetic acid ionic liquid (n=2)+10%NaF is molten
Liquid.Charging and discharging currents are 200mA, and electrolyte flow rate is 5mL/min.The energy density of battery is 203Wh/L, is aqueous medium zinc bromine
4.51 times of flow battery energy density (45Wh/L).
Embodiment 7：
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 is 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, and electrolyte flow rate is 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 (2)
1. a kind of preparation method of flow battery negative pole zinc-base il electrolyte, it is characterized in that：Comprise the following steps：
A, zinc fluoride is put into beaker, be placed in 40-60 DEG C of baking oven 6-18 hours；
B, zinc fluoride obtained by step A is ground to 500-1000 mesh, be placed in 40-60 DEG C of baking oven 2-6 hours；
C, zinc fluoride obtained by step B is added in 1- methyl, 3- propyl imidazole trifluoroacetates, zinc fluoride and 1- methyl, 3-
The mol ratio of propyl imidazole trifluoroacetate is (1-3):1；The sodium fluoride of 500-1000 mesh is added simultaneously, is stirred continuously 2-5 small
When, required electrolyte is produced, wherein sodium fluoride accounts for 0.5-the 10% of electrolyte gross mass；
Described flow battery negative pole zinc-base il electrolyte, by 1- methyl, 3- propyl imidazole zinc fluorine trifluoroacetates
With sodium fluoride composition, the weight/mass percentage composition of sodium fluoride in the electrolytic solution is 0.5% -10%；
Described 1- methyl, 3- propyl imidazole zinc fluorine trifluoroacetates are both solvent and active material, and its structural formula is as follows：
Wherein n=1-3.
2. a kind of preparation method of flow battery negative pole zinc-base il electrolyte according to claim 1, it is special
Levying is：53.58 grams of zinc fluorides are weighed first, are placed in 250mL beakers, are placed in 50 DEG C of baking ovens 12 hours；Then by zinc fluoride
800 mesh are ground to, are placed in 50 DEG C of baking ovens 4 hours；Finally weigh 36.42 grams of 1- methyl, 3- propyl imidazoles trifluoroacetate from
Sub- liquid, is moved into beaker；The zinc fluoride of above-mentioned drying is added into beaker, fully reaction；And add 10 gram of 800 mesh sodium fluoride,
Stirring 3 hours；The electrolyte of preparation needed for producing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610179436.0A CN105591142B (en) | 2016-03-26 | 2016-03-26 | A kind of flow battery negative pole zinc-base il electrolyte and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610179436.0A CN105591142B (en) | 2016-03-26 | 2016-03-26 | A kind of flow battery negative pole zinc-base il electrolyte and preparation method thereof |
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| CN105591142A CN105591142A (en) | 2016-05-18 |
| CN105591142B true CN105591142B (en) | 2017-10-27 |
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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 |
| CN102324550A (en) * | 2011-08-19 | 2012-01-18 | 李桂云 | Semi-liquid lithium-sulfur battery |
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