CN105633440A - Cerium-based ionic liquid electrolyte for positive electrode of flow battery and preparation method of cerium-based ionic liquid electrolyte - Google Patents
Cerium-based ionic liquid electrolyte for positive electrode of flow battery and preparation method of cerium-based ionic liquid electrolyte Download PDFInfo
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- CN105633440A CN105633440A CN201610177723.8A CN201610177723A CN105633440A CN 105633440 A CN105633440 A CN 105633440A CN 201610177723 A CN201610177723 A CN 201610177723A CN 105633440 A CN105633440 A CN 105633440A
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- cerium
- ionic liquid
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- fluoride
- flow battery
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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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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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 invention relates to a large-scale energy storage flow battery technology, in particular to a cerium-based ionic liquid electrolyte for a positive electrode of a flow battery and a preparation method of the cerium-based ionic liquid electrolyte, and belongs to the field of electrochemical energy storage. The cerium-based ionic liquid electrolyte is characterized in that a cerium-based ionic liquid is a solvent as well as an active material; and the molar ratio of a cerium element to the cerium-based ionic liquid as the solvent is (1-3) to 1, and is far more than that of the cerium element to solvent water in an aqueous medium cerium electrolyte being (1 to 56). Therefore, the energy density of a non-aqueous medium flow battery system employing the cerium-based ionic liquid as a positive electrolyte is much greater than that of a corresponding aqueous medium system, and is more than three times that of the corresponding aqueous medium system in general.
Description
Technical field
The present invention relates to extensive energy storage flow battery technology, particularly a kind of flow battery positive pole cerium base il electrolyte and its preparation method, belong to electrochemical energy storage field.
Background technology
Flow battery is the electro-chemical systems of the extensive energy storage of a kind of energy. It has the battery structure different from conventional batteries, its active substance not on electrode, but in the electrolytic solution; This kind of constructional feature and fuel cell are similar, but manufacturing cost is lower than fuel cell, and relatively lead-acid cell is relative with fuel cell simple for production technique. Flow battery deep discharge, energy efficiency height, power can reach MW class, Application Areas is very wide, can be used as emergency power power supply, the supporting energy storage device of grid-connected power generation system, and peak load regulation network etc., in extensive energy storage field, there is the superiority of effectiveness exceeding lithium ion battery and nickel metal hydride battery. Water medium zinc cerium flow battery, owing to active substance restriction of solubleness in water solvent causes its energy density to be difficult to further lifting; Energy density, generally at below 50Wh/L, can not meet the demand to energy-storage battery high-energy-density that people are growing.
Summary of the invention
It is an object of the invention to provide a kind of flow battery positive pole cerium base il electrolyte and its preparation method.
The technical scheme of the present invention:
A kind of flow battery positive pole cerium base il electrolyte, by 1-methyl, 3-propyl imidazole cerium fluorine trifluoroacetate and Sodium Fluoride composition, Sodium Fluoride mass percentage in the electrolytic solution is 0.5% 10%;
Described 1-methyl, 3-propyl imidazole cerium fluorine trifluoroacetate is solvent and active substance, and its structural formula is as follows:
Wherein n=1-3.
A preparation method for flow battery positive pole cerium base il electrolyte, comprises the following steps:
A, cerous fluoride is put into beaker, it is placed in 40-60 DEG C of baking oven 6-18 hour;
B, steps A gained cerous fluoride is ground to 500-1000 order, it is placed in 40-60 DEG C of baking oven 2-6 hour;
C, step B gained cerous fluoride is joined 1-methyl, in 3-propyl imidazole trifluoroacetate, cerous fluoride and 1-methyl, the mol ratio of 3-propyl imidazole trifluoroacetate is (1-3): 1; Adding 500-1000 object Sodium Fluoride simultaneously, constantly stir 2-5 hour, obtain required electrolytic solution, wherein Sodium Fluoride accounts for the 0.5 10% of electrolytic solution total mass.
The present invention uses cerous fluoride and 1-methyl, and 3-propyl imidazole trifluoroacetic acid reactant salt generates 1-methyl, 3-propyl imidazole cerium fluorine trifluoroacetate. The composition of electrolytic solution is 1-methyl, 3-propyl imidazole cerium fluorine trifluoroacetate and Sodium Fluoride. Sodium Fluoride mass percentage in the electrolytic solution is 0.5 10%.
The electrolytic solution of the present invention can form zinc cerium base ionic liquid flow battery system with the collocation of non-aqueous media zinc-base ionic liquid.
The key of the present invention is that cerium base ionic liquid is solvent and active substance, and Ce elements and the mol ratio as the cerium base ionic liquid of solvent are (1-3): 1. This is considerably beyond the mol ratio (1:56) of Ce elements in water medium cerium electrolytic solution and aqueous solvent. Thus non-aqueous media flow battery system by anode electrolyte of cerium base ionic liquid is all much bigger than the energy density of corresponding water medium system, and generally the former is more than 3 times of the latter. Sodium Fluoride is conducive to strengthening the ionic conduction ability of inside battery.
Accompanying drawing explanation
Fig. 1 is the cell structural representation using the cerium base il electrolyte of the present invention as anode electrolyte.
Embodiment
Below by specific embodiment, the invention will be further described, but should not be understood as limitation of the invention, the scope according to the content of the present invention, make the amendment of other various ways, replacing the technology that realizes and all belong to the present invention. In embodiment, the content of NaF is mass percentage, and embodiment 4,5,6 is the performance perameter using the cerium base il electrolyte of the present invention as the cell of anode electrolyte.
Embodiment 1:
Prepare 100 grams of 1-methyl, 3-propyl imidazole cerium fluorine trifluoroacetic acid ionic liquid (n=1)+0.5%NaF electrolytic solution.
First take 48.16 grams of cerous fluorides, it is placed in 250mL beaker, be placed in 60 DEG C of baking ovens 6 hours; Then cerous fluoride is ground to 1000 orders, is placed in 60 DEG C of baking ovens 2 hours; Finally take 51.34 grams of 1-methyl, 3-propyl imidazole trifluoroacetic acid ionic liquid, move in beaker; In beaker, add the cerous fluoride of above-mentioned oven dry, fully react; Gram 500 order Sodium Fluorides that add 0.50, stir 2 hours; Obtain the electrolytic solution of required preparation.
Embodiment 2:
Prepare 100 grams of 1-methyl, 3-propyl imidazole cerium fluorine trifluoroacetic acid ionic liquid (n=2)+5%NaF electrolytic solution.
First take 61.97 grams of cerous fluorides, it is placed in 250mL beaker, be placed in 40 DEG C of baking ovens 18 hours; Then cerous fluoride is ground to 500 orders, is placed in 40 DEG C of baking ovens 6 hours; Finally take 33.03 grams of 1-methyl, 3-propyl imidazole trifluoroacetic acid ionic liquid, move in beaker; In beaker, add the cerous fluoride of above-mentioned oven dry, fully react; Gram 1000 order Sodium Fluorides that add 5, stir 5 hours; Obtain the electrolytic solution of required preparation.
Embodiment 3:
Prepare 100 grams of 1-methyl, 3-propyl imidazole cerium fluorine trifluoroacetic acid ionic liquid (n=3)+10%NaF electrolytic solution.
First take 66.40 grams of cerous fluorides, it is placed in 250mL beaker, be placed in 50 DEG C of baking ovens 12 hours; Then cerous fluoride is ground to 800 orders, is placed in 50 DEG C of baking ovens 4 hours; Finally take 23.60 grams of 1-methyl, 3-propyl imidazole trifluoroacetic acid ionic liquid, move in beaker; In beaker, add the cerous fluoride of above-mentioned oven dry, fully react; Gram 800 order Sodium Fluorides that add 10, stir 3 hours; Obtain the electrolytic solution of required preparation.
Embodiment 4:
The positive and negative electrode room of battery is separated by anion-exchange membrane; Doing positive and negative electrode 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=1)+5%NaF solution, anode electrolyte is 200 grams of 1-methyl, 3-propyl imidazole cerium fluorine trifluoroacetic acid ionic liquid (n=1)+5%NaF solution. Charging and discharging currents is 200mA, and electrolyte flow rate is 5mL/min. The energy density of battery is 123Wh/L, is 3.15 times of water medium zinc cerium flow battery energy density (39Wh/L).
Embodiment 5:
The positive and negative electrode room of battery is separated by anion-exchange membrane; Doing positive and negative electrode 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, 3-propyl imidazole cerium fluorine trifluoroacetic acid ionic liquid (n=2)+10%NaF solution. Charging and discharging currents is 200mA, and electrolyte flow rate is 5mL/min. The energy density of battery is 185Wh/L, is 4.74 times of water medium zinc cerium flow battery energy density (39Wh/L).
Embodiment 6:
The positive and negative electrode room of battery is separated by anion-exchange membrane; Doing positive and negative electrode 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, 3-propyl imidazole cerium fluorine trifluoroacetic acid ionic liquid (n=3)+5%NaF solution. Charging and discharging currents is 200mA, and electrolyte flow rate is 5mL/min. The energy density of battery is 249Wh/L, is 6.38 times of water medium zinc cerium flow battery energy density (39Wh/L).
Claims (4)
1. a flow battery positive pole cerium base il electrolyte, is characterized in that: by 1-methyl, 3-propyl imidazole cerium fluorine trifluoroacetate and Sodium Fluoride composition, and Sodium Fluoride mass percentage in the electrolytic solution is 0.5% 10%;
Described 1-methyl, 3-propyl imidazole cerium fluorine trifluoroacetate is solvent and active substance, and its structural formula is as follows:
Wherein n=1-3.
2. a kind of flow battery positive pole cerium base il electrolyte according to claim 1, it is characterized in that: described 1-methyl, 3-propyl imidazole cerium fluorine trifluoroacetate by cerous fluoride and 1-methyl, 3-propyl imidazole trifluoroacetate in molar ratio (1-3): 1 preparation.
3. prepare the method for flow battery positive pole cerium base il electrolyte according to claim 1, it is characterized in that: comprise the following steps:
A, cerous fluoride is put into beaker, it is placed in 40-60 DEG C of baking oven 6-18 hour;
B, steps A gained cerous fluoride is ground to 500-1000 order, it is placed in 40-60 DEG C of baking oven 2-6 hour;
C, step B gained cerous fluoride is joined 1-methyl, in 3-propyl imidazole trifluoroacetate, cerous fluoride and 1-methyl, the mol ratio of 3-propyl imidazole trifluoroacetate is (1-3): 1; Adding 500-1000 object Sodium Fluoride simultaneously, constantly stir 2-5 hour, obtain required electrolytic solution, wherein Sodium Fluoride accounts for the 0.5 10% of electrolytic solution total mass.
4. the preparation method of flow battery positive pole cerium base il electrolyte according to claim 3, is characterized in that: first take 66.40 grams of cerous fluorides, be placed in 250mL beaker, is placed in 50 DEG C of baking ovens 12 hours; Then cerous fluoride is ground to 800 orders, is placed in 50 DEG C of baking ovens 4 hours; Finally take 23.60 grams of 1-methyl, 3-propyl imidazole trifluoroacetic acid ionic liquid, move in beaker; In beaker, add the cerous fluoride of above-mentioned oven dry, fully react; And gram 800 order Sodium Fluorides that add 10, stir 3 hours; Obtain the electrolytic solution of required preparation.
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| CN201610177723.8A CN105633440B (en) | 2016-03-26 | 2016-03-26 | A kind of flow battery positive pole cerium base il electrolyte and preparation method thereof |
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| CN201610177723.8A CN105633440B (en) | 2016-03-26 | 2016-03-26 | A kind of flow battery positive pole cerium base il electrolyte and preparation method thereof |
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| CN105633440A true CN105633440A (en) | 2016-06-01 |
| CN105633440B CN105633440B (en) | 2017-10-27 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102142571A (en) * | 2010-01-29 | 2011-08-03 | 三星电子株式会社 | Organic electrolyte solution and redox flow battery including the same |
| 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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2016
- 2016-03-26 CN CN201610177723.8A patent/CN105633440B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102142571A (en) * | 2010-01-29 | 2011-08-03 | 三星电子株式会社 | Organic electrolyte solution and redox flow battery including the same |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 谢志鹏等: "锌铈液流电池研究进展", 《有色金属科学与工程》 * |
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