CN105591142A - Zinc-based ionic liquid electrolyte for liquid flow battery negative electrode and preparation method of zinc based ionic liquid electrolyte - Google Patents

Zinc-based ionic liquid electrolyte for liquid flow battery negative electrode and preparation method of zinc based ionic liquid electrolyte Download PDF

Info

Publication number
CN105591142A
CN105591142A CN201610179436.0A CN201610179436A CN105591142A CN 105591142 A CN105591142 A CN 105591142A CN 201610179436 A CN201610179436 A CN 201610179436A CN 105591142 A CN105591142 A CN 105591142A
Authority
CN
China
Prior art keywords
zinc
electrolyte
ionic liquid
methyl
fluoride
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610179436.0A
Other languages
Chinese (zh)
Other versions
CN105591142B (en
Inventor
谢志鹏
杨斌
刘柏雄
舒琪
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangxi University of Science and Technology
Original Assignee
Jiangxi University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangxi University of Science and Technology filed Critical Jiangxi University of Science and Technology
Priority to CN201610179436.0A priority Critical patent/CN105591142B/en
Publication of CN105591142A publication Critical patent/CN105591142A/en
Application granted granted Critical
Publication of CN105591142B publication Critical patent/CN105591142B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Secondary Cells (AREA)

Abstract

The invention relates to a large-scale energy storage liquid flow battery technology, in particular to zinc based ionic liquid electrolyte for a liquid flow battery negative electrode and a preparation method of the zinc-based ionic liquid electrolyte and belongs to the field of electrochemical energy storage. The zinc-based ionic liquid electrolyte for the liquid flow battery negative electrode and the preparation method of the zinc-based ionic liquid electrolyte are characterized in that zinc-based ionic liquid is solvent and also an active substance, and the molar ratio of the zinc element to the zinc based ionic liquid serving as solvent is (1-3):1 which far exceeds the molar ratio, namely 1:28, of the zinc element in water medium zinc electrolyte to solvent water, so that energy and density of a non-water medium liquid flow system with the zinc based ion liquid as the negative electrode electrolyte are far larger than a corresponding water medium system and are generally three times or above that of the corresponding water medium system.

Description

A kind of zinc-base il electrolyte and preparation method thereof for flow battery negative pole
Technical field
The present invention relates to extensive energy-storage liquid galvanic battery technology, particularly a kind of flow battery negative pole zinc-base il electrolyteAnd preparation method thereof, 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, and it is livedProperty material is not on electrode, but in electrolyte; This design feature and fuel cell are similar, but manufacturing cost lower thanFuel cell, production technology is relative with fuel cell simple compared with lead-acid battery. Flow battery can deep discharge, energy efficiency is high,Power can reach MW class, and application is very wide, can be used as emergency standby power, the supporting energy storage dress of grid-connected power generation systemPut, and peak load regulation network etc., there is in extensive energy storage field the superiority of effectiveness that exceedes lithium ion battery and Ni-MH battery. WaterMedium zinc negative pole flow battery, because active material restriction of solubility in aqueous solvent causes its energy density to be difficult to further carryRise; Energy density generally, below 50Wh/L, can not meet the growing demand to energy-storage battery high-energy-density of people.
Summary of the invention
The object of this invention is to provide a kind of flow battery negative pole zinc-base il electrolyte and preparation method thereof.
Technical scheme of the present invention:
A kind of flow battery negative pole zinc-base il electrolyte, by 1-methyl, 3-propyl imidazole zinc fluorine trifluoroacetate with fluoridizeSodium composition, the quality percentage composition of sodium fluoride in electrolyte is 0.5%-10%;
Described 1-methyl, 3-propyl imidazole zinc fluorine trifluoroacetate is solvent and active material, and its structural formula is as follows:
Wherein n=1-3.
A preparation method for zinc-base il electrolyte for flow battery negative pole, comprises the following steps:
A, zinc fluoride is put into beaker, be placed in 40-60 DEG C of baking oven 6-18 hour;
B, steps A gained zinc fluoride is ground to 500-1000 order, is placed in 40-60 DEG C of baking oven 2-6 hour;
C, step B gained zinc fluoride is joined to 1-methyl, in 3-propyl imidazole trifluoroacetate, zinc fluoride and 1-methyl, 3-The mol ratio of propyl imidazole trifluoroacetate is (1-3): 1; Add 500-1000 object sodium fluoride simultaneously, constantly stir 2-5 hour,Obtain required electrolyte, wherein sodium fluoride accounts for 0.5-10% of electrolyte gross mass.
The present invention uses zinc fluoride and 1-methyl, and 3-propyl imidazole trifluoroacetic acid reactant salt generates 1-methyl, 3-propyl imidazole zinc fluorine threeFluoroacetate. The composition of electrolyte is 1-methyl, 3-propyl imidazole zinc fluorine trifluoroacetate and sodium fluoride. Sodium fluoride is in electrolyteQuality percentage composition be 0.5-10%.
Electrolyte of the present invention can be respectively and non-aqueous media iron-based ionic liquid, vanadium base ionic liquid, bromo ionic liquid and ceriumThe collocation of base ionic liquid forms zinc iron-based ionic liquid flow battery system, almagrerite base ionic liquid flow battery system, zinc bromoIonic liquid flow battery system and zinc cerium base ionic liquid flow battery system.
Key of the present invention is that zinc-base ionic liquid is solvent and active material, and zinc element with as the zinc-base of solventThe mol ratio of ionic liquid is (1-3): 1. This considerably beyond the mol ratio of zinc element and aqueous solvent in aqueous medium zinc electrolyte (1:28). Thereby non-aqueous media flow battery system taking zinc-base ionic liquid as negative pole electrolyte is all than corresponding aqueous medium systemEnergy density is much bigger, and generally the former is the more than 3 times of the latter. Sodium fluoride is conducive to strengthen the ionic conduction ability of inside battery.
Brief description of the drawings
Fig. 1 is the monomer battery structure schematic diagram using zinc-base il electrolyte of the present invention as negative pole electrolyte.
Detailed description of the invention
Below by specific embodiment, the invention will be further described, but should not be understood as limitation of the invention, according to thisThe content of invention, make other various ways amendment, replace the technology that realizes and all belong to scope of the present invention. In embodimentThe content of NaF is quality percentage composition, and embodiment 4,5,6,7 is using zinc-base il electrolyte of the present invention as negative electricitySeparate the performance parameter of the cell of liquid.
Embodiment 1:
Prepare 100 grams of 1-methyl, 3-propyl imidazole zinc fluorine trifluoroacetate ionic liquid (n=1)+0.5%NaF electrolyte.
First take 32.74 grams of zinc fluorides, be placed in 250mL beaker, be placed in 60 DEG C of baking ovens 6 hours; Then zinc fluoride is groundTo 1000 orders, be placed in 60 DEG C of baking ovens 2 hours; Finally take 66.76 grams of 1-methyl, 3-propyl imidazole trifluoroacetate ionic liquid,Move in beaker; Toward the zinc fluoride that adds above-mentioned oven dry in beaker, fully reaction; Add 0.50 gram of 1000 order sodium fluoride, stir 2Hour; Obtain the electrolyte of required preparation.
Embodiment 2:
Prepare 100 grams of 1-methyl, 3-propyl imidazole zinc fluorine trifluoroacetate ionic liquid (n=2)+5%NaF electrolyte.
First take 47.04 grams of zinc fluorides, be placed in 250mL beaker, be placed in 40 DEG C of baking ovens 18 hours; Then zinc fluoride is groundBe ground to 500 orders, be placed in 40 DEG C of baking ovens 6 hours; Finally take 47.96 grams of 1-methyl, 3-propyl imidazole trifluoroacetate ionic liquidBody, moves in beaker; Toward the zinc fluoride that adds above-mentioned oven dry in beaker, fully reaction; Add 5 gram of 500 order sodium fluoride, stir 5Hour; Obtain the electrolyte of required preparation.
Embodiment 3:
Prepare 100 grams of 1-methyl, 3-propyl imidazole zinc fluorine trifluoroacetate ionic liquid (n=3)+10%NaF electrolyte.
First take 53.58 grams of zinc fluorides, be placed in 250mL beaker, be placed in 50 DEG C of baking ovens 12 hours; Then zinc fluoride is groundBe ground to 800 orders, be placed in 50 DEG C of baking ovens 4 hours; Finally take 36.42 grams of 1-methyl, 3-propyl imidazole trifluoroacetate ionic liquidBody, moves in beaker; Toward the zinc fluoride that adds above-mentioned oven dry in beaker, fully reaction; Add 10 gram of 800 order sodium fluoride, stir 3Hour; Obtain the electrolyte of required preparation.
Embodiment 4:
Anion-exchange membrane separates the both positive and negative polarity chamber of battery; Do positive and negative electrode with carbon felt, the apparent area of the two is 20cm2。Negative pole electrolyte is 100 grams of 1-methyl, 3-propyl imidazole zinc fluorine trifluoroacetate ionic liquid (n=1)+5%NaF solution, positive poleElectrolyte is 200 grams of 1-methyl, 3-propyl imidazole iron fluorine trifluoroacetate ionic liquid (n=1)+5%NaF solution. Charging and discharging currentsFor 200mA, electrolyte flow rate is 5mL/min. The energy density of battery is 106Wh/L, is that aqueous medium zinc-iron flow battery energy is closeDegree (35Wh/L) 3.03 times.
Embodiment 5:
Anion-exchange membrane separates the both positive and negative polarity chamber of battery; Do positive and negative electrode with carbon felt, the apparent area of the two is 20cm2。Negative pole electrolyte is 100 grams of 1-methyl, 3-propyl imidazole zinc fluorine trifluoroacetate ionic liquid (n=3)+10%NaF solution, positive poleElectrolyte is 200 grams of 1-methyl, 3-propyl imidazole vanadium fluorine trifluoroacetate ionic liquid (n=3)+5%NaF solution. Charging and discharging currents is200mA, electrolyte flow rate is 5mL/min. The energy density of battery is 251Wh/L, is that aqueous medium almagrerite flow battery energy is closeDegree (41Wh/L) 6.12 times.
Embodiment 6:
Anion-exchange membrane separates the both positive and negative polarity chamber of battery; Do positive and negative electrode with carbon felt, the apparent area of the two is 20cm2。Negative pole electrolyte is 100 grams of 1-methyl, 3-propyl imidazole zinc fluorine trifluoroacetate ionic liquid (n=2)+0.5%NaF solution, positive poleElectrolyte is 200 grams of 1-methyl, 3-propyl imidazole aluminium bromine trifluoroacetate ionic liquid (n=2)+10%NaF solution. Charging and discharging currentsFor 200mA, electrolyte flow rate is 5mL/min. The energy density of battery is 203Wh/L, is that aqueous medium zinc bromine flow battery energy is closeDegree (45Wh/L) 4.51 times.
Embodiment 7:
Anion-exchange membrane separates the both positive and negative polarity chamber of battery; Do positive and negative electrode with carbon felt, the apparent area of the two is 20cm2。Negative pole electrolyte is 100 grams of 1-methyl, 3-propyl imidazole zinc fluorine trifluoroacetate ionic liquid (n=3)+10%NaF solution, positive poleElectrolyte is 200 grams of 1-methyl, 3-propyl imidazole cerium fluorine trifluoroacetate ionic liquid (n=3)+5%NaF solution. Charging and discharging currents is200mA, electrolyte flow rate is 5mL/min. The energy density of battery is 249Wh/L, is that aqueous medium zinc cerium flow battery energy is closeDegree (39Wh/L) 6.38 times.

Claims (4)

1. a flow battery negative pole zinc-base il electrolyte, is characterized in that: by 1-methyl, and 3-propyl imidazole zinc fluorine threeFluoroacetate and sodium fluoride composition, the quality percentage composition of sodium fluoride in electrolyte is 0.5%-10%;
Described 1-methyl, 3-propyl imidazole zinc fluorine trifluoroacetate is solvent and active material, and its structural formula is as follows:
Wherein n=1-3.
2. a kind of flow battery negative pole zinc-base il electrolyte according to claim 1, is characterized in that: described1-methyl, 3-propyl imidazole zinc fluorine trifluoroacetate is by zinc fluoride and 1-methyl, and 3-propyl imidazole trifluoroacetate is in molar ratio(1-3): 1 preparation.
3. the method for zinc-base il electrolyte for preparation flow battery negative pole claimed in claim 1, is characterized in that: compriseFollowing steps:
A, zinc fluoride is put into beaker, be placed in 40-60 DEG C of baking oven 6-18 hour;
B, steps A gained zinc fluoride is ground to 500-1000 order, is placed in 40-60 DEG C of baking oven 2-6 hour;
C, step B gained zinc fluoride is joined to 1-methyl, in 3-propyl imidazole trifluoroacetate, zinc fluoride and 1-methyl, 3-The mol ratio of propyl imidazole trifluoroacetate is (1-3): 1; Add 500-1000 object sodium fluoride simultaneously, constantly stir 2-5 hour,Obtain required electrolyte, wherein sodium fluoride accounts for 0.5-10% of electrolyte gross mass.
4. the preparation method of zinc-base il electrolyte for flow battery negative pole according to claim 3, is characterized in that:First take 53.58 grams of zinc fluorides, be placed in 250mL beaker, be placed in 50 DEG C of baking ovens 12 hours; Then zinc fluoride is ground to800 orders, are placed in 50 DEG C of baking ovens 4 hours; Finally take 36.42 grams of 1-methyl, 3-propyl imidazole trifluoroacetate ionic liquid,Move in beaker; Toward the zinc fluoride that adds above-mentioned oven dry in beaker, fully reaction; And adding 10 gram of 800 order sodium fluoride, stirring 3 is littleTime; Obtain the electrolyte of required preparation.
CN201610179436.0A 2016-03-26 2016-03-26 A kind of flow battery negative pole zinc-base il electrolyte and preparation method thereof Expired - Fee Related CN105591142B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
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

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
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

Publications (2)

Publication Number Publication Date
CN105591142A true CN105591142A (en) 2016-05-18
CN105591142B CN105591142B (en) 2017-10-27

Family

ID=55930526

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610179436.0A Expired - Fee Related CN105591142B (en) 2016-03-26 2016-03-26 A kind of flow battery negative pole zinc-base il electrolyte and preparation method thereof

Country Status (1)

Country Link
CN (1) CN105591142B (en)

Citations (3)

* Cited by examiner, † Cited by third party
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
CN102324550A (en) * 2011-08-19 2012-01-18 李桂云 Semi-liquid lithium-sulfur battery
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
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
CN102324550A (en) * 2011-08-19 2012-01-18 李桂云 Semi-liquid lithium-sulfur battery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
尤洪星等: ""过渡金属配合物功能化离子液体的合成及其在均相催化中的应用"", 《化学进展》 *

Also Published As

Publication number Publication date
CN105591142B (en) 2017-10-27

Similar Documents

Publication Publication Date Title
WO2012162390A1 (en) Flow battery and mn/v electrolyte system
CN108630458A (en) Aqueous electrolyte and application thereof
CN110034340B (en) Aqueous electrolyte and aqueous metal ion battery
CN104362393A (en) Rechargeable aqueous ion battery
CN106981371A (en) A kind of water system electrolyte super capacitance cell
CN106549179B (en) A kind of organic system lithium quinone flow battery
CN107359372B (en) Aqueous electrolyte and aqueous metal ion battery
CN104064824A (en) Water system rechargeable battery
CN110867587A (en) Neutral water system mixed liquid flow battery with high power and long service life based on pyridylphenoxazine
CN107256986A (en) A kind of aqueous electrolyte and Water based metal ion battery
CN113690397B (en) Zinc cathode pole piece and preparation method and application thereof
CN108390110B (en) Lead-manganese secondary battery
CN110085864A (en) The preparation method and application of potassium or based lithium-ion battery positive plate
CN114447446A (en) Aqueous zinc ion battery additive, electrolyte prepared from same and application of electrolyte
CN103904352B (en) Zinc electrolyte for flow battery and preparation method thereof
CN104300169A (en) Alkaline zinc vanadium flow battery
CN112952172A (en) Alkaline iron-nickel flow battery
CN114335643A (en) Iron complex-air flow battery
CN114447445A (en) Preparation and application of aqueous zinc ion battery electrolyte
CN106450400A (en) All-vanadium redox flow battery
CN105591142A (en) Zinc-based ionic liquid electrolyte for liquid flow battery negative electrode and preparation method of zinc based ionic liquid electrolyte
CN112467233A (en) High-performance aqueous electrolyte for chargeable and dischargeable zinc-manganese battery
CN105702996B (en) A kind of flow battery positive pole bromo il electrolyte and preparation method thereof
CN105633440B (en) A kind of flow battery positive pole cerium base il electrolyte and preparation method thereof
CN105826587B (en) A kind of flow battery positive pole iron-based ionic liquid electrolyte and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20171027