CN105655621A - Zinc-cerium-based ionic liquid flow battery - Google Patents

Zinc-cerium-based ionic liquid flow battery Download PDF

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Publication number
CN105655621A
CN105655621A CN201610178691.3A CN201610178691A CN105655621A CN 105655621 A CN105655621 A CN 105655621A CN 201610178691 A CN201610178691 A CN 201610178691A CN 105655621 A CN105655621 A CN 105655621A
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ionic liquid
zinc
cerium
flow battery
positive
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CN201610178691.3A
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CN105655621B (en
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谢志鹏
杨斌
袁华丽
刘宏萱
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Jiangxi University of Science and Technology
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Jiangxi University of Science and Technology
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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

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  • 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)
  • Hybrid Cells (AREA)

Abstract

The invention relates to a novel zinc-cerium-based ionic liquid flow battery, which can be widely applied to the large-scale energy storage of a now energy source, and belongs to the field of electrochemistry. According to the novel zinc-cerium-based ionic liquid flow battery, as ionic liquids which are quite strong in dissolving capacities are selected for preparing positive and negative electrolytes, active substances which are high in concentration are acquired. For a zinc-based ionic liquid of a negative electrode, the molar ratio of a precursor zinc fluoride to a precursor ionic liquid is (1 to 3): 1. For a cerium-based ionic liquid of a positive electrode, the molar ratio of a precursor cerous fluoride to a precursor ionic liquid is (1 to 3): 1. The energy density of the zinc-cerium-based ionic liquid flow battery can be up to above 3 times the energy density of an existing aqueous medium zinc-cerium flow battery.

Description

Zinc cerium base ionic liquid flow battery
Technical field
The present invention relates to a kind of novel zinc cerium base ionic liquid flow battery, belong to electrochemical field, the extensive energy storage of new forms of energy can be widely used in.
Background technology
The two eleventh century mankind face multiple stern challenge, such as climate warming, desertification of land, lack of energy etc. Countries in the world government pays much attention to the exploitation of new forms of energy. Energy storage technology is the gordian technique of utilization of new energy resources. Existing power energy storage technology is drawn water power station, pressurized air, superconducting magnetic and battery etc. Flow battery is a kind of novel Large Copacity redox electrochemical energy storage device. Different from conventional batteries, the active substance of flow battery is not on electrode, but dissolves in the electrolytic solution, is the moiety of electrolytic solution. The electrode of flow battery is electrochemistry inert material, only for electrode reaction provides place, and does not participate in into the electrode reaction of stream. Thus, the power of flow battery and capacity can independent design. Its power depends on the size of electrode and pile, and capacity then depends on amount and the concentration of electrolytic solution.
Currently, the research of zinc cerium flow battery is only limitted to water medium system,
Negative reaction is:
Positive pole reaction is:
The concentration of this water medium system electrolyte liquid active substance is about 2.0mol/L, and the concentration of anode electrolyte active substance is about 1mol/L. If the mol ratio being converted into solute and solvent, electrolyte liquid is 1:28, and anode electrolyte is 1:56. From energy density, so low active material concentration can not meet actual needs.
Summary 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, overcome the weak point of existing flow battery, that widens zinc cerium resource utilizes scope.
The present invention improves on the basis of existing flow battery and becomes. The pile that the multiple batteries monomer that the present invention forms primarily of negative pole, electrolyte liquid, positive pole, anode electrolyte and ion-exchange membrane (barrier film) is unified into, electrolyte liquid is placed in negative pole container for storing liquid, the conveying of electrolyte liquid is carried out by pump, anode electrolyte is placed in positive pole container for storing liquid, carries out the conveying of anode electrolyte by pump. Anode chamber electrolysis fluid catheter and negative pole container for storing liquid, electrolyte liquid transferpump in pile are linked to be loop, and electrolyte liquid circulates in this loop. Cathode chamber in pile is linked to be loop by electrolytic solution conduit and positive pole container for storing liquid, anode electrolyte transferpump, and anode electrolyte circulates in this loop. The key of the present invention is that described electrolyte liquid is zinc-base ionic liquid, and anode electrolyte is cerium base ionic liquid.
The zinc-base ionic liquid of described electrolyte liquid, selects zinc fluoride to be dissolved in 1,3-dialkylimidazolium trifluoroacetate and is made into zinc-base ionic liquid, and its structural formula is as follows:
N=1-3, zinc-base ionic liquid is one matter, is not mixture, and it is solvent and active substance;
The cerium base ionic liquid of described anode electrolyte, selects cerous fluoride to be dissolved in 1,3-dialkylimidazolium trifluoroacetate and is made into cerium base ionic liquid, and its structural formula is as follows:
N=1-3, cerium base ionic liquid is one matter, is not mixture, and it is solvent and active substance.
All containing the Sodium Fluoride that mass percent is 0.5% 10% in positive and negative electrode electrolytic solution.
The zinc cerium base ionic liquid flow battery of the present invention is using zinc-base ionic liquid as negative electrode active material, and cerium base ionic liquid is positive active material, and its electrode reaction is as follows:
Negative reaction:
Positive pole reacts:
Its principle of work utilizes the redox reaction between different valence state zinc cerium base ionic liquid to realize the conversion of energy, and positive and negative electrode active substance is liquid cerium zinc-base ionic liquid, and redox reaction occurs on noble electrode. During discharge and recharge, positive and negative electrode electrolytic solution circulates in respective loop. During charging, zinc-base ionic liquid is reduced into zinc, and 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 reduced 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, owing to selecting ionic liquid that solvency power is very strong to prepare positive and negative electrode electrolytic solution, thus obtains the active substance of high density. 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. Considering the molecular weight of ionic liquid and wanting greatly of volume ratio water molecules, the concentration of zinc cerium base ionic liquid active substance is about more than 3 times of water medium zinc cerium flow battery active material concentration; Also it is exactly that the energy density of zinc cerium base ionic liquid flow battery provided by the invention can reach more than 3 times of existing water medium zinc cerium flow battery energy density.
Accompanying drawing explanation
Fig. 1 is the structural representation of the zinc cerium base ionic liquid flow battery monomer of the present invention.
Embodiment
As shown in Figure 1 (in figure arrow be electrolyte stream to), the pile that the multiple batteries monomer that the present invention forms primarily of negative pole, electrolyte liquid, positive pole, anode electrolyte and ion-exchange membrane (barrier film) is unified into, electrolyte liquid is placed in negative pole container for storing liquid, the conveying of electrolyte liquid is carried out by pump, anode electrolyte is placed in positive pole container for storing liquid, carries out the conveying of anode electrolyte by pump. Anode chamber electrolysis fluid catheter and negative pole container for storing liquid, electrolyte liquid transferpump in pile are linked to be loop, and electrolyte liquid circulates in this loop. Cathode chamber in pile is linked to be loop by electrolytic solution conduit and positive pole container for storing liquid, anode electrolyte transferpump, and anode electrolyte circulates in this loop. Described electrolyte liquid is zinc-base ionic liquid, and anode electrolyte is cerium base ionic liquid.
The zinc-base ionic liquid of described electrolyte liquid, selects presoma zinc fluoride to be dissolved in presoma 1,3-dialkylimidazolium trifluoroacetic acid ionic liquid and obtains.
The cerium base ionic liquid of described anode electrolyte, selects presoma cerous fluoride to be dissolved in presoma 1,3-dialkylimidazolium trifluoroacetic acid ionic liquid and obtains.
The positive and negative electrode of battery cell can select the inert materials such as carbon felt, graphite felt, graphite cake, graphite paper or carbon cloth. Ion-exchange membrane is divided into battery cell cathode chamber and anode chamber two portions, and positive pole is in cathode chamber, and negative pole is in anode chamber. Described ion-exchange membrane selects anion-exchange membrane.
The present invention is in charge and discharge process, and positive and negative electrode electrolytic solution enters in battery cell by the positive and negative electrode continuous pump of electrolytic solution transferpump respectively, and the flowing of electrolytic solution accelerates the material transfer process in electrode interface, is conducive to the electrochemistry in reduction electrode reaction and concentration polarization.The rated output of battery depends on the size of pile, and amount of capacity depends on electrolytic solution.
During discharge and recharge of the present invention, the negative, positive pole electrolytic solution in the container for storing liquid of negative, positive pole, under the promotion of electrolytic solution transferpump, is entered in room, negative, positive pole by electrolytic solution conduit and carries out electrode reaction, then flow back in the container for storing liquid of negative, positive pole again.
In embodiment, the content of NaF is mass percentage content.
Embodiment 1:
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 2:
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 3:
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 (6)

1. a zinc cerium base ionic liquid flow battery, comprises positive and negative electrode and positive and negative electrode electrolytic solution, it is characterized in that: described electrolyte liquid is zinc-base ionic liquid, and anode electrolyte is cerium base ionic liquid;
The zinc-base ionic liquid of described electrolyte liquid, selects zinc fluoride to be dissolved in 1,3-dialkylimidazolium trifluoroacetate and is made into zinc-base ionic liquid, and its structural formula is as follows:
Wherein: n=1-3, zinc-base ionic liquid is one matter, is not mixture, and it is solvent and active substance;
The cerium base ionic liquid of described anode electrolyte, selects cerous fluoride to be dissolved in 1,3-dialkylimidazolium trifluoroacetate and is made into cerium base ionic liquid, and its structural formula is as follows:
Wherein: n=1-3, cerium base ionic liquid is one matter, is not mixture, and it is solvent and active substance;
All containing the Sodium Fluoride that mass percent is 0.5% 10% in positive and negative electrode electrolytic solution.
2. a kind of zinc cerium base ionic liquid flow battery according to claim 1, is characterized in that: positive and negative electrode 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: the zinc-base ionic liquid of described electrolyte liquid, presoma zinc fluoride is selected to be dissolved in presoma 1, obtaining in 3-dialkylimidazolium trifluoroacetic acid ionic liquid, the mol ratio of presoma zinc fluoride and presoma ionic liquid is (1-3): 1;
The cerium base ionic liquid of described anode electrolyte, selects presoma cerous fluoride to be dissolved in presoma 1,3-dialkylimidazolium trifluoroacetic acid ionic liquid and obtains, and 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, is characterized in that: the positive and negative electrode standard electric potential difference of cell is 2.60V.
5. a kind of zinc cerium base ionic liquid flow battery according to claim 1, is characterized in that: positive and negative electrode selects the one in carbon felt, 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, is characterized in that: do positive and negative electrode with carbon felt, and 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 and mass percent are the NaF solution of 10%; Anode electrolyte is 200 grams of 1-methyl, and 3-propyl imidazole cerium fluorine trifluoroacetic acid ionic liquid and mass percent are the NaF solution of 5%; Charging and discharging currents is 200mA, and electrolyte flow rate is 5mL/min, and the energy density of battery is 249Wh/L, is 6.38 times of water medium zinc cerium flow battery energy density;
Wherein: 1-methyl, the n=3 of 3-propyl imidazole zinc fluorine trifluoroacetic acid ionic liquid; 1-methyl, the n=3 of 3-propyl imidazole cerium fluorine trifluoroacetic acid ionic liquid.
CN201610178691.3A 2016-03-26 2016-03-26 Zinc cerium base ionic liquid flow battery Expired - Fee Related CN105655621B (en)

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Citations (2)

* 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

Patent Citations (2)

* 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

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
王少鹏: "硝酸作为阳极电解液在锌铈液流电池中的应用", 《材料开发与应用》 *
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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