CN111180777A - Positive electrode electrolyte for zinc-bromine single flow battery - Google Patents
Positive electrode electrolyte for zinc-bromine single flow battery Download PDFInfo
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- CN111180777A CN111180777A CN201811343442.0A CN201811343442A CN111180777A CN 111180777 A CN111180777 A CN 111180777A CN 201811343442 A CN201811343442 A CN 201811343442A CN 111180777 A CN111180777 A CN 111180777A
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- electrolyte
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
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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 the technical field of electrodes for zinc bromine single flow batteries, in particular to a positive electrolyte for a zinc bromine single flow battery. The electrolyte component comprises a bromine ion-containing main salt, a complexing agent, a dispersing agent, an ion conductive auxiliary agent and an electronic conductive auxiliary agent. The invention provides a novel positive electrode electrolyte for a zinc-bromine single flow battery, which comprises the components of the electrolyte, namely, a bromine ion-containing main salt, a complexing agent, an ion conductive auxiliary agent, a dispersing agent and an electron conductive auxiliary agent, and is used for solving the problems of bromine simple substance complex agglomeration and insufficient electron conductive capability. The addition of the organic water-soluble dispersing agent can ensure that the bromine simple substance complex and the electrolyte have good compatibility. The uniform distribution of the bromine simple substance complex in the electrolyte is ensured. The addition of the electron conduction auxiliary agent increases the electron conduction capability of the electrolyte and solves the problem of reduction of the reaction rate of the battery caused by the non-flowing electrolyte.
Description
Technical Field
The invention relates to the technical field of electrodes for zinc bromine single flow batteries, in particular to a positive electrolyte for a zinc bromine single flow battery.
Background
Compared with the all-vanadium redox flow battery, the zinc-bromine redox flow battery has the advantages of high energy density and low cost. The theoretical open-circuit voltage of the zinc-bromine flow energy storage battery is about 1.80V, and the theoretical energy density is 430 Wh/kg. The positive electrode and the negative electrode of the zinc-bromine flow battery are separated by a diaphragm, and electrolyte solutions on both sides are ZnBr2And (3) solution. Under the action of the power pump, the electrolyte solution circulates in a closed loop formed by the liquid storage tank and the battery. The potential difference between the positive electrode pair and the negative electrode pair is the power for reaction, and the electrode reaction of the zinc-bromine flow battery is as follows:
and (3) positive electrode: 2Br-↔ Br2+ 2e （Eθ= 1.076 V）
Negative electrode: zn2++ 2e ↔ Zn （Eθ= -0.76 V）
The bromine environmental pollution and the penetration of the positive electrode of the zinc bromine battery are key problems which restrict the practicability and the industrialization of the zinc bromine flow battery. Bromine generated during battery charging can not be completely changed into bromine ions in a discharging stage, which causes the coulomb efficiency of the battery in subsequent circulation to be reduced on one hand, and easily causes the over-high concentration of the bromine in the positive electrode to permeate into the environment to cause pollution on the other hand, so that the zinc-bromine single flow battery technology is provided.
The positive electrode of the zinc-bromine single flow battery adopts a full-sealing structure, and bromine is sealed in the positive electrode and does not participate in the flow of electrolyte, so that the corrosion risk of a circulating pipeline can be relieved. However, the positive electrolyte does not flow and also has some problems: 1. the bromine generated by the anode reaction is combined with the complex to generate a bromine complex. The complex is insoluble in electrolyte, so that bromine simple substance complex is locally gathered, and the problems of increased concentration polarization, uneven reaction and the like are caused; 2. compared with the traditional zinc-bromine flow battery with flowing electrolyte, the contact sites of the bromine simple substance complex and the surface of the electrode are reduced, so that the electronic conductivity of the electrode is not enough to meet the reaction requirement of the bromine simple substance complex far away from the surface of the electrode.
Disclosure of Invention
The purpose of the invention is as follows: in order to provide a positive electrode electrolyte for a zinc-bromine single flow battery with better effect, the specific purpose is to see a plurality of substantial technical effects of the specific implementation part.
In order to achieve the purpose, the invention adopts the following technical scheme:
the further technical scheme of the invention is as follows: the electrolyte component comprises a bromine ion-containing main salt, a complexing agent, a dispersing agent, an ion conductive auxiliary agent and an electronic conductive auxiliary agent.
The further technical scheme of the invention is as follows: the bromide ion main salt is one or more of zinc bromide, sodium bromide and potassium bromide; the concentration of bromide ion is 1.0-4.0 mol/L.
The further technical scheme of the invention is as follows: the complexing agent is quaternary ammonium salt containing halogen ions and comprises one or more of tetrabutylammonium bromide, azomethylethylpyrrolidine bromide and azomethylethylmorpholine bromide; the concentration of the complexing agent is 0.1-2.0 mol/L.
The further technical scheme of the invention is as follows: the dispersing agent is a water-soluble organic substance and comprises one or more of sorbitol, polyvinylpyrrolidone and polyethylene glycol; the concentration of the dispersant is 0.1-2.0 mol/L.
The further technical scheme of the invention is as follows: the ionic conduction auxiliary agent is water-soluble salt containing halogen ions, and comprises one or more of potassium chloride, potassium iodide and ammonium fluoride; the concentration of the halogen ions is 1.0-4.0 mol/L.
The further technical scheme of the invention is as follows: the electronic conductive additive is a nano carbon material and comprises one or more of acetylene black, BP2000 and super P; the mass solid-liquid ratio between the electronic conductive additive and the electrolyte solution is 0.01-0.1.
The further technical scheme of the invention is as follows: after the battery is assembled, the electrolyte is poured into the positive electrode and then the battery operates.
Compared with the prior art, the invention adopting the technical scheme has the following beneficial effects: the invention provides a novel positive electrode electrolyte for a zinc-bromine single flow battery, which comprises the components of the electrolyte, namely, a bromine ion-containing main salt, a complexing agent, an ion conductive auxiliary agent, a dispersing agent and an electron conductive auxiliary agent, and is used for solving the problems of bromine simple substance complex agglomeration and insufficient electron conductive capability.
The addition of the organic water-soluble dispersing agent can ensure that the bromine simple substance complex and the electrolyte have good compatibility. The uniform distribution of the bromine simple substance complex in the electrolyte is ensured. The addition of the electron conduction auxiliary agent increases the electron conduction capability of the electrolyte and solves the problem of reduction of the reaction rate of the battery caused by the non-flowing electrolyte.
Drawings
To further illustrate the present invention, further description is provided below with reference to the accompanying drawings:
FIG. 1, comparative example, cell efficiency of conventional zinc-bromine single flow battery
FIG. 2, cell efficiency of Zinc bromine Single flow cell of example 1
FIG. 3 shows cell efficiency of the zinc-bromine single flow battery of example 2
Fig. 4 shows the cell efficiency of the zinc-bromine single flow battery of example 3.
Detailed Description
The present invention will be further illustrated with reference to the accompanying drawings and specific embodiments, which are to be understood as merely illustrative of the invention and not as limiting the scope of the invention.
Comparative example
The positive and negative electrodes are 36 cm2Carbon felt (5 mm thickness) with nafion membrane in the middle as the membrane. The electrolyte of the anode and the cathode is 2mol/L zinc bromide solution, the concentration of complexing agent N-methyl ethyl pyrrolidine bromide is 0.8mol/L, and the concentration of ionic conduction auxiliary agent potassium chloride is 2.0 mol/L. The cathode electrolyte 60 mol/LL circularly flows between the liquid storage tank and the cathode of the battery through a circulating pipeline. The anode is filled with 10 mol/LL of anode electrolyte. The battery adopts 40mA/cm2Charging and discharging at current density for 1 h; the discharge cut-off voltage was 1.0V. Cell efficiency and cycling performance are shown in figure 1.
As can be seen from fig. 1, the cell voltage efficiency of the comparative example was 80%, and the cell energy efficiency was 71%.
Example 1
The positive and negative electrodes are 36 cm2Carbon felt (5 mm thickness) with nafion membrane in the middle as the membrane. The electrolyte of the negative electrode is 2mol/L zinc bromide solution, the concentration of complexing agent N-methyl ethyl pyrrolidine bromide is 0.8mol/L, and the concentration of ionic conduction auxiliary agent potassium chloride is 2.0 mol/L. The cathode electrolyte 60 mol/LL circularly flows between the liquid storage tank and the cathode of the battery through a circulating pipeline.
The electrolyte of the anode is 2mol/L zinc bromide solution, the concentration of complexing agent N-methyl ethyl pyrrolidine bromide is 0.8mol/L, and the concentration of ionic conduction auxiliary agent potassium chloride is 2.0 mol/L. The concentration of sorbitol serving as a dispersant is 0.5 mol/L, and the mass ratio of the electronic conductive additive acetylene black to the electrolyte is 0.05. The anode is filled with 10 mol/LL of anode electrolyte.
The battery adopts 40mA/cm2Charging and discharging at current density for 1 h; the discharge cut-off voltage was 1.0V. Cell efficiency and cycling performance are shown in figure 2.
As can be seen from fig. 2, the cell voltage efficiency of the comparative example was 86%, and the cell energy efficiency was 83%.
Example 2
The positive and negative electrodes are 36 cm2Carbon felt (5 mm thickness) with nafion membrane in the middle as the membrane. The electrolyte of the negative electrode is 2mol/L zinc bromide solution, the concentration of complexing agent N-methyl ethyl pyrrolidine bromide is 0.8mol/L, and the concentration of ionic conduction auxiliary agent potassium chloride is 2.0 mol/L. The cathode electrolyte 60 mol/LL circularly flows between the liquid storage tank and the cathode of the battery through a circulating pipeline.
The electrolyte of the anode is 3 mol/L sodium bromide solution, the concentration of complexing agent N-methyl ethyl morpholine bromide is 2.0mol/L, and the concentration of ionic conduction auxiliary agent sodium chloride is 4.0 mol/L. The concentration of the dispersant polyvinylpyrrolidone is 2.0mol/L, and the mass ratio of the electronic conductive additive BP2000 to the electrolyte is 0.05. The anode is filled with 10 mol/LL of anode electrolyte.
The battery adopts 40mA/cm2Charging and discharging at current density for 1 h; the discharge cut-off voltage was 1.0V. Cell efficiency and cycling performance are shown in figure 3.
As can be seen from fig. 3, the cell voltage efficiency of the comparative example was 87%, and the cell energy efficiency was 84%.
Example 3
The positive and negative electrodes are 36 cm2Carbon felt (5 mm thickness) with nafion membrane in the middle as the membrane. The electrolyte of the negative electrode is 2mol/L zinc bromide solution, the concentration of complexing agent N-methyl ethyl pyrrolidine bromide is 0.8mol/L, and the concentration of ionic conduction auxiliary agent potassium chloride is 2.0 mol/L. The cathode electrolyte 60 mol/LL circularly flows between the liquid storage tank and the cathode of the battery through a circulating pipeline.
The positive electrode electrolyte is a sodium bromide solution with the concentration of 4.0 mol/L, the concentration of a complexing agent tetrabutyl ammonium bromide is 0.1 mol/L, the concentration of an ionic conduction auxiliary agent sodium chloride is 1.0 mol/L, the concentration of a dispersing agent polyethylene glycol is 0.1 mol/L, and the mass ratio of the electronic conduction auxiliary agent super P to the electrolyte is 0.1. The anode is filled with 10 mol/LL of anode electrolyte.
The battery adopts 40mA/cm2Charging and discharging at current density for 1 h; the discharge cut-off voltage was 1.0V. Cell efficiency and cycling performance are shown in figure 4.
As can be seen from fig. 4, the cell voltage efficiency of the comparative example was 80%, and the cell energy efficiency was 78%.
The invention provides a novel positive electrode electrolyte for a zinc-bromine single flow battery, which comprises the components of the electrolyte, namely, a bromine ion-containing main salt, a complexing agent, an ion conductive auxiliary agent, a dispersing agent and an electron conductive auxiliary agent, and is used for solving the problems of bromine simple substance complex agglomeration and insufficient electron conductive capability.
The addition of the organic water-soluble dispersing agent can ensure that the bromine simple substance complex and the electrolyte have good compatibility. The uniform distribution of the bromine simple substance complex in the electrolyte is ensured. The addition of the electron conduction auxiliary agent increases the electron conduction capability of the electrolyte and solves the problem of reduction of the reaction rate of the battery caused by the non-flowing electrolyte.
Creatively, the above effects exist independently, and the combination of the above results can be completed by a set of structure.
The technical effect that above structure was realized realizes clearly, if do not consider additional technical scheme, this patent name can also be a novel electrolyte. Some details are not shown in the figures.
It should be noted that the plurality of schemes provided in this patent include their own basic schemes, which are independent of each other and are not restricted to each other, but they may be combined with each other without conflict, so as to achieve a plurality of effects.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are intended to illustrate the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, and the invention is to be limited to the embodiments described above.
Claims (7)
1. The positive electrode electrolyte for the zinc-bromine single flow battery is characterized by comprising a bromine ion-containing main salt, a complexing agent, a dispersing agent, an ion conduction auxiliary agent and an electron conduction auxiliary agent.
2. The zinc-bromine single flow battery positive electrode electrolyte as claimed in claim 1, wherein the bromine ion main salt is one or more of zinc bromide, sodium bromide and potassium bromide; the concentration of bromide ion is 1.0-4.0 mol/L.
3. The zinc-bromine single flow battery positive electrode electrolyte as claimed in claim 1, wherein the complexing agent is a quaternary ammonium salt containing halogen ions, which comprises one or more of tetrabutylammonium bromide, azomethylethylpyrrolidine bromide, azomethylethylmorpholine bromide; the concentration of the complexing agent is 0.1-2.0 mol/L.
4. The zinc-bromine single flow battery positive electrode electrolyte as claimed in claim 1, wherein: the dispersing agent is a water-soluble organic substance and comprises one or more of sorbitol, polyvinylpyrrolidone and polyethylene glycol; the concentration of the dispersant is 0.1-2.0 mol/L.
5. The zinc-bromine single flow battery positive electrode electrolyte as claimed in claim 1, wherein: the ionic conduction auxiliary agent is water-soluble salt containing halogen ions, and comprises one or more of potassium chloride, potassium iodide and ammonium fluoride; the concentration of the halogen ions is 1.0-4.0 mol/L.
6. The zinc-bromine single flow battery positive electrode electrolyte as claimed in claim 1, wherein: the electronic conductive additive is a nano carbon material and comprises one or more of acetylene black, BP2000 and super P; the mass solid-liquid ratio between the electronic conductive additive and the electrolyte solution is 0.01-0.1.
7. The use of the zinc-bromine single flow battery positive electrolyte as claimed in claim 1, wherein: after the battery is assembled, the electrolyte is poured into the positive electrode and then the battery operates.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811343442.0A CN111180777A (en) | 2018-11-13 | 2018-11-13 | Positive electrode electrolyte for zinc-bromine single flow battery |
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| CN201811343442.0A CN111180777A (en) | 2018-11-13 | 2018-11-13 | Positive electrode electrolyte for zinc-bromine single flow battery |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113437339A (en) * | 2021-05-10 | 2021-09-24 | 中国科学院金属研究所 | Positive electrode electrolyte for zinc-iodine flow battery |
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| CN103137986A (en) * | 2011-12-05 | 2013-06-05 | 张华民 | Zinc bromine single flow cell |
| CN106099151A (en) * | 2008-06-12 | 2016-11-09 | 麻省理工学院 | High energy density redox flow device |
| CN106463750A (en) * | 2013-11-22 | 2017-02-22 | DWI莱布尼茨互动材料研究所e.V. | Oxygen-vanadium redox flow battery with vanadium electrolyte having carbon particles dispersed therein |
| CN106920983A (en) * | 2017-04-14 | 2017-07-04 | 南开大学 | A kind of symmetrical organic flow battery of non-water system of low temperature |
| CN107482243A (en) * | 2017-08-11 | 2017-12-15 | 北京理工大学 | The flowing electrode and its low cost preparation method of a kind of quinonyl flow battery |
| CN108134141A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of no diaphragm static state zinc-bromine bettery |
| CN108711633A (en) * | 2018-05-28 | 2018-10-26 | 犀望新能源科技（昆山）有限公司 | Electrolyte for zinc-bromine flow battery |
-
2018
- 2018-11-13 CN CN201811343442.0A patent/CN111180777A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106099151A (en) * | 2008-06-12 | 2016-11-09 | 麻省理工学院 | High energy density redox flow device |
| CN103137986A (en) * | 2011-12-05 | 2013-06-05 | 张华民 | Zinc bromine single flow cell |
| CN106463750A (en) * | 2013-11-22 | 2017-02-22 | DWI莱布尼茨互动材料研究所e.V. | Oxygen-vanadium redox flow battery with vanadium electrolyte having carbon particles dispersed therein |
| CN108134141A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of no diaphragm static state zinc-bromine bettery |
| CN106920983A (en) * | 2017-04-14 | 2017-07-04 | 南开大学 | A kind of symmetrical organic flow battery of non-water system of low temperature |
| CN107482243A (en) * | 2017-08-11 | 2017-12-15 | 北京理工大学 | The flowing electrode and its low cost preparation method of a kind of quinonyl flow battery |
| CN108711633A (en) * | 2018-05-28 | 2018-10-26 | 犀望新能源科技（昆山）有限公司 | Electrolyte for zinc-bromine flow battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113437339A (en) * | 2021-05-10 | 2021-09-24 | 中国科学院金属研究所 | Positive electrode electrolyte for zinc-iodine flow battery |
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