CN112928298A - Zinc-bromine single flow battery structure - Google Patents
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- CN112928298A CN112928298A CN201911239795.0A CN201911239795A CN112928298A CN 112928298 A CN112928298 A CN 112928298A CN 201911239795 A CN201911239795 A CN 201911239795A CN 112928298 A CN112928298 A CN 112928298A
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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
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/0273—Sealing or supporting means around electrodes, matrices or membranes with sealing or supporting means in the form of a frame
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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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- 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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Abstract
The invention relates to an internal electrode structure in a neutral zinc-bromine liquid single flow battery, belonging to the field of flow batteries. The method is to improve the electrode frame structure of the existing zinc-bromine single flow battery to achieve the following purposes: ensuring that the generated bromine is completely attached to the carbon felt, and ensuring that the cathode: prevent the growth of negative pole zinc dendrite into the negative pole electrolyte main runner to make the battery discharge more fully, improve battery performance. The method has the advantages of simple operation, stable process, obvious application effect and the like. The zinc-bromine single flow battery manufactured by the method can effectively improve the coulomb efficiency of the battery and prolong the service life of the battery.
Description
Technical Field
The invention relates to a zinc-bromine single flow battery structure.
Technical Field
With the increasing exhaustion of fossil energy, the development and utilization of renewable energy sources such as wind energy and solar energy have become the focus of attention of various countries. Because wind energy and solar energy are affected by factors such as weather and the like and have discontinuity and instability, impact can be caused to a power grid in the renewable energy power generation grid connection process, and power supply quality and power grid stability are affected. The energy storage technology can solve the problem and ensure the efficient and stable operation of the renewable energy power generation grid connection. Energy storage technologies are mainly classified into two categories, physical energy storage and chemical energy storage. The chemical energy storage represented by the all-vanadium redox flow battery and the zinc-bromine redox flow battery has the most advantages in large-scale energy storage due to the advantages of mutual independence of power and capacity, quick response, simple structure, easiness in design, long cycle life, environmental friendliness and the like. Compared with the electrolyte of the all-vanadium redox flow battery, the electrolyte of the zinc-bromine redox flow battery has the advantages of low price, abundant resources and wide sources.
For a zinc-bromine system flow battery, the problem that a zinc dendrite on a battery cathode blocks a flow channel always restricts the development of the battery. In the charging process of the battery, zinc dendrites generated in the negative electrode are irregular in shape, the situation that zinc elementary substances at individual parts are accumulated excessively easily occurs, an electrolyte flow channel is further blocked, the flow of the negative electrode electrolyte is not smooth, and the negative electrode of the battery has a hydrogen evolution side reaction due to insufficient supply of zinc ions, so that the performance of the battery is influenced. For a zinc bromine single flow battery, due to a special single flow structure, electrolyte of a positive electrode does not flow, bromine generated by the positive electrode in the charging process is completely sealed in an electrode frame, bromine molecules can only pass through conductive carbon felt fibers to perform a reaction of converting electrons into bromine ions, and therefore, the bromine molecules of the positive electrode are required to be ensured to be completely contacted with the carbon felt fibers.
A zinc-bromine single flow battery structure is characterized in that the internal structure of a positive electrode frame and a negative electrode frame is redesigned, the internal of the positive electrode frame is completely filled with a carbon felt, and bromine molecules generated by the positive electrode in the charging process are completely attached to the carbon felt; inside the negative electrode frame, leave the cavity between business turn over liquid runner mouth and carbon felt, guarantee that deposited zinc simple substance is not direct and runner mouth contact on the carbon felt, prevent that accumulated zinc simple substance from blockking up the runner mouth, and then influence the inside electrolyte of negative pole and flow. The zinc-bromine single flow battery operated by using the structure inhibits the accumulation of bromine molecules of the positive electrode, improves the deposition and dissolution stability of zinc of the negative electrode, improves the coulombic efficiency of the battery, and improves the operation stability of the battery.
Disclosure of Invention
The invention combines the structural characteristics of the zinc-bromine single flow battery, redesigns the internal structure of the positive and negative electrode frames, and improves the coulombic efficiency and stability of the battery by using the design that the positive electrode is completely filled with the carbon felt, the negative electrode is filled with the carbon felt and the cavity is reserved.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the hollow part of the positive electrode frame is designed to be rectangular (the length is 40cm, the width is 30cm), the rectangular shape is the shape of the positive electrode, the shape of the carbon felt used by the positive electrode is completely the same as that of the hollow part in the electrode frame, and the condition that the carbon felt is fully filled in the positive electrode frame without a cavity is ensured. In the negative electrode frame, use the cavity with carbon felt and electrolyte liquid business turn over liquid mouth and separate, let carbon felt not with electrolyte business turn over liquid mouth contact, guarantee that the zinc simple substance that the negative pole generated in the charging process can not direct contact electrolyte runner mouth, prevent that accumulated zinc from blockking up the runner.
A zinc-bromine single flow battery structure comprises a single cell between a positive end plate and a negative end plate or a pile formed by connecting more than two single cells in series between the positive end plate and the negative end plate, a negative electrolyte storage tank, a negative circulation pipeline and a pump; the monocell comprises a positive current collector, a positive electrode, a battery diaphragm, a negative electrode and a negative current collector, wherein the positive current collector, the positive electrode and the battery diaphragm are sequentially overlapped from bottom to top; the positive electrolyte is filled in a closed chamber surrounded by the positive electrode frame, the positive current collector and the battery diaphragm; the method is characterized in that: the cathode electrode frame is a flat plate with a through hole in the middle, a cathode electrolyte inlet and an outlet are respectively arranged on the upper side and the lower side of the cathode electrode frame, the cathode electrolyte inlet is communicated with the middle through hole through an inlet distribution runner, the cathode electrolyte outlet is communicated with the middle through hole through an outlet distribution runner, the rectangular cathode is arranged in the middle through hole, a gap is reserved between the upper side and the lower side of the rectangular cathode and the corresponding inlet distribution runner and outlet distribution runner respectively, and the left side and the right side of the rectangular cathode are respectively attached to the inner wall surfaces of the left side and the right side of the middle through hole;
the anode electrode frame is a flat plate with a through hole in the middle, the anode is arranged in the through hole in the middle, and the peripheral edge of the anode is attached to the inner wall surface of the through hole in the middle.
The shape and size of the through hole in the middle of the positive electrode and the positive electrode frame are the same. Wherein the positive electrode is a flexible electrode, the negative electrode is also a flexible electrode, and the positive electrolyte and the negative electrolyte are the same; the electrolyte is a mixed aqueous solution of zinc bromide and potassium chloride, wherein the mixed aqueous solution contains zinc bromide with the final concentration of 2-5M, potassium chloride or ammonium chloride with the final concentration of 1-3M, and the molar ratio of the zinc bromide to the additive is 7: 1-4: 1, preferably 5: 1. the positive and negative flexible electrodes are carbon felts.
In the positive electrode frame, the carbon felt is completely filled in the cavity, the carbon felt in the negative electrode frame is not completely filled, and a cavity is reserved near the liquid inlet and outlet end.
The negative electrode is sealed in the electrode frame, the thickness of the electrode frame is 2.5-4mm, and the thickness of the negative electrode is 4-6 mm; the positive electrode is sealed in the electrode frame, the thickness of the electrode frame is 2.5-4mm, and the thickness of the positive electrode is 4-6 mm.
The battery separator is an ion conducting membrane.
The positive electrolyte is sealed in the positive electrode frame, the negative electrolyte comes from the liquid storage tank, and the electrolyte is circulated by a pump.
The cathode electrode frame is a flat plate with a through hole in the middle, the middle of the cross section of the surface of the through hole parallel plate is rectangular, the upper part of the cross section is trapezoidal which is on the same side with the rectangle, the lower part of the cross section is inverted trapezoidal which is on the same side with the rectangle, and the shape and the size of the through hole rectangle in the middle of the cathode electrode frame are the same.
The invention has the beneficial effects that:
compared with the zinc bromine single flow battery operated by the traditional structure, the coulombic efficiency of the zinc bromine single flow battery operated by the battery structure is 2-3 percent higher. The interior of the positive electrode frame is completely filled with the carbon felt, so that bromine molecules generated by the positive electrode in the charging process are completely attached to the carbon felt; inside the negative electrode frame, leave the cavity between business turn over liquid runner mouth and carbon felt, guarantee that deposited zinc simple substance is not direct and runner mouth contact on the carbon felt, prevent that accumulated zinc simple substance from blockking up the runner mouth, and then influence the inside electrolyte of negative pole and flow. The zinc-bromine single flow battery operated by using the structure inhibits the accumulation of bromine molecules of the positive electrode, improves the deposition and dissolution stability of zinc of the negative electrode, improves the coulombic efficiency of the battery, and improves the operation stability of the battery.
The method has low cost, rapid action, and simple operation. The problems of low coulombic efficiency and poor stability of the zinc-bromine single flow battery are solved in a short time and high efficiency mode, and the development of the zinc-bromine single flow battery can be greatly promoted.
Drawings
FIG. 1 is a schematic structural view of comparative example 1, in which a is a positive electrode frame structure and b is a negative electrode frame structure;
FIG. 2 is a schematic structural view of comparative example 2, in which a is a positive electrode frame structure and b is a negative electrode frame structure;
fig. 3 is a schematic structural diagram of example 1, in which a is a positive electrode frame structure and b is a negative electrode frame structure.
Detailed Description
Example 1
By using the structure designed by the invention, the zinc-bromine single flow battery is operated by using the structure that the cavity is not reserved in the positive electrode frame and the cavity is reserved in the negative electrode frame, and the performance and the stability of the zinc-bromine single flow battery are inspected. (the diagonally shaded portions in the figure are carbon felt electrodes). The anode frame is a flat plate with a through hole in the middle, the middle of the cross section of the through hole parallel plate body is rectangular, the edges of the periphery of the anode are attached to the inner wall surface of the through hole in the middle, and the anode electrolyte is packaged in the rectangular middle of the anode frame. The cathode electrode frame is a flat plate with a through hole in the middle, the middle of the cross section of the surface of the through hole parallel plate is rectangular, the upper part of the cross section of the surface of the through hole parallel plate is trapezoidal, and the lower part of the cross section of the surface of the through hole parallel plate is inverted trapezoidal; the rectangular negative electrode is arranged in a rectangular position with the same shape in the middle of the through hole, a negative electrolyte inlet and an outlet are respectively arranged on the upper side and the lower side of the rectangular negative electrode, the negative electrolyte inlet is communicated with the middle through hole through an inlet distribution flow channel, the negative electrolyte outlet is communicated with the middle through hole through an outlet distribution flow channel, trapezoidal gaps are respectively reserved between the upper side and the lower side of the rectangular negative electrode and the corresponding inlet distribution flow channel and outlet distribution flow channel, and the left side and the right side of the rectangular negative electrode are respectively attached to the inner wall surfaces of the left side. The positive electrode and the negative electrode are both flexible carbon felts, the positive electrolyte and the negative electrolyte are mixed aqueous solutions of zinc bromide and potassium chloride, wherein the final concentrations of the zinc bromide and the potassium chloride are 2M and 3M, and the molar ratio of the zinc bromide to the additive is 5: 2.
comparative example 1
The difference from the embodiment 1 lies in that the cathode electrode frame is a flat plate with a through hole in the middle, the middle of the section of the through hole parallel plate body is rectangular, the peripheral edge of the anode is attached to the inner wall surface of the through hole in the middle, and the anode electrolyte is packaged in the rectangular middle of the anode electrode frame. Otherwise, the same procedure as in example 1 was repeated.
Comparative example 2
The difference from the embodiment 1 is that the anode electrode frame is a flat plate with a through hole in the middle, the middle of the section of the plate body parallel to the through hole is rectangular, the upper part of the section of the plate body is trapezoidal and is in common with the rectangle, and the lower part of the section of the plate body parallel to the through hole is inverted trapezoidal and is in common with the rectangle; the rectangular negative electrode is arranged in a rectangular position with the same shape in the middle of the through hole, a negative electrolyte inlet and an outlet are respectively arranged on the upper side and the lower side of the rectangular negative electrode, the negative electrolyte inlet is communicated with the middle through hole through an inlet distribution flow channel, the negative electrolyte outlet is communicated with the middle through hole through an outlet distribution flow channel, trapezoidal gaps are respectively reserved between the upper side and the lower side of the rectangular negative electrode and the corresponding inlet distribution flow channel and outlet distribution flow channel, and the left side and the right side of the rectangular negative electrode are respectively attached to the inner wall surfaces of the left side. Otherwise, the same procedure as in example 1 was repeated.
In the embodiment 1, the inside of the positive electrode frame is completely filled with the carbon felt, so that bromine molecules generated by the positive electrode in the charging process are completely attached to the carbon felt; inside the negative electrode frame, leave the cavity between business turn over liquid runner mouth and carbon felt, guarantee that deposited zinc simple substance is not direct and runner mouth contact on the carbon felt, prevent that accumulated zinc simple substance from blockking up the runner mouth, and then influence the inside electrolyte of negative pole and flow. The zinc-bromine single flow battery operated by using the structure inhibits the accumulation of bromine molecules of the positive electrode, improves the deposition and dissolution stability of zinc of the negative electrode, improves the coulombic efficiency of the battery, and improves the operation stability of the battery.
In the comparative example 1, no cavity is left between the cathode inlet and outlet flow passage port and the carbon felt, and the zinc simple substance accumulated in the cathode can directly block the cathode flow passage, so that the cathode electrolyte can not flow smoothly, the cathode polarization is increased, and the stability of the battery is influenced.
In comparative example 2, the positive electrode frame and the negative electrode frame are symmetrically designed, a gap is reserved between the positive electrode and the negative electrode and an electrolyte inlet and outlet in the electrode frame, a bromine simple substance generated by the positive electrode cannot enter the gap region inevitably in the charging process, and the bromine simple substance entering the gap region cannot obtain electrons to be changed into bromine ions in the discharging process, so that incomplete discharge of the positive electrode is caused, the coulomb efficiency of the battery is influenced, and the stability of the battery is further influenced.
The zinc bromine single liquid flow battery has the performance of charging 60mins @ current density of 40mA/cm2Discharge @ Current Density 40mA/cm2。
Claims (9)
1. A zinc-bromine single flow battery structure comprises a single cell between a positive end plate and a negative end plate or a pile formed by connecting more than two single cells in series between the positive end plate and the negative end plate, a negative electrolyte storage tank, a negative circulation pipeline and a pump; the monocell comprises a positive current collector, a positive electrode, a battery diaphragm, a negative electrode and a negative current collector, wherein the positive current collector, the positive electrode and the battery diaphragm are sequentially overlapped from bottom to top; the positive electrolyte is filled in a closed chamber surrounded by the positive electrode frame, the positive current collector and the battery diaphragm; the method is characterized in that: the cathode electrode frame is a flat plate with a through hole in the middle, a cathode electrolyte inlet and an outlet are respectively arranged on the upper side and the lower side of the cathode electrode frame, the cathode electrolyte inlet is communicated with the middle through hole through an inlet distribution runner, the cathode electrolyte outlet is communicated with the middle through hole through an outlet distribution runner, the rectangular cathode is arranged in the middle through hole, a gap is reserved between the upper side and the lower side of the rectangular cathode and the corresponding inlet distribution runner and outlet distribution runner respectively, and the left side and the right side of the rectangular cathode are respectively attached to the inner wall surfaces of the left side and the right side of the middle through hole;
the anode electrode frame is a flat plate with a through hole in the middle, the anode is arranged in the through hole in the middle, and the peripheral edge of the anode is attached to the inner wall surface of the through hole in the middle.
2. The structure of claim 1, wherein the shape and size of the central through holes of the positive electrode and the positive electrode frame are the same.
3. The structure of claim 1, wherein the positive electrode is a flexible electrode, the negative electrode is a flexible electrode, and the electrolytes of the positive electrode and the negative electrode are the same; the electrolyte is a mixed aqueous solution of zinc bromide and potassium chloride, wherein the mixed aqueous solution contains zinc bromide with the final concentration of 2-5M, potassium chloride or ammonium chloride with the final concentration of 1-3M, and the molar ratio of the zinc bromide to the additive is 7: 1-4: 1, preferably 5: 1.
4. the zinc-bromine single flow battery structure of claim 3, wherein the positive and negative flexible electrodes are both carbon felts.
5. The zinc-bromine single flow battery structure of claim 1, wherein: in the positive electrode frame, the carbon felt is completely filled in the cavity, the carbon felt in the negative electrode frame is not completely filled, and a cavity is reserved near the liquid inlet and outlet end.
6. The zinc-bromine single flow battery structure of claim 1 or 5, characterized in that: the negative electrode is sealed in the electrode frame, the thickness of the electrode frame is 2.5-4mm, and the thickness of the negative electrode is 4-6 mm; the positive electrode is sealed in the electrode frame, the thickness of the electrode frame is 2.5-4mm, and the thickness of the positive electrode is 4-6 mm.
7. The zinc-bromine single flow battery structure of claim 1, wherein the battery membrane is an ion conducting membrane.
8. The zinc-bromine single flow battery structure of claim 1, wherein the positive electrolyte is enclosed in a positive electrode frame, the negative electrolyte is from a reservoir, and the electrolyte is circulated by a pump.
9. The structure of claim 1, wherein the negative electrode frame is a flat plate with a through hole in the middle, the cross section of the surface of the through hole parallel plate has a rectangular middle part, a trapezoidal upper part which is the same as the rectangular middle part, and an inverted trapezoidal lower part which is the same as the rectangular middle part, and the shapes and sizes of the through hole rectangles in the middle parts of the negative electrode frame and the negative electrode frame are the same.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI796024B (en) * | 2021-11-30 | 2023-03-11 | 財團法人金屬工業研究發展中心 | Fluid battery module |
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