CN114497670B - Zinc bromine single-liquid flow galvanic pile - Google Patents
Zinc bromine single-liquid flow galvanic pile Download PDFInfo
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- CN114497670B CN114497670B CN202011259960.1A CN202011259960A CN114497670B CN 114497670 B CN114497670 B CN 114497670B CN 202011259960 A CN202011259960 A CN 202011259960A CN 114497670 B CN114497670 B CN 114497670B
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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
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/2455—Grouping of fuel cells, e.g. stacking of fuel cells with liquid, solid or electrolyte-charged reactants
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/2465—Details of groupings of fuel cells
- H01M8/2483—Details of groupings of fuel cells characterised by internal manifolds
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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
A zinc bromine single liquid flow electric pile comprises a battery pack formed by connecting m+n single cells in series, wherein m and n are integers larger than or equal to 2 respectively, each single cell comprises a negative electrode frame, a diaphragm and a positive electrode frame which are sequentially laminated, and a negative carbon felt electrode and a positive carbon felt electrode are respectively arranged in a through hole in the middle of the negative electrode frame and a through hole in the middle of the positive electrode frame; the negative electrode frame is a flat plate with a through hole in the middle, and the plate body is provided with a through hole which is perpendicular to the surface of the plate body and is used as a common electrolyte inlet flow channel A; in the n single cells, a common inlet flow channel B is connected with the negative electrolyte inlet flow channel on each negative electrode frame, and a common outlet flow channel B is connected with the negative electrolyte outlet flow channel on each negative electrode frame. The distribution uniformity of electrolyte in the electric pile is improved, and the stability of the electric pile is improved; and the public flow channels of the galvanic pile are separated, so that the influence of leakage current can be effectively reduced, and the coulomb efficiency of the galvanic pile is increased.
Description
Technical Field
The invention relates to the technical field of energy storage of flow batteries, in particular to the field of zinc-bromine single flow batteries.
Background
The zinc-bromine single flow battery is a novel low-cost, high-efficiency and long-service-life flow battery energy storage technology and has higher energy density. The zinc-bromine single-flow battery is used as a deposition battery, and the cycle stability of the zinc-bromine single-flow battery is a key point of the reliability of the battery. The average distribution of the electrolyte to the individual cells is an effective way to improve the stability of the cells. In the prior art, because the number of serial connection nodes of single cells in a cell stack is large, the flow rate of each single cell flowing into the cell stack cannot be ensured to be equal or the phase difference is small, so that the optimization of the flow mode of electrolyte of the cell stack is a key point for solving the flow uniformity of the cell stack. In addition, due to the characteristics of the zinc-bromine single flow battery and the adopted diaphragm, the coulomb efficiency of the electric pile is often low, and due to the non-uniformity of each section of material, the self-discharge degree of each section of the electric pile is different, and the non-uniformity degree of each section of the electric pile is aggravated, so that the improvement of the coulomb efficiency of the electric pile is also a necessary condition for ensuring the stability of the electric pile.
Disclosure of Invention
The invention provides a zinc-bromine single-liquid flow galvanic pile structure.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a zinc bromine single liquid flow electric pile comprises a battery pack formed by connecting m+n single cells in series, wherein m and n are integers larger than or equal to 2 respectively, each single cell comprises a negative electrode frame, a diaphragm and a positive electrode frame which are sequentially laminated, and a negative carbon felt electrode and a positive carbon felt electrode are respectively arranged in a through hole in the middle of the negative electrode frame and a through hole in the middle of the positive electrode frame;
the negative electrode frame is a flat plate with a through hole in the middle, and the through hole which is perpendicular to the surface of the plate body and is used as a common electrolyte inlet runner A, a common electrolyte outlet runner A, a common electrolyte inlet runner B and a common electrolyte outlet runner B are arranged on the plate body; the public inlet flow channels A in the battery pack are sequentially communicated, the public outlet flow channels A are sequentially communicated, the public inlet flow channels B are sequentially communicated, and the public outlet flow channels B are sequentially communicated;
in the m single cells, a public inlet runner A is connected with a negative electrolyte inlet runner on each negative electrode frame, the negative electrolyte inlet runner is connected with a middle through hole area of the negative electrode frame through a distribution runner, a public outlet runner A is connected with a negative electrolyte outlet runner on each negative electrode frame, and the negative electrolyte outlet runner is connected with the middle through hole area of the negative electrode frame through the distribution runner;
in the n single cells, a common inlet runner B is connected with a negative electrolyte inlet runner on each negative electrode frame, the negative electrolyte inlet runner is connected with a middle through hole area of the negative electrode frame through a distribution runner, a common outlet runner B is connected with a negative electrolyte outlet runner on each negative electrode frame, and the negative electrolyte outlet runner is connected with the middle through hole area of the negative electrode frame through the distribution runner.
After the galvanic pile is assembled, the negative electrode electrolyte is divided into A, B two flow paths when the galvanic pile operates; flow path a: the negative electrolyte flows into the public inlet flow channel A through the galvanic pile liquid inlet guide plate, flows into the negative electrode frame through the negative electrode inlet A, flows out of the negative electrode frame from the negative electrode outlet to the public outlet flow channel A, and flows out of the galvanic pile through the galvanic pile liquid guide plate; flow path B: the negative electrolyte flows into the public inlet flow channel B through the galvanic pile liquid inlet guide plate, flows into the negative electrode frame through the negative electrode inlet B, flows out of the negative electrode frame from the negative electrode outlet to the public outlet flow channel B, and flows out of the galvanic pile through the galvanic pile liquid guide plate.
The negative electrode frame is a flat plate with a through middle part, and a negative electrolyte inlet runner and a negative electrolyte outlet runner are respectively arranged on two opposite sides of a through hole on one side surface of the flat plate, and an electrolyte inlet distribution runner communicated with the negative electrolyte inlet runner and the middle through hole and an electrolyte outlet distribution runner communicated with the negative electrolyte outlet runner and the middle through hole.
m and n are integers greater than or equal to 2 respectively; after being sequentially laminated, the m single cells are sequentially laminated and connected with the n single cells in series to form a battery pack; or more than 1 single cell in m single cells and more than 1 single cell in n single cells are alternately stacked in series to form the battery pack.
Advantageous effects
According to the zinc-bromine single-flow galvanic pile structure provided by the invention, the negative electrode frame is composed of A, B groups, the negative electrode frame A is provided with 1 inlet common flow passage and 1 outlet common flow passage, the negative electrode frame B is provided with the other 1 inlet common flow passage and the other 1 outlet common flow passage, the negative electrolyte is divided into A, B flow passages, the number of battery sections to be distributed in each common flow passage is reduced, the distribution uniformity of the electrolyte in the galvanic pile is increased, and the stability of the galvanic pile is improved; and the public flow channels of the galvanic pile are separated, so that the influence of leakage current can be effectively reduced, and the coulomb efficiency of the galvanic pile is increased.
Drawings
FIG. 1 is a schematic diagram of a conventional electrode frame;
FIG. 2 is a schematic view of a negative electrode frame A of the present invention;
FIG. 3 is a schematic view of a negative electrode frame B of the present invention;
FIG. 4 is a schematic view of a positive electrode frame of the present invention;
FIG. 5 is a schematic view of an assembled electrode frame according to the present invention;
wherein 1 is a liquid inlet guide plate, 2 is a negative electrode frame A,3 is a positive electrode frame, 4 is a negative electrode frame B,5 is a liquid outlet guide plate, 6 is a positive electrolyte flow path, 7 is a negative electrolyte flow path A, and 8 is a negative electrolyte flow path B; fig. 6 shows a charge-discharge performance curve of the comparative example.
Fig. 7 shows the charge-discharge performance curve of example 1.
Fig. 8 shows the charge-discharge performance curve of example 2.
Detailed Description
Comparative example
The comparative example adopts a traditional electrode frame structure to assemble a zinc-bromine single-flow galvanic pile. The single cell comprises a negative electrode frame, a diaphragm and a positive electrode frame which are sequentially laminated, and a negative carbon felt electrode and a positive carbon felt electrode are respectively arranged in a through hole in the middle of the negative electrode frame and a through hole in the middle of the positive electrode frame; the negative electrode frame is a flat plate with a through hole in the middle, and the plate body is provided with a through hole which is perpendicular to the surface of the plate body and is used as a common inlet runner of electrolyte and a through hole which is used as a common outlet runner of electrolyte; the public inlet flow channels in the battery pack are sequentially communicated, and the public outlet flow channels are sequentially communicated; the public inlet runner is connected with the negative electrolyte inlet runner on each negative electrode frame, the negative electrolyte inlet runner is connected with the middle through hole area of the negative electrode frame through the distribution runner, the public outlet runner is connected with the negative electrolyte outlet runner on each negative electrode frame, and the negative electrolyte outlet runner is connected with the middle through hole area of the negative electrode frame through the distribution runner;
the electrolyte adopts 2mol/l zinc bromide solution, 3mol/l potassium chloride solution and 0.8mol/l MEP complexing agent. The specific electrode size, the number of cell stacks and the charge-discharge system are as follows:
electrode area: 1000cm 2 。
Number of galvanic pile: 20 sections
Current density: 40mA/cm 2 Charging time: discharge cut-off voltage for 1 hour: 16V
The coulomb efficiency of charge and discharge of the galvanic pile is 89.2%, the voltage efficiency is 82.4%, and the energy efficiency is 73.5%
Example 1
Embodiment 1 adopts the electrode frame structure provided by the invention to assemble a zinc bromine single liquid flow electric pile, and a single cell comprises a negative electrode frame, a diaphragm and a positive electrode frame which are sequentially stacked, wherein a negative carbon felt electrode and a positive carbon felt electrode are respectively arranged in a through hole in the middle of the negative electrode frame and a through hole in the middle of the positive electrode frame; the cathode electrode frame is a flat plate with a through hole in the middle, and the through hole which is perpendicular to the surface of the plate body and is used as a common electrolyte inlet flow channel A, a common electrolyte outlet flow channel A, a common electrolyte inlet flow channel B and a common electrolyte outlet flow channel B are arranged on the plate body; the public inlet flow channels A in the battery pack are sequentially communicated, the public outlet flow channels A are sequentially communicated, the public inlet flow channels B are sequentially communicated, and the public outlet flow channels B are sequentially communicated; in 10 single cells, a common inlet runner A is connected with a negative electrolyte inlet runner on each negative electrode frame, the negative electrolyte inlet runner is connected with a middle through hole area of the negative electrode frame through a distribution runner, a common outlet runner A is connected with a negative electrolyte outlet runner on each negative electrode frame, and the negative electrolyte outlet runner is connected with a middle through hole area of the negative electrode frame through a distribution runner; in another 10 single cells, a common inlet runner B is connected with the negative electrolyte inlet runner on each negative electrode frame, the negative electrolyte inlet runner is connected with the middle through hole area of the negative electrode frame through a distribution runner, a common outlet runner B is connected with the negative electrolyte outlet runner on each negative electrode frame, and the negative electrolyte outlet runner is connected with the middle through hole area of the negative electrode frame through a distribution runner. After the galvanic pile is assembled, the negative electrode electrolyte is divided into A, B two flow paths when the galvanic pile operates; flow path a: the negative electrolyte flows into the public inlet flow channel A through the galvanic pile liquid inlet guide plate, flows into the negative electrode frame through the negative electrode inlet A, flows out of the negative electrode frame from the negative electrode outlet to the public outlet flow channel A, and flows out of the galvanic pile through the galvanic pile liquid guide plate; flow path B: the negative electrolyte flows into the public inlet flow channel B through the galvanic pile liquid inlet guide plate, flows into the negative electrode frame through the negative electrode inlet B, flows out of the negative electrode frame from the negative electrode outlet to the public outlet flow channel B, and flows out of the galvanic pile through the galvanic pile liquid guide plate. The negative electrode frame is a flat plate with a through middle part, and a negative electrolyte inlet runner and a negative electrolyte outlet runner are respectively arranged on two opposite sides of a through hole on one side surface of the flat plate, and an electrolyte inlet distribution runner communicated with the negative electrolyte inlet runner and the middle through hole and an electrolyte outlet distribution runner communicated with the negative electrolyte outlet runner and the middle through hole. And after the 10 common inlet flow passages A are sequentially laminated with single cells connected with the negative electrolyte inlet flow passages on each negative electrode frame, the 10 common inlet flow passages A are sequentially laminated with the other 10 single cells connected with the negative electrolyte inlet flow passages on each negative electrode frame in series to form the battery pack.
The electrolyte adopts 2mol/l zinc bromide solution, 3mol/l potassium chloride solution and 0.8mol/l MEP complexing agent. The specific electrode size, the number of cell stacks and the charge-discharge system are as follows:
electrode area: 1000cm 2 。
Number of galvanic pile: 20 sections
Current density: 40mA/cm 2 Charging time: discharge cut-off voltage for 1 hour: 16V
The coulomb efficiency of charge and discharge of the galvanic pile is 95.6%, the voltage efficiency is 84.1%, and the energy efficiency is 80.3%
Example 2
Embodiment 2A zinc bromine single liquid flow galvanic pile assembled by adopting the electrode frame structure provided by the invention, wherein a single cell comprises a negative electrode frame, a diaphragm and a positive electrode frame which are sequentially laminated, and a negative carbon felt electrode and a positive carbon felt electrode are respectively arranged in a through hole in the middle of the negative electrode frame and a through hole in the middle of the positive electrode frame; the cathode electrode frame is a flat plate with a through hole in the middle, and the through hole which is perpendicular to the surface of the plate body and is used as a common electrolyte inlet flow channel A, a common electrolyte outlet flow channel A, a common electrolyte inlet flow channel B and a common electrolyte outlet flow channel B are arranged on the plate body; the public inlet flow channels A in the battery pack are sequentially communicated, the public outlet flow channels A are sequentially communicated, the public inlet flow channels B are sequentially communicated, and the public outlet flow channels B are sequentially communicated; in 15 single cells, a common inlet runner A is connected with a negative electrolyte inlet runner on each negative electrode frame, the negative electrolyte inlet runner is connected with a middle through hole area of the negative electrode frame through a distribution runner, a common outlet runner A is connected with a negative electrolyte outlet runner on each negative electrode frame, and the negative electrolyte outlet runner is connected with a middle through hole area of the negative electrode frame through a distribution runner; in another 15 single cells, a common inlet runner B is connected with the negative electrolyte inlet runner on each negative electrode frame, the negative electrolyte inlet runner is connected with the middle through hole area of the negative electrode frame through a distribution runner, a common outlet runner B is connected with the negative electrolyte outlet runner on each negative electrode frame, and the negative electrolyte outlet runner is connected with the middle through hole area of the negative electrode frame through a distribution runner. After the galvanic pile is assembled, the negative electrode electrolyte is divided into A, B two flow paths when the galvanic pile operates; flow path a: the negative electrolyte flows into the public inlet flow channel A through the galvanic pile liquid inlet guide plate, flows into the negative electrode frame through the negative electrode inlet A, flows out of the negative electrode frame from the negative electrode outlet to the public outlet flow channel A, and flows out of the galvanic pile through the galvanic pile liquid guide plate; flow path B: the negative electrolyte flows into the public inlet flow channel B through the galvanic pile liquid inlet guide plate, flows into the negative electrode frame through the negative electrode inlet B, flows out of the negative electrode frame from the negative electrode outlet to the public outlet flow channel B, and flows out of the galvanic pile through the galvanic pile liquid guide plate. The negative electrode frame is a flat plate with a through middle part, and a negative electrolyte inlet runner and a negative electrolyte outlet runner are respectively arranged on two opposite sides of a through hole on one side surface of the flat plate, and an electrolyte inlet distribution runner communicated with the negative electrolyte inlet runner and the middle through hole and an electrolyte outlet distribution runner communicated with the negative electrolyte outlet runner and the middle through hole. And after 15 common inlet flow passages A are sequentially laminated with single cells connected with the negative electrolyte inlet flow passages on each negative electrode frame, the single cells connected with the other 15 common inlet flow passages B and the negative electrolyte inlet flow passages on each negative electrode frame are sequentially laminated and connected in series to form the battery pack.
The electrolyte adopts 2mol/l zinc bromide solution, 3mol/l potassium chloride solution and 0.8mol/l MEP complexing agent. The specific electrode size, the number of cell stacks and the charge-discharge system are as follows:
electrode area: 1000cm 2 。
Number of galvanic pile: 30 knots
Current density: 40mA/cm 2 Charging time: discharge cut-off voltage for 1 hour: 24V
The coulomb efficiency of charge and discharge of the galvanic pile is 91.6%, the voltage efficiency is 83.1%, and the energy efficiency is 76.1%
In the comparative example, the traditional electrode frame structure is adopted to assemble the zinc-bromine single-flow electric pile 20 sections, the coulomb efficiency of the electric pile is 89.2%, and from the view of the cycle performance curve of the electric pile, the performance of the electric pile is greatly attenuated after each 20 cycles of continuous operation, and the stability of the electric pile is poor.
In the embodiment 1, the zinc-bromine single-flow galvanic pile 20 is assembled by adopting the electrode frame structure provided by the invention, the coulomb efficiency of the galvanic pile is 95.6%, and compared with the galvanic pile in the comparative example, the performance of the galvanic pile is greatly improved. The electrode frame structure provided by the invention reduces the leakage current of the electric pile and reduces the capacity loss of the electric pile. In addition, from the view of the cycle performance curve of the electric pile, the performance of the electric pile is still not attenuated after 140 cycles of continuous operation, and can be kept above 95%, so that the stability of the electric pile is also greatly improved.
In the embodiment 2, the electrode frame structure provided by the invention is adopted to assemble the zinc-bromine single-flow galvanic pile 30 sections, the coulomb efficiency of the galvanic pile is 91.5%, and the performance of the galvanic pile is reduced compared with that of the embodiment 1 due to the increase of the number of the galvanic pile sections, but the performance of the galvanic pile is still higher than that of the comparative example, and the galvanic pile continuously runs for 140 times, so that the retention rate of the cyclic performance is good and the stability of the galvanic pile can still be maintained from the view of a cyclic performance curve.
Therefore, after the zinc-bromine single-flow galvanic pile is assembled by adopting the electrode frame structure provided by the invention, the number of the battery sections occupied by 1 common flow channel in the galvanic pile is reduced, so that the leakage current of the galvanic pile is inhibited, and the coulomb efficiency of the galvanic pile can be greatly improved; also, as the inlet of the electric pile is divided into A, B two flow paths, the number of the battery sections allocated to each flow path is reduced, the flow rate of the electrolyte allocated to each electrode frame is more uniform, and the stability of the electric pile can be greatly improved.
Claims (3)
1. A zinc bromine single liquid flow electric pile comprises a battery pack formed by connecting m+n single cells in series, wherein m and n are integers larger than or equal to 2 respectively, each single cell comprises a negative electrode frame, a diaphragm and a positive electrode frame which are sequentially laminated, and a negative carbon felt electrode and a positive carbon felt electrode are respectively arranged in a through hole in the middle of the negative electrode frame and a through hole in the middle of the positive electrode frame;
the negative electrode frame is a flat plate with a through hole in the middle, and the through hole which is perpendicular to the surface of the plate body and is used as a common electrolyte inlet runner A, a common electrolyte outlet runner A, a common electrolyte inlet runner B and a common electrolyte outlet runner B are arranged on the plate body; the public inlet flow channels A in the battery pack are sequentially communicated, the public outlet flow channels A are sequentially communicated, the public inlet flow channels B are sequentially communicated, and the public outlet flow channels B are sequentially communicated;
in the m single cells, a public inlet runner A is connected with a negative electrolyte inlet runner on each negative electrode frame, the negative electrolyte inlet runner is connected with a middle through hole area of the negative electrode frame through a distribution runner, a public outlet runner A is connected with a negative electrolyte outlet runner on each negative electrode frame, and the negative electrolyte outlet runner is connected with the middle through hole area of the negative electrode frame through the distribution runner;
in the n single cells, a public inlet runner B is connected with a negative electrolyte inlet runner on each negative electrode frame, the negative electrolyte inlet runner is connected with a middle through hole area of the negative electrode frame through a distribution runner, a public outlet runner B is connected with a negative electrolyte outlet runner on each negative electrode frame, and the negative electrolyte outlet runner is connected with a middle through hole area of the negative electrode frame through a distribution runner; after the galvanic pile is assembled, the negative electrode electrolyte is divided into A, B two flow paths when the galvanic pile operates; flow path a: the negative electrolyte flows into the public inlet flow channel A through the galvanic pile liquid inlet guide plate, flows into the negative electrode frame through the negative electrode inlet A, flows out of the negative electrode frame from the negative electrode outlet to the public outlet flow channel A, and flows out of the galvanic pile through the galvanic pile liquid guide plate; flow path B: the negative electrolyte flows into the public inlet flow channel B through the galvanic pile liquid inlet guide plate, flows into the negative electrode frame through the negative electrode inlet, flows out of the negative electrode frame from the negative electrode outlet to the public outlet flow channel B, and flows out of the galvanic pile through the galvanic pile liquid guide plate.
2. The zinc bromine single flow galvanic pile of claim 1 wherein: the negative electrode frame is a flat plate with a through middle part, and a negative electrolyte inlet runner and a negative electrolyte outlet runner are respectively arranged on two opposite sides of a through hole on one side surface of the flat plate, and an electrolyte inlet distribution runner communicated with the negative electrolyte inlet runner and the middle through hole and an electrolyte outlet distribution runner communicated with the negative electrolyte outlet runner and the middle through hole.
3. The zinc bromine single flow galvanic pile of claim 1 wherein: m and n are integers greater than or equal to 2 respectively; after being sequentially laminated, the m single cells are sequentially laminated and connected with the n single cells in series to form a battery pack; or more than 1 single cell in m single cells and more than 1 single cell in n single cells are alternately stacked in series to form the battery pack.
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