CN114497670A - Zinc-bromine single-flow galvanic pile - Google Patents
Zinc-bromine single-flow galvanic pile Download PDFInfo
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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
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- 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
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Abstract
A zinc-bromine single-liquid galvanic pile comprises a battery pack formed by connecting m + n single cells in series, wherein m and n are integers more than or equal to 2 respectively, the single cells comprise a negative electrode frame, a diaphragm and a positive electrode frame which are sequentially stacked, and a negative carbon felt electrode and a positive carbon felt electrode are respectively placed 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 plate body is provided with a through hole which is vertical to the surface of the plate body and is used as a common electrolyte inlet channel A and the like; in the n single cells, the common inlet flow channel B is connected with the cathode electrolyte inlet flow channel on each cathode electrode frame, and the common outlet flow channel B is connected with the cathode electrolyte outlet flow channel on each cathode electrode frame. The distribution uniformity of the electrolyte in the galvanic pile is improved, and the stability of the galvanic pile is improved; and the common flow channel of the galvanic pile is 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 flow battery energy storage, in particular to the field of a zinc bromine single flow battery.
Background
The zinc-bromine single flow battery is a novel flow battery energy storage technology with low cost, high efficiency and long service life, and has higher energy density. The cycling stability of a zinc-bromine single flow battery as a sedimentary battery is critical to the reliability of the battery. The electrolyte is evenly distributed to each battery, which is an effective way to improve the stability of the battery. In the prior art, because the number of the series-connected sections of the single cells in the stack is large, the flow rate of each single cell flowing into the stack cannot be equal or has small difference, and therefore, the optimization of the electrolyte flowing mode of the stack is the key point for solving the flow uniformity of the stack. In addition, due to the characteristics of the zinc-bromine single flow battery and the adopted diaphragm, the coulomb efficiency of the galvanic pile is often low, and due to the nonuniformity of materials of all sections, the self-discharge degrees of all sections of the galvanic pile are different, so that the nonuniformity degree of all sections of the galvanic pile is aggravated, and therefore, the improvement of the coulomb efficiency of the galvanic pile is also a necessary condition for ensuring the stability of the galvanic pile.
Disclosure of Invention
The invention provides a zinc-bromine single-flow galvanic pile structure.
In order to achieve the purpose, the invention adopts the following technical scheme:
a zinc-bromine single-liquid galvanic pile comprises a battery pack formed by connecting m + n single cells in series, wherein m and n are integers more than or equal to 2 respectively, the single cells comprise a negative electrode frame, a diaphragm and a positive electrode frame which are sequentially stacked, and a negative carbon felt electrode and a positive carbon felt electrode are respectively placed 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 plate body is provided with a through hole which is vertical to the surface of the plate body and is used as an electrolyte common inlet flow passage A, a through hole which is used as an electrolyte common outlet flow passage A, a through hole which is used as an electrolyte common inlet flow passage B and a through hole which is used as an electrolyte common outlet flow passage B; the common inlet runners A in the battery pack are sequentially communicated, the common outlet runners A are sequentially communicated, the common inlet runners B are sequentially communicated, and the common outlet runners B are sequentially communicated;
in m single cells, a common inlet flow channel A is connected with a negative electrolyte inlet flow channel on each negative electrode frame, the negative electrolyte inlet flow channel is connected with the middle through hole area of the negative electrode frame through a distribution flow channel, a common outlet flow channel A is connected with a negative electrolyte outlet flow channel on each negative electrode frame, and the negative electrolyte outlet flow channel is connected with the middle through hole area of the negative electrode frame through the distribution flow channel;
in the n monocells, the public inlet flow channel B is connected with the negative electrolyte inlet flow channel on each negative electrode frame, the negative electrolyte inlet flow channel is connected with the middle through hole area of the negative electrode frame through the distribution flow channel, the public outlet flow channel B is connected with the negative electrolyte outlet flow channel on each negative electrode frame, and the negative electrolyte outlet flow channel is connected with the middle through hole area of the negative electrode frame through the distribution flow channel.
After the electric pile is assembled, the cathode electrolyte is divided into A, B two flow paths when the electric pile operates; flow path A: the cathode electrolyte flows into the common inlet flow channel A through the electrolyte inlet guide plate, flows into the cathode electrode frame through the cathode inlet A, flows out of the cathode electrode frame from the cathode outlet to the common outlet flow channel A, and flows out of the galvanic pile through the galvanic pile liquid outlet guide plate; flow path B: the cathode electrolyte flows into the public inlet flow channel B through the electrolyte inlet guide plate, flows into the cathode electrode frame through the cathode inlet, flows out of the cathode electrode frame from the cathode outlet to the public outlet flow channel B, and flows out of the pile through the pile liquid outlet guide plate.
The cathode electrode frame is a flat plate with a middle part provided with a through hole, a cathode electrolyte inlet flow channel and a cathode electrolyte outlet flow channel are respectively arranged on two opposite sides of the through hole on the surface of one side of the flat plate, and an electrolyte inlet distribution flow channel communicated with the cathode electrolyte inlet flow channel and the middle through hole, an electrolyte outlet distribution flow channel communicated with the cathode electrolyte outlet flow channel and the middle through hole are respectively arranged on two opposite sides of the through hole.
m and n are integers of 2 or more; m single batteries are sequentially stacked and then sequentially connected with n single batteries 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 and connected 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 consists of A, B groups, the negative electrode frame A is provided with 1 inlet common flow channel and 1 outlet common flow channel, the negative electrode frame B is provided with the other 1 inlet common flow channel and 1 outlet common flow channel, and the negative electrolyte is divided into A, B flow channels, so that the number of batteries needing to be distributed in each common flow channel 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 common flow channel of the galvanic pile is 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 view of a conventional electrode frame;
FIG. 2 is a schematic view of a negative electrode frame A according to the present invention;
FIG. 3 is a schematic view of a negative electrode frame B according to 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 electrode frame assembly 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 is a graph showing charge and discharge characteristics of the comparative example.
Fig. 7 is a charge and discharge performance curve of example 1.
Fig. 8 is a charge and discharge performance curve of example 2.
Detailed Description
Comparative example
Comparative example a zinc-bromine single flow cell stack was assembled using a conventional electrode frame structure. The single battery comprises a negative electrode frame, a diaphragm and a positive electrode frame which are sequentially stacked, 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 plate body is provided with a through hole which is vertical to the surface of the plate body and is used as a common electrolyte inlet flow passage and a through hole which is used as a common electrolyte outlet flow passage; the common inlet runners in the battery pack are sequentially communicated, and the common outlet runners are sequentially communicated; the public inlet runner is connected with the cathode electrolyte inlet runner on each cathode electrode frame, the cathode electrolyte inlet runner is connected with the middle through hole area of the cathode electrode frame through the distribution runner, the public outlet runner is connected with the cathode electrolyte outlet runner on each cathode electrode frame, and the cathode electrolyte outlet runner is connected with the middle through hole area of the cathode 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 the electrode stacks and the charging and discharging system are as follows:
electrode area: 1000cm2。
The number of the electric pile sections: 20 section
Current density: 40mA/cm2And charging time: 1 hour, discharge cut-off voltage: 16V
The coulombic efficiency of the charge and discharge of the galvanic pile is 89.2 percent, the voltage efficiency is 82.4 percent, and the energy efficiency is 73.5 percent
Example 1
In embodiment 1, a zinc-bromine single-liquid flow galvanic pile is assembled by adopting the electrode frame structure provided by the invention, a single cell comprises a negative electrode frame, a diaphragm and a positive electrode frame which are sequentially stacked, 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 plate body is provided with a through hole which is vertical to the surface of the plate body and is used as an electrolyte common inlet flow passage A, a through hole which is used as an electrolyte common outlet flow passage A, a through hole which is used as an electrolyte common inlet flow passage B and a through hole which is used as an electrolyte common outlet flow passage B; the common inlet runners A in the battery pack are sequentially communicated, the common outlet runners A are sequentially communicated, the common inlet runners B are sequentially communicated, and the common outlet runners B are sequentially communicated; in 10 single cells, a common inlet flow channel A is connected with a negative electrolyte inlet flow channel on each negative electrode frame, the negative electrolyte inlet flow channel is connected with the middle through hole area of the negative electrode frame through a distribution flow channel, a common outlet flow channel A is connected with a negative electrolyte outlet flow channel on each negative electrode frame, and the negative electrolyte outlet flow channel is connected with the middle through hole area of the negative electrode frame through the distribution flow channel; in the other 10 monocells, the public inlet flow channel B is connected with the negative electrolyte inlet flow channel on each negative electrode frame, the negative electrolyte inlet flow channel is connected with the middle through hole area of the negative electrode frame through the distribution flow channel, the public outlet flow channel B is connected with the negative electrolyte outlet flow channel on each negative electrode frame, and the negative electrolyte outlet flow channel is connected with the middle through hole area of the negative electrode frame through the distribution flow channel. After the stack is assembled, the cathode electrolyte is divided into A, B two flow paths when the stack operates; flow path A: the cathode electrolyte flows into the common inlet flow channel A through the electrolyte inlet guide plate, flows into the cathode electrode frame through the cathode inlet A, flows out of the cathode electrode frame from the cathode outlet to the common outlet flow channel A, and flows out of the galvanic pile through the galvanic pile liquid outlet guide plate; flow path B: the cathode electrolyte flows into the public inlet flow channel B through the electrolyte inlet guide plate, flows into the cathode electrode frame through the cathode inlet, flows out of the cathode electrode frame from the cathode outlet to the public outlet flow channel B, and flows out of the pile through the pile liquid outlet guide plate. The cathode electrode frame is a flat plate with a middle part provided with a through hole, a cathode electrolyte inlet flow channel and a cathode electrolyte outlet flow channel are respectively arranged on two opposite sides of the through hole on the surface of one side of the flat plate, and an electrolyte inlet distribution flow channel communicated with the cathode electrolyte inlet flow channel and the middle through hole, an electrolyte outlet distribution flow channel communicated with the cathode electrolyte outlet flow channel and the middle through hole are respectively arranged on two opposite sides of the through hole. And after 10 sections of the common inlet flow channels A are sequentially stacked with the monocells connected with the negative electrolyte inlet flow channels on each negative electrode frame, the other 10 sections of the common inlet flow channels B are sequentially stacked with the monocells connected with the negative electrolyte inlet flow channels 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 the electrode stacks and the charging and discharging system are as follows:
electrode area: 1000cm2。
The number of the electric pile sections: 20 section
Current density: 40mA/cm2And charging time: 1 hour, discharge cut-off voltage: 16V
The coulombic efficiency of charging and discharging the galvanic pile is 95.6 percent, the voltage efficiency is 84.1 percent, and the energy efficiency is 80.3 percent
Example 2
Embodiment 2 adopts the electrode frame structure provided by the present invention to assemble a zinc-bromine single liquid galvanic pile, wherein a single cell comprises a negative electrode frame, a diaphragm and a positive electrode frame which are sequentially stacked, and a negative carbon felt electrode and a positive carbon felt electrode are respectively placed 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 plate body is provided with a through hole which is vertical to the surface of the plate body and is used as an electrolyte common inlet flow passage A, a through hole which is used as an electrolyte common outlet flow passage A, a through hole which is used as an electrolyte common inlet flow passage B and a through hole which is used as an electrolyte common outlet flow passage B; the common inlet runners A in the battery pack are sequentially communicated, the common outlet runners A are sequentially communicated, the common inlet runners B are sequentially communicated, and the common outlet runners B are sequentially communicated; in 15 single cells, a common inlet flow channel A is connected with a negative electrolyte inlet flow channel on each negative electrode frame, the negative electrolyte inlet flow channel is connected with the middle through hole area of the negative electrode frame through a distribution flow channel, a common outlet flow channel A is connected with a negative electrolyte outlet flow channel on each negative electrode frame, and the negative electrolyte outlet flow channel is connected with the middle through hole area of the negative electrode frame through the distribution flow channel; in the other 15 monocells, the public inlet flow channel B is connected with the negative electrolyte inlet flow channel on each negative electrode frame, the negative electrolyte inlet flow channel is connected with the middle through hole area of the negative electrode frame through the distribution flow channel, the public outlet flow channel B is connected with the negative electrolyte outlet flow channel on each negative electrode frame, and the negative electrolyte outlet flow channel is connected with the middle through hole area of the negative electrode frame through the distribution flow channel. After the stack is assembled, the cathode electrolyte is divided into A, B two flow paths when the stack operates; flow path A: the cathode electrolyte flows into the common inlet flow channel A through the electrolyte inlet guide plate, flows into the cathode electrode frame through the cathode inlet A, flows out of the cathode electrode frame from the cathode outlet to the common outlet flow channel A, and flows out of the galvanic pile through the galvanic pile liquid outlet guide plate; flow path B: the cathode electrolyte flows into the public inlet flow channel B through the electrolyte inlet guide plate, flows into the cathode electrode frame through the cathode inlet, flows out of the cathode electrode frame from the cathode outlet to the public outlet flow channel B, and flows out of the pile through the pile liquid outlet guide plate. The cathode electrode frame is a flat plate with a middle part provided with a through hole, a cathode electrolyte inlet flow channel and a cathode electrolyte outlet flow channel are respectively arranged on two opposite sides of the through hole on the surface of one side of the flat plate, and an electrolyte inlet distribution flow channel communicated with the cathode electrolyte inlet flow channel and the middle through hole, an electrolyte outlet distribution flow channel communicated with the cathode electrolyte outlet flow channel and the middle through hole are respectively arranged on two opposite sides of the through hole. And after the 15 sections of the common inlet flow channels A are sequentially stacked with the single cells connected with the negative electrolyte inlet flow channels on each negative electrode frame, the other 15 sections of the common inlet flow channels B are sequentially stacked with the single cells connected with the negative electrolyte inlet flow channels on each negative electrode frame and are 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 the electrode stacks and the charging and discharging system are as follows:
electrode area: 1000cm2。
The number of the electric pile sections: 30 section
Current density: 40mA/cm2And charging time: 1 hour, discharge cut-off voltage: 24V
The coulombic efficiency of the charge and discharge of the galvanic pile is 91.6 percent, the voltage efficiency is 83.1 percent, and the energy efficiency is 76.1 percent
In the comparative example, 20 sections of the zinc-bromine single-flow galvanic pile are assembled by adopting a traditional electrode frame structure, the coulombic efficiency of the galvanic pile is 89.2 percent, and from the cycle performance curve of the galvanic pile, after the galvanic pile continuously runs for about 20 cycles, the performance of the galvanic pile is greatly attenuated, and the stability of the galvanic pile is poor.
In the embodiment 1, 20 sections of the zinc-bromine single-flow galvanic pile are assembled by adopting the improved electrode frame structure, the coulombic efficiency of the galvanic pile is 95.6 percent, 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 is adopted, so that the leakage current of the galvanic pile is reduced, and the capacity loss of the galvanic pile is reduced. And from the cycle performance curve of the electric pile, after the electric pile continuously runs for 140 cycles, the performance of the electric pile still does not attenuate, and can be kept above 95%, therefore, the stability of the electric pile is also greatly improved.
In the embodiment 2, 30 sections of the zinc-bromine single-flow galvanic pile are assembled by adopting the electrode frame structure provided by the invention, the coulombic efficiency of the galvanic pile is 91.5%, the performance of the galvanic pile is reduced compared with that of the embodiment 1 due to the increase of the number of the sections of the galvanic pile, but the performance of the galvanic pile is still higher than that of the comparative example, the maintenance rate of 140 continuous running cycling performances of the galvanic pile is good, and the stability of the galvanic pile can still be maintained.
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 cell 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; similarly, because the inlet of the electric pile is divided into A, B flow paths, the number of the battery sections distributed by each flow path is reduced, the flow rate of the electrolyte distributed to each electrode frame is more uniform, and the stability of the electric pile can be greatly improved.
Claims (4)
1. A zinc-bromine single-liquid galvanic pile comprises a battery pack formed by connecting m + n single cells in series, wherein m and n are integers more than or equal to 2 respectively, the single cells comprise a negative electrode frame, a diaphragm and a positive electrode frame which are sequentially stacked, and a negative carbon felt electrode and a positive carbon felt electrode are respectively placed 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 plate body is provided with a through hole which is vertical to the surface of the plate body and is used as an electrolyte common inlet flow passage A, a through hole which is used as an electrolyte common outlet flow passage A, a through hole which is used as an electrolyte common inlet flow passage B and a through hole which is used as an electrolyte common outlet flow passage B; the common inlet runners A in the battery pack are sequentially communicated, the common outlet runners A are sequentially communicated, the common inlet runners B are sequentially communicated, and the common outlet runners B are sequentially communicated;
in m single cells, a common inlet flow channel A is connected with a negative electrolyte inlet flow channel on each negative electrode frame, the negative electrolyte inlet flow channel is connected with the middle through hole area of the negative electrode frame through a distribution flow channel, a common outlet flow channel A is connected with a negative electrolyte outlet flow channel on each negative electrode frame, and the negative electrolyte outlet flow channel is connected with the middle through hole area of the negative electrode frame through the distribution flow channel;
in the n monocells, the public inlet flow channel B is connected with the negative electrolyte inlet flow channel on each negative electrode frame, the negative electrolyte inlet flow channel is connected with the middle through hole area of the negative electrode frame through the distribution flow channel, the public outlet flow channel B is connected with the negative electrolyte outlet flow channel on each negative electrode frame, and the negative electrolyte outlet flow channel is connected with the middle through hole area of the negative electrode frame through the distribution flow channel.
2. The zinc-bromine single flow cell stack of claim 1, wherein: after the stack is assembled, the cathode electrolyte is divided into A, B two flow paths when the stack operates; flow path a: the cathode electrolyte flows into the common inlet flow channel A through the electrolyte inlet guide plate, flows into the cathode electrode frame through the cathode inlet A, flows out of the cathode electrode frame from the cathode outlet to the common outlet flow channel A, and flows out of the galvanic pile through the galvanic pile liquid outlet guide plate; flow path B: the cathode electrolyte flows into the public inlet flow channel B through the electrolyte inlet guide plate, flows into the cathode electrode frame through the cathode inlet, flows out of the cathode electrode frame from the cathode outlet to the public outlet flow channel B, and flows out of the pile through the pile liquid outlet guide plate.
3. The zinc-bromine single flow cell stack of claim 1, wherein: the cathode electrode frame is a flat plate with a middle part provided with a through hole, a cathode electrolyte inlet flow channel and a cathode electrolyte outlet flow channel are respectively arranged on two opposite sides of the through hole on the surface of one side of the flat plate, and an electrolyte inlet distribution flow channel communicated with the cathode electrolyte inlet flow channel and the middle through hole, an electrolyte outlet distribution flow channel communicated with the cathode electrolyte outlet flow channel and the middle through hole are respectively arranged on two opposite sides of the through hole.
4. The zinc-bromine single flow cell stack of claim 1, wherein: m and n are integers of 2 or more; m single batteries are sequentially stacked and then sequentially connected with n single batteries 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 and connected in series to form the battery pack.
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| CN116979116A (en) * | 2023-09-22 | 2023-10-31 | 艾博特瑞能源科技(苏州)有限公司 | Flow battery pile and flow battery |
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| CN109786783A (en) * | 2019-01-26 | 2019-05-21 | 杭州德海艾科能源科技有限公司 | A kind of flow battery electrode frame of multi-cavity structure and its battery stack of composition |
| CN110048141A (en) * | 2019-04-22 | 2019-07-23 | 高岩 | A kind of electrode of liquid flow cell sheet frame runner and flow battery runner |
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| CN116979116A (en) * | 2023-09-22 | 2023-10-31 | 艾博特瑞能源科技(苏州)有限公司 | Flow battery pile and flow battery |
| CN116979116B (en) * | 2023-09-22 | 2024-01-09 | 艾博特瑞能源科技(苏州)有限公司 | Flow battery pile and flow battery |
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