CN107845826B - Zinc bromine single flow battery - Google Patents
Zinc bromine single flow battery Download PDFInfo
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- CN107845826B CN107845826B CN201610838983.5A CN201610838983A CN107845826B CN 107845826 B CN107845826 B CN 107845826B CN 201610838983 A CN201610838983 A CN 201610838983A CN 107845826 B CN107845826 B CN 107845826B
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8892—Impregnation or coating of the catalyst layer, e.g. by an ionomer
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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 a zinc bromine single flow battery, wherein the positive electrode of the battery is made of porous material or a cavity is arranged between the positive electrode and a diaphragm, and electrolyte is filled in a porous material hole of the positive electrode or in the cavity between the positive electrode and the diaphragm. When the battery is operated for the first time, electrolyte is poured into the positive electrode through a pipeline provided with a valve. The battery has the characteristics of high energy density, long cycle life, low cost, simple structure and simple manufacturing process.
Description
Technical Field
The invention relates to the technical field of single flow batteries, in particular to the field of zinc-bromine single flow batteries.
Background
The Zinc-bromine flow battery (Zinc-bromine redox flow battery, ZBB) is a low-cost, high-efficiency and environment-friendly flow energy storage battery, has the advantages of high energy density and current efficiency, simple and easy operation of the device, long service life, low cost and the like, and is mainly applied to the fields of renewable energy power generation such as power grid peak regulation, wind energy and solar energy, electric automobiles and the like.
The traditional zinc-bromine flow battery adopts a double-pump and double-pipeline design, and in the charge and discharge process, the circulating pump is used for driving electrolyte to circularly flow in the battery. When the battery does not work, electrolyte is pumped out from the battery cavity and stored in the liquid storage tank, so that the electrolyte circuit breaking is realized between the anode and the cathode in the battery, and the self-discharge caused by the direct chemical reaction of the bromine in the charged state of the anode to the cathode can be prevented. The circulating electrolyte can also prevent zinc dendrite from growing through the diaphragm to cause short circuit of the anode and the cathode during charging.
However, because the zinc-bromine flow battery needs electrolyte circulation systems such as a circulating pump, a liquid storage tank and the like, the energy efficiency of the zinc-bromine flow battery is reduced due to the influence of system loss, and on the other hand, the auxiliary equipment of the battery makes the structure of the zinc-bromine flow battery system complex, so that the zinc-bromine flow battery system is not beneficial to miniaturization, and the energy density of the battery is reduced.
For this reason, patent CN99245261.9 describes a zinc-bromine storage battery, which eliminates the electrolyte circulation systems such as the circulation pump and the liquid storage tank of the zinc-bromine flow battery, so that the battery structure is simple and compact, and the energy consumption of the system is reduced. However, because of the pump-free design on both sides, the actual energy density of the battery is low, and large-current charge and discharge cannot be performed. The patent introduces a zinc bromine single flow battery technology, which cancels a positive electrode circulation pipeline, and the positive electrode adopts a mode of mixing and pasting active substances, complexing agents and carbon materials, and has a complex structure. In addition, although the positive electrode adopts a method of coating active substances by using carbon felt, so that the positive electrode does not need to be filled with electrolyte, the content of the active substances in the positive electrode cavity is small, and the charging capacity of the battery is affected.
Disclosure of Invention
The invention aims at the problems and provides a zinc-bromine single flow battery structure, and an electrolyte circulation system is improved according to the structure.
In order to achieve the above purpose, the invention adopts the following technical scheme,
a zinc-bromine single-flow battery structure, which comprises a zinc-bromine battery, an electrolyte storage tank, a circulating pump, a negative electrode electrolyte input pipeline and a negative electrode electrolyte output pipeline,
the zinc-bromine battery comprises a positive electrode, a diaphragm and a negative electrode, wherein the electrolyte storage tank is connected with the negative electrode through a negative electrode electrolyte input pipeline and a negative electrode electrolyte output pipeline, and a circulating pump is arranged on the negative electrode electrolyte input pipeline;
the positive electrode is made of porous material or a cavity is arranged between the positive electrode and the diaphragm, and electrolyte is filled in the porous material hole of the positive electrode or the cavity between the positive electrode and the diaphragm.
A branch pipe used as an anode electrolyte input pipe is arranged on the anode electrolyte input pipe between the anode and the circulating pump, and the anode electrolyte input pipe is communicated with a porous material of the anode or a cavity between the anode and the diaphragm;
a branch pipe used as a positive electrode electrolyte output pipe is arranged on the negative electrode electrolyte output pipe, and the positive electrode electrolyte output pipe is communicated with a porous material of the positive electrode or a cavity between the positive electrode and the diaphragm;
valves are arranged on the positive electrolyte input pipeline and the positive electrolyte output pipeline.
The zinc-bromine battery is formed by connecting one or more than two single cells in series, wherein each single cell comprises a positive electrode current collector, a positive electrode, a diaphragm, a negative electrode and a negative electrode current collector which are sequentially overlapped between positive and negative electrode end plates;
when more than two single cells are connected in series, the battery comprises more than 2 groups of serially connected and sequentially overlapped positive current collectors, positive electrodes, diaphragms, negative electrodes and negative current collectors which are arranged between the positive end plate and the negative end plate.
The positive electrode side adopts a sealing structure, and a positive electrode electrolyte circulation system is not required to be configured independently;
when the battery is operated for the first time, electrolyte is infused into the positive electrode through the electrolyte conveying pipeline.
The battery electrolyte circulation system is provided with an anode electrolyte conveying pipeline, and valves are arranged at the anode electrolyte inlet and outlet in the electrolyte conveying pipeline to control the conveying of the electrolyte; when the device runs for the first time, valves on the output and input pipelines of the positive electrolyte are opened, and the valves are closed after the electrolyte is input into the positive electrode; when the battery is in charge and discharge operation, the electrolyte is only conveyed to the negative electrode for circulation.
And the anode and the cathode are made of carbon felt or graphite felt. The carbon felt is a porous material.
The electrolyte is zinc bromide acid solution, the concentration is 1 multiplied by 10M, and the pH value is 2-5..
The membrane is an ion exchange membrane or a microporous membrane.
The invention has the beneficial effects that:
1. the battery structure eliminates the paste coating step of the anode of the original zinc-bromine single flow battery, adopts a simple carbon felt or graphite felt as an electrode, ensures that the anode has larger space, stores more electrolyte and improves the charge capacity of the battery.
2. In order to solve the problem that the designed positive electrode does not carry electrolyte active substances, a positive electrode electrolyte infusion pipeline is designed in a circulation pipeline, and the positive electrode is filled with electrolyte before the battery is operated for the first time through the system. During the primary operation, electrolyte is poured into the positive electrode through a pipeline provided with a valve. When the battery is charged and discharged, the electrolyte is only conveyed to the negative electrode, free zinc ions are directly deposited in the form of zinc simple substance on the electrode, and bromine ions are oxidized into bromine simple substance in the positive electrode and then form a bromine complex with the complexing agent. During discharge, zinc simple substance is oxidized into zinc ions, the zinc ions are returned to the liquid storage tank through the pump, and the bromine complex is reduced into bromine ions. The battery has the characteristics of high energy density, long cycle life, low cost, simple structure and simple manufacturing process.
Drawings
FIG. 1 is a schematic diagram of a zinc-bromine single flow battery of the present invention;
wherein: 1. a positive electrode end plate; 2. a negative end plate; 3. a positive electrode current collector; 4. an electrode; 5. a diaphragm; 6. a negative electrode current collector; 7. a negative electrode electrolyte storage tank; 8. a circulation pump; 9. an anode electrolyte outlet valve; 10. an anode electrolyte outlet valve;
FIG. 2 is a schematic diagram of a conventional zinc-bromine single flow battery of comparative example 1;
1. a positive electrode end plate; 2. a negative end plate; 3. a positive electrode current collector; 4. an electrode; 5. a diaphragm; 6. a negative electrode current collector; 7. a negative electrode electrolyte storage tank; 8. a circulation pump;
FIG. 3 example 1 cycle performance plot, wherein CE-coulombic efficiency, VE-voltage efficiency, EE-energy efficiency;
FIG. 4 example 2 cycle performance chart;
FIG. 5 example 3 cycle performance chart;
FIG. 6 is a graph of cycle performance for the comparative example.
Detailed Description
Example 1
1) The positive electrode adopts one piece of carbon felt with the specification of 4x4x0.5cm, and the negative electrode adopts one piece of carbon felt with the specification of 4x4x0.5cm
2) 60ml of a 2mol/L zinc bromide solution was prepared for use.
And (3) battery assembly:
as shown in fig. 1, the unit cell sequentially includes a positive electrode end plate, a positive electrode current collector, a positive electrode (carbon felt), a PE porous membrane, a negative electrode current collector, and a negative electrode end plate.
A branch pipe used as an anode electrolyte infusion pipeline is arranged on a cathode electrolyte input pipeline between the cathode and the circulating pump, and the anode electrolyte infusion pipeline is communicated with a porous material of the anode or a cavity between the anode and the diaphragm;
a branch pipeline serving as a positive electrolyte pouring output pipeline is arranged on the negative electrolyte output pipeline, and the positive electrolyte pouring output pipeline is communicated with a porous material of the positive electrode or a cavity between the positive electrode and the diaphragm;
valves are arranged on the anode electrolyte infusion pipeline and the anode electrolyte infusion output pipeline.
The battery electrolyte circulation system is provided with an anode electrolyte conveying pipeline, and valves are arranged at the anode electrolyte inlet and outlet in the electrolyte conveying pipeline to control the conveying of the electrolyte; when the device runs for the first time, valves on the output and input pipelines of the positive electrolyte are opened, and the valves are closed after the electrolyte is input into the positive electrode; when the battery is in charge and discharge operation, the electrolyte is only conveyed to the negative electrode for circulation.
As can be seen from FIG. 3, the cell electrode area is 36cm 2 Charge-discharge current density: 40mA/cm 2 Charging time 1h, battery coulombic efficiency: 96%, voltage efficiency: 86%, energy efficiency: 83%.
Example 2
1) The anode adopts three carbon felts with the specification of 4x4x0.5cm, and the cathode adopts one carbon felt with the specification of 4x4x0.5cm
2) 60ml of a 2mol/L zinc bromide solution was prepared for use.
The battery was assembled and operated in the same manner as in example 1
The single cell sequentially comprises a positive electrode end plate, a positive electrode current collector, a positive electrode, a Nafion117 membrane, a negative electrode current collector and a negative electrode end plate.
As can be seen from FIG. 4, the cell electrode area is 36cm 2 Charge-discharge current density: 40mA/cm 2 Charging time 1.5h, coulombic efficiency of battery: 96%, voltage efficiency: 86%, energy efficiency: 81%.
Example 3
1) The anode adopts two carbon felts with the specification of 4x4x0.5cm, and the cathode adopts one carbon felt with the specification of 4x4x0.5cm
2) 60ml of a 2mol/L zinc bromide solution was prepared for use.
The battery was assembled and operated in the same manner as in example 1
The single cell sequentially comprises a positive electrode end plate, a positive electrode current collector, a positive electrode, a PP porous membrane, a negative electrode current collector and a negative electrode end plate.
As can be seen from FIG. 5, the cell electrode area is 36cm 2 Charge-discharge current density: 40mA/cm 2 Charging time 2h, battery coulombic efficiency: 94%, voltage efficiency: 86%, energy efficiency: 81%.
Comparative example 1
The assembly of a conventional zinc-bromine single flow battery is shown in fig. 2.
Preparation of positive and negative electrode paste:
1) Preparing polar paste slurry: according to the weight portions, 1 portion of carbon powder, 1 portion of trimethyl ammonium bromide, 10 portions of zinc bromide and 3 portions of deionized water are mechanically mixed and stirred into paste for standby;
2) Uniformly coating the polar paste slurry on one side surface of the carbon felt by adopting a doctor blade method; load: 20mg/cm 2 。
3) Preparing zinc bromide solution: preparing a zinc bromide solution with the concentration of 4mol/L, immersing the prepared anode and cathode in the solution for 20min, assembling the battery, and assembling the side coated with the electrode paste facing the diaphragm.
And (3) battery assembly:
the single cell sequentially comprises a positive electrode end plate, a positive electrode current collector, a positive electrode, a PE porous membrane, a negative electrode current collector and a negative electrode end plate.
As can be seen from FIG. 6, the cell electrode area is 36cm 2 Charge-discharge current density: 40mA/cm 2 Charging time is 1h,1.5h and 2h, and coulomb efficiency of the battery is respectively as follows: 96%,80%,60% voltage efficiencies are respectively: 83%,83%,83% energy efficiency is respectively: 80%,66% and 50%.
The battery structure of the invention eliminates the paste coating step of the prior zinc-bromine single flow battery anode, adopts a simple carbon felt or graphite felt as an electrode, ensures that the anode has larger space, stores more electrolyte and improves the charge capacity of the battery. The battery has the characteristics of high energy density, long cycle life, low cost, simple structure and simple manufacturing process.
Claims (7)
1. A zinc-bromine single-flow battery, which comprises a zinc-bromine battery, an electrolyte storage tank, a circulating pump, a negative electrode electrolyte input pipeline and a negative electrode electrolyte output pipeline,
the zinc-bromine battery comprises a positive electrode, a diaphragm and a negative electrode, wherein the electrolyte storage tank is connected with the negative electrode through a negative electrode electrolyte input pipeline and a negative electrode electrolyte output pipeline, and a circulating pump is arranged on the negative electrode electrolyte input pipeline; the method is characterized in that:
the positive electrode is made of porous material or a cavity is arranged between the positive electrode and the diaphragm, and electrolyte is filled in the porous material hole of the positive electrode or the cavity between the positive electrode and the diaphragm;
a branch pipe used as an anode electrolyte input pipe is arranged on the anode electrolyte input pipe between the anode and the circulating pump, and the anode electrolyte input pipe is communicated with a porous material of the anode or a cavity between the anode and the diaphragm;
a branch pipe used as a positive electrode electrolyte output pipe is arranged on the negative electrode electrolyte output pipe, and the positive electrode electrolyte output pipe is communicated with a porous material of the positive electrode or a cavity between the positive electrode and the diaphragm;
valves are arranged on the positive electrolyte input pipeline and the positive electrolyte output pipeline.
2. The zinc-bromine single flow battery of claim 1 wherein:
the zinc-bromine battery is formed by connecting one or more than two single cells in series, wherein each single cell comprises a positive electrode current collector, a positive electrode, a diaphragm, a negative electrode and a negative electrode current collector which are sequentially overlapped between positive and negative electrode end plates;
when more than two single cells are connected in series, the battery comprises more than 2 groups of serially connected and sequentially overlapped positive current collectors, positive electrodes, diaphragms, negative electrodes and negative current collectors which are arranged between the positive end plate and the negative end plate.
3. The zinc-bromine single flow battery of claim 1 wherein: the positive electrode side adopts a sealing structure, and a positive electrode electrolyte circulation system is not required to be configured independently.
4. The zinc-bromine single flow battery of claim 1 wherein: the battery electrolyte circulation system is provided with an anode electrolyte conveying pipeline, and valves are arranged at the anode electrolyte inlet and outlet in the electrolyte conveying pipeline to control the conveying of the electrolyte; when the device runs for the first time, valves on the output and input pipelines of the positive electrolyte are opened, and the valves are closed after the electrolyte is input into the positive electrode; when the battery is in charge and discharge operation, the electrolyte is only conveyed to the negative electrode for circulation.
5. The zinc-bromine single flow battery of claim 1 wherein the anode and the cathode are both carbon felt or graphite felt.
6. The zinc-bromine single flow battery of claim 1 wherein the electrolyte is an acidic solution of zinc bromide at a concentration of 1 x 10m and a ph of 2-5.
7. The zinc-bromine single flow battery of claim 1 wherein the separator is an ion exchange membrane or a microporous membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610838983.5A CN107845826B (en) | 2016-09-21 | 2016-09-21 | Zinc bromine single flow battery |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610838983.5A CN107845826B (en) | 2016-09-21 | 2016-09-21 | Zinc bromine single flow battery |
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| CN107845826A CN107845826A (en) | 2018-03-27 |
| CN107845826B true CN107845826B (en) | 2023-08-11 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112993359A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院大连化学物理研究所 | Zinc-nickel single flow battery |
| CN114497644B (en) * | 2020-11-12 | 2023-09-15 | 中国科学院大连化学物理研究所 | Zinc-based single flow battery operation method |
| CN114597455A (en) * | 2020-12-03 | 2022-06-07 | 中国科学院大连化学物理研究所 | Discharging operation method of zinc-bromine single flow battery and intermittent discharging zinc-bromine single flow battery |
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| JP2003100337A (en) * | 2001-09-25 | 2003-04-04 | Sumitomo Electric Ind Ltd | Intermittent circulation type redox flow cell |
| CN101299476A (en) * | 2008-06-16 | 2008-11-05 | 中南大学 | Zinc-nickel static single fluid flow battery |
| CN202153549U (en) * | 2011-06-27 | 2012-02-29 | 深圳市氢动力科技有限公司 | Zinc-bromine flow battery and battery pack |
| CN102479968A (en) * | 2010-11-29 | 2012-05-30 | 中国科学院大连化学物理研究所 | Zinc / polyhalide energy storage cell |
| CN102780018A (en) * | 2012-08-13 | 2012-11-14 | 北京百能汇通科技股份有限公司 | Integrated liquid storage pot and novel zinc-bromine redox flow battery |
| JP2013025964A (en) * | 2011-07-19 | 2013-02-04 | Sumitomo Electric Ind Ltd | Electrolyte circulation cell |
| CN103137986A (en) * | 2011-12-05 | 2013-06-05 | 张华民 | Zinc bromine single flow cell |
| JP2014127263A (en) * | 2012-12-25 | 2014-07-07 | Mitsubishi Motors Corp | Redox flow battery |
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2016
- 2016-09-21 CN CN201610838983.5A patent/CN107845826B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003100337A (en) * | 2001-09-25 | 2003-04-04 | Sumitomo Electric Ind Ltd | Intermittent circulation type redox flow cell |
| CN101299476A (en) * | 2008-06-16 | 2008-11-05 | 中南大学 | Zinc-nickel static single fluid flow battery |
| CN102479968A (en) * | 2010-11-29 | 2012-05-30 | 中国科学院大连化学物理研究所 | Zinc / polyhalide energy storage cell |
| CN202153549U (en) * | 2011-06-27 | 2012-02-29 | 深圳市氢动力科技有限公司 | Zinc-bromine flow battery and battery pack |
| JP2013025964A (en) * | 2011-07-19 | 2013-02-04 | Sumitomo Electric Ind Ltd | Electrolyte circulation cell |
| CN103137986A (en) * | 2011-12-05 | 2013-06-05 | 张华民 | Zinc bromine single flow cell |
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| JP2014127263A (en) * | 2012-12-25 | 2014-07-07 | Mitsubishi Motors Corp | Redox flow battery |
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