CN108448187B - Charging and discharging method for lead methane sulfonate liquid flow single battery - Google Patents
Charging and discharging method for lead methane sulfonate liquid flow single battery Download PDFInfo
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- CN108448187B CN108448187B CN201810141279.3A CN201810141279A CN108448187B CN 108448187 B CN108448187 B CN 108448187B CN 201810141279 A CN201810141279 A CN 201810141279A CN 108448187 B CN108448187 B CN 108448187B
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
- H01M10/446—Initial charging measures
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
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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
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- 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
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a charge and discharge method of a lead methanesulfonate flow monomer battery, which comprises the following steps: (1) measuring and calculating the oxygen evolution voltage V0 of the single battery system; (2) pre-charging at constant voltage; (3) charging at constant current; (4) constant voltage current-limiting charging; (5) discharging at constant current; (6) a small current density discharge. The invention solves the problem of accumulation of positive and negative electrode sediments caused by over-high first-time charging voltage and discharging under rated current density in the constant-current charging and discharging process, and improves the charging and discharging efficiency and the service life of the lead methane sulfonate flow battery.
Description
Technical Field
The invention relates to the technical field of flow batteries, in particular to a charge and discharge method of a lead methane sulfonate flow single battery.
Background
Due to the unstable and discontinuous characteristics of new energy power generation such as wind energy, solar energy and the like, the bottleneck for restricting the healthy and rapid development of the new energy power generation system is that an energy storage device with low cost and long service life is not matched with the new energy power generation system. The lead methane sulfonate flow battery is a new power station type energy storage battery in recent years, is suitable for a kW-MW grade new energy storage power station, and is concerned about due to the fact that a single electrolyte is adopted, a proton exchange membrane is not used, and the battery has the advantages of being low in cost, simple in structure, high in conversion efficiency and the like.
The principle of the lead methane sulfonate flow battery is that soluble lead methane sulfonate solution is adopted as electrolyte, and PbO is respectively formed on the surfaces of a positive electrode and a negative electrode through electrodeposition during charging2Pb, PbO of positive and negative electrodes during discharge2Dissolve with Pb to Pb2+Into solution. It can be seen that the essence of the charging process is Pb2+The electrodeposition process in acidic aqueous solution, and the oxygen evolution potential of the anode is only slightly higher than that of PbO2The deposition potential of (1). Therefore, only a proper deposition potential can reduce the occurrence of oxygen evolution side reactions, and the essence of the discharge is PbO2The Pb is dissolved into solution at the required current density (i.e., dissolution rate) to form Pb2+Thus, the slower the dissolution rate, the more favorable the dissolution reaction proceeds sufficiently.
Currently, a common charge and discharge method for a lead methanesulfonate flow battery is constant current charge-constant current discharge, as shown in fig. 1, in the figure, a vertical axis V represents voltage, a vertical axis J represents current density, a horizontal axis t represents time, S1 represents a charge time period, S2 represents a discharge time period, V1 represents a charge voltage, V2 represents a discharge voltage, and J represents a charge and discharge current density. The principle of constant current charging is a method for keeping the current intensity unchanged by changing the output voltage of a charging device, and the applicant finds that the charging voltage is higher than the charging voltage of a subsequent cycle due to the large driving force required by the first charging process, particularly when charging is carried out under a large current density, the high voltage of the first charging easily causes the occurrence of oxygen evolution reaction to cause the loss of the battery capacity, and the oxygen evolution reaction is also caused by the increase of the charging voltage along with the progress of the charging process. In addition, during discharge, the rated discharge current density may result in some degree of incomplete discharge.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art, provide a three-stage charging method and a two-stage discharging method for a lead methylsulfonate flow single battery, solve the problem of accumulation of positive and negative electrode sediments caused by over-high first charging voltage and discharging under rated current density in the constant current charging and discharging process, improve the charging and discharging efficiency of the lead methylsulfonate flow battery and prolong the service life of the lead methylsulfonate flow battery.
In order to solve the technical problems, the invention adopts the following technical scheme:
a charge and discharge method of a lead methane sulfonate liquid flow single battery comprises the following steps:
(1) measuring the oxygen evolution potential of the lead methanesulfonate flow monomer battery system, and converting to obtain the oxygen evolution voltage V0 in the charging process of the flow monomer battery;
(2) constant-voltage pre-charging: charging with a first preset voltage V1 until the charging current density reaches a first preset current density J2, wherein 1.95V<V1<V0, the first predetermined current density J2 is 10-30 mA/cm2；
(3) Constant current charging, namely performing constant current charging at a first preset current density J2 until the charging voltage reaches a second preset voltage V3, wherein V3 is 1.95+0.005 × J2;
(4) constant voltage current limiting charging: performing constant-voltage charging at a second preset voltage V3 until the charging capacity reaches the capacity threshold of the single battery;
(5) constant current discharging: discharging to the discharge cut-off voltage of the single flow battery at a first preset current density;
(6) low current density discharge: and discharging to the discharge cut-off voltage of the flow single battery at a second preset current density J5, wherein J5 < J2.
Preferably, the second preset current density J5 is 1-5 mA/cm2。
Preferably, the discharge cut-off voltage is 1.1V.
Compared with the prior art, the invention has the advantages that:
the invention adopts a constant voltage pre-charging-constant current charging-constant voltage current limiting three-stage charging method and a rated current density-low current density two-stage discharging method, and particularly adds a constant voltage charging stage before constant current charging to prevent capacity loss caused by overhigh first charging voltage, and adopts constant voltage current limiting charging in the later stage of constant current charging. The constant voltage charging voltage in the constant voltage charging stage is lower than the oxygen evolution voltage in the methanesulfonic acid system, and the side reaction in the initial charging stage and the energy loss caused by the side reaction are effectively reduced. Constant current charging is carried out under the rated current density, and constant voltage current-limiting charging is carried out after the constant current charging is carried out to a certain voltage. In addition, after the battery discharges under the rated current density, a small-current-density discharging stage is added, so that the sufficient dissolution of the residual deposits of the positive electrode and the negative electrode can be effectively promoted, the charge-discharge efficiency of the lead methane sulfonate flow battery is improved, and the service life of the lead methane sulfonate flow battery is prolonged.
Drawings
Fig. 1 is a schematic charge-discharge diagram of a lead methane sulfonate flow single cell battery in the prior art.
Fig. 2 is a schematic charge-discharge diagram of the lead methanesulfonate flow battery of the present invention.
Detailed Description
The invention is further described below with reference to specific preferred embodiments, without thereby limiting the scope of protection of the invention.
Example 1:
A4.5W/9 Wh lead methane sulfonate flow battery monomer comprises a battery, electrolyte and a circulating system, wherein the positive electrode and the negative electrode of the battery are made of self-made carbon polymer conductive plates, and the effective area is 10 x 10cm2The electrolyte composition was 1.0M Pb (CH)2SO3)2+1.0M CH2SO3H, the oxygen evolution voltage of the battery under the system is about 2.14V as measured by linear voltammetry scanning (L SV), and as shown in figure 2, the curve of the whole charging and discharging process is schematic, and the charging and discharging process is divided into five stages:
the first stage is a constant voltage pre-charging stage, when the lead methane sulfonate flow battery is charged, constant voltage charging is carried out at a first preset voltage of 2.05V, at the moment, the charging current of the lead methane sulfonate flow battery is gradually increased, and when the charging time reaches S1, the charging current density reaches a first preset current density of 30mA/cm2I.e. 3A (30 mA/cm)2*10*10cm2) At this time, the next stage of charging is performed.
The second stage is a constant current charging stage, and the first preset maximum current density is 30mA/cm2That is, charging is performed, in which the charging voltage of the battery is lower than 2.1V, the charging voltage of the battery gradually increases as the constant current charging is performed, and when the charging voltage of the battery reaches 1.95+0.005 × 30 (i.e., 2.1V), the charging time reaches S2, and the next charging stage is performed.
The third stage is a constant voltage current-limiting charging stage, the highest charging voltage 2.1V of the second stage is used as constant voltage charging, the charging current of the battery gradually decreases, when the capacity of the battery reaches a rated threshold (6Ah), the charging time reaches S3, the charging is completed, and the discharging stage is entered.
The fourth stage is a rated current density discharge stage, and the first preset current density is 30mA/cm2The discharge is performed, the battery voltage gradually decreases as the discharge proceeds, and when the voltage is low to the discharge cutoff voltage of 1.1V, the discharge time reaches S4, and the next stage is performed.
The fifth stage is a low current density discharge stage with a second preset current density of 2mA/cm2When the discharge voltage was reduced to 1.1V, the discharge time reached S5, and the discharge was terminated.
Example 2:
A3W/12 Wh lead methane sulfonate flow battery monomer comprises a battery, electrolyte and a circulating system, wherein the positive electrode and the negative electrode of the battery are both conductive by adopting self-made carbon polymersPlate with effective area of 10 × 10cm2The electrolyte composition was 1.0M Pb (CH)2SO3)2+1.0M CH2SO3H, the oxygen evolution voltage of the battery under the system is about 2.08V measured by L SV, as shown in figure 2, a curve diagram of the whole charge-discharge process is shown, and the charge-discharge process is divided into five stages:
the first stage is a constant voltage pre-charging stage, when the lead methane sulfonate flow battery is charged, constant voltage charging is carried out at a first preset voltage of 2.05V, at the moment, the charging current of the lead methane sulfonate flow battery is gradually increased, and when the charging time reaches S1, the charging current density reaches a first preset current density of 20mA/cm2I.e. 2A (20 mA/cm)2*10*10cm2) At this time, the next stage of charging is performed.
The second stage is a constant current charging stage with a first preset maximum current density of 20mA/cm2That is, charging is performed, in which the charging voltage of the battery is lower than 2.1V, and the charging voltage of the battery gradually increases as the constant current charging is performed, and when the charging voltage of the battery reaches 1.95+0.005 × 20 (i.e., 2.05V), the charging time reaches S2, and the next charging stage is performed.
The third stage is a constant voltage current-limiting charging stage, the highest charging voltage of 2.05V in the second stage is used as constant voltage charging, the charging current of the battery gradually decreases, when the capacity of the battery reaches a rated threshold (8Ah), the charging time reaches S3, the charging is completed, and the discharging stage is entered.
The fourth stage is a rated current density discharge stage, and the first preset current density is 20mA/cm2The discharge is performed, the battery voltage gradually decreases as the discharge proceeds, and when the voltage is low to the discharge cutoff voltage of 1.1V, the discharge time reaches S4, and the next stage is performed.
The fifth stage is a low current density discharge stage with a second preset current density of 2mA/cm2When the discharge voltage was reduced to 1.1V, the discharge time reached S5, and the discharge was terminated.
The above description is only for the preferred embodiment of the present application and should not be taken as limiting the present application in any way, and although the present application has been disclosed in the preferred embodiment, it is not intended to limit the present application, and those skilled in the art should understand that they can make various changes and modifications within the technical scope of the present application without departing from the scope of the present application, and therefore all the changes and modifications can be made within the technical scope of the present application.
Claims (3)
1. A charge and discharge method of a lead methane sulfonate liquid flow single battery comprises the following steps:
(1) measuring the oxygen evolution potential of the lead methanesulfonate flow monomer battery system, and converting to obtain the oxygen evolution voltage V0 in the charging process of the flow monomer battery;
(2) constant-voltage pre-charging: charging with a first preset voltage V1 until the charging current density reaches a first preset current density J2, wherein 1.95V<V1<V0, the first predetermined current density J2 is 10-30 mA/cm2；
(3) Constant current charging, namely performing constant current charging at a first preset current density J2 until the charging voltage reaches a second preset voltage V3, wherein V3 is 1.95+0.005 × J2;
(4) constant voltage current limiting charging: performing constant-voltage charging at a second preset voltage V3 until the charging capacity reaches the capacity threshold of the single battery;
(5) constant current discharging: discharging to the discharge cut-off voltage of the single flow battery at a first preset current density;
(6) low current density discharge: and discharging to the discharge cut-off voltage of the flow single battery at a second preset current density J5, wherein J5 < J2.
2. The method for charging and discharging the lead methanesulfonate flow monomer battery of claim 1, wherein the second predetermined current density J5 is 1-5 mA/cm2。
3. The method for charging and discharging a lead methanesulfonate flow cell according to claim 1 or 2, characterized in that the discharge cut-off voltage is 1.1V.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN202121013U (en) * | 2011-05-13 | 2012-01-18 | 安徽硕日光电科技有限公司 | Intelligent on-line monitoring management system of large capacity vanadium ion redox flow battery |
| CN103036286A (en) * | 2012-12-07 | 2013-04-10 | 重庆大学 | Safe charge-discharge control method of all-vanadium redox flow battery comprising direct current / direct current (DC / DC) converter |
| CN103259059A (en) * | 2013-04-17 | 2013-08-21 | 大连尚能科技发展有限公司 | Initial charging method of flow battery and circuit |
| WO2014189503A2 (en) * | 2013-05-22 | 2014-11-27 | United Technologies Corporation | In-situ electrolyte preparation in flow battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20130177789A1 (en) * | 2010-08-13 | 2013-07-11 | Squirrel Holdings Ltd | Redox flow battery system employing different charge and discharge cells |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN202121013U (en) * | 2011-05-13 | 2012-01-18 | 安徽硕日光电科技有限公司 | Intelligent on-line monitoring management system of large capacity vanadium ion redox flow battery |
| CN103036286A (en) * | 2012-12-07 | 2013-04-10 | 重庆大学 | Safe charge-discharge control method of all-vanadium redox flow battery comprising direct current / direct current (DC / DC) converter |
| CN103259059A (en) * | 2013-04-17 | 2013-08-21 | 大连尚能科技发展有限公司 | Initial charging method of flow battery and circuit |
| WO2014189503A2 (en) * | 2013-05-22 | 2014-11-27 | United Technologies Corporation | In-situ electrolyte preparation in flow battery |
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