CN111244519B - Reducible regenerative electrolyte suitable for single flow battery and preparation method thereof - Google Patents

Reducible regenerative electrolyte suitable for single flow battery and preparation method thereof Download PDF

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CN111244519B
CN111244519B CN202010071203.5A CN202010071203A CN111244519B CN 111244519 B CN111244519 B CN 111244519B CN 202010071203 A CN202010071203 A CN 202010071203A CN 111244519 B CN111244519 B CN 111244519B
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electrolyte
flow battery
single flow
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trifluoromethanesulfonate
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CN111244519A (en
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刘政
罗小飞
计东东
蒋百铃
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Xian University of Technology
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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
    • 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 discloses reducible regenerative electrolyte suitable for a single flow battery and a preparation method thereof, wherein the reducible regenerative electrolyte of the single flow battery is a mixed solution of lead trifluoromethanesulfonate, trifluoromethanesulfonic acid and a proper amount of additive, wherein the concentration of the lead trifluoromethanesulfonate is 2-3mol/L, and the concentration of the trifluoromethanesulfonic acid is 0-1mol/L. The electrolyte can be used for making a single flow battery in hydrogen peroxide (H) 2 O 2 ) No PbSO is generated in the reduction regeneration process 4 The generation and efficiency recovery is as new, the coulombic efficiency is basically over 90 percent, and the energy efficiency is over 70 percent.

Description

Reducible and renewable electrolyte suitable for single flow battery and preparation method thereof
Technical Field
The invention belongs to the technical field of single flow batteries, relates to a reducible and renewable electrolyte of a single flow battery, and also relates to a preparation method of the reducible and renewable electrolyte of the single flow battery.
Background
The single flow battery mainly adopts single electrolyte, and the electrolyte in the liquid storage tank is continuously conveyed to electrode reaction sites, namely the surfaces of the positive electrode and the negative electrode, through a circulating pump. Wherein the active substance is deposited on the electrode surface in the form of solid without expensive proton exchange membrane, thus the structure is simple. The explosion-proof device has the characteristics of low cost of raw materials and production, reliable operation, no explosion even if short circuit occurs when the explosion-proof device fails, convenient maintenance, long service life and the like. At present, the electrolyte of the single flow battery mainly comprises a soluble lead methylsulfonate solution. Soluble Pb during charging 2+ Respectively generate oxidation and reduction reactions on the positive electrode and the negative electrode to generate conductive PbO 2 Depositing on the surface of electrode together with Pb, and oxidizing and reducing the positive and negative deposits to generate Pb 2+ And dissolved in the electrolyte, thereby realizing the charge and discharge cycle use. However, when the single flow battery fails in a circulating way, if the positive electrode and the negative electrode are short-circuited, the efficiency of the battery is reduced to 0%. At this time, the surfaces of the positive electrode and the negative electrodePbO on 2 And Pb can be reductively regenerated using hydrogen peroxide, the reaction mechanism is as follows:
and (3) positive electrode: pbO 2 +H 2 O 2 +2H + →Pb 2+ +2H 2 O+O 2
Negative electrode: pb + H 2 O 2 +2H + →Pb 2+ +2H 2 O
But during regeneration, pbO is especially on the positive electrode side 2 And H 2 O 2 The reaction is vigorous, a large amount of heat is generated, and anionic methylsulfonate (CH) adsorbed on the surface of the electrode is generated 3 SO 3 -) C-S bond is broken to produce sulfate SO 4 2- With Pb 2+ The reaction generates insoluble PbSO 4 A large amount of PbSO deposited or released from the electrode surface without contacting the electrode during charging 4 Can not be oxidized to generate PbO 2 And the reduction regeneration rate is low. Thus, the concentration of lead ions in the electrolyte is reduced, which leads to serious problems of reduced efficiency, shortened service life and the like when the electrolyte is restarted.
Under such circumstances, it is necessary to develop an electrolyte and a corresponding preparation method, which are suitable for a single flow battery and can be regenerated by hydrogen peroxide reduction, so as to improve the cycle performance of the flow battery.
Disclosure of Invention
The first purpose of the invention is to provide a reducible and renewable electrolyte of a single flow battery, which solves the problem of low reduction and regeneration rate of the electrolyte of the single flow battery in the prior art.
Another object of the present invention is to provide a method for preparing a reducible and renewable electrolyte of a single flow battery, which also solves the problem of low reducible and renewable rate of the single flow battery in the prior art.
The first technical scheme adopted by the invention is that the reducible and renewable electrolyte of the single flow battery comprises the following components: lead trifluoromethanesulfonate, trifluoromethanesulfonic acid, deionized water and additives.
The invention adopts another technical scheme that a preparation method of reducible and renewable electrolyte of a single flow battery is implemented according to the following steps:
step 1, preparing a new electrolyte containing lead trifluoromethanesulfonate and trifluoromethanesulfonic acid;
and 2, adding an additive into the new electrolyte obtained in the step 1, and performing constant volume to obtain the electrolyte with stable performance of the single flow battery.
The invention is also characterized in that:
the concentration of the lead trifluoromethanesulfonate in the electrolyte which can be reduced and regenerated by the single flow battery is 2-3mol/L, and the concentration of the trifluoromethanesulfonic acid is 0-1mol/L.
The additive consists of sodium fluoride and stannous oxide, wherein the molar ratio of the sodium fluoride to the stannous oxide is 10:1, the concentration of sodium fluoride in electrolyte which can be reduced and regenerated by the single flow battery is 0.01-0.1mol/L, and the concentration of stannous oxide is 0.001-0.01mol/L.
The step 1 is implemented according to the following steps:
step 1.1, dissolving lead trifluoromethanesulfonate in deionized water, and stirring until the solution is clear to obtain an electrolyte;
and step 1.2, adding trifluoromethanesulfonic acid into the electrolyte obtained in step 1.1, stirring for 5-10 minutes, and clarifying the solution to obtain a new electrolyte.
In the step 1.2, the concentration of the lead trifluoromethanesulfonate in the new electrolyte is 2-3mol/L, and the concentration of the trifluoromethanesulfonic acid is 0-1mol/L.
In the step 1, the additive consists of sodium fluoride and stannous oxide, and the molar ratio of the sodium fluoride to the stannous oxide is 10:1, the concentration of sodium fluoride in electrolyte which can be reduced and regenerated by the single flow battery is 0.01-0.1mol/L, and the concentration of stannous oxide is 0.001-0.01mol/L.
The invention has the beneficial effects that:
1. the invention adopts the lead trifluoromethanesulfonate/trifluoromethanesulfonic acid as the electrolyte, has stable performance and does not generate a side reaction PbSO 4.
2. The fluorine methyl sulfonate can not generate carbon-sulfur bond fracture under the action of strong electronegative F element, effectively improves the regenerability of the electrolyte, and is environment-friendly.
3. The additive can improve the conductivity and the oxidizability of the positive electrode deposit lead dioxide, and can effectively inhibit the generation of dendritic lead for a negative electrode.
Drawings
Fig. 1 is a graph of the change of voltage (current) with charge and discharge time before and after short-circuit failure regeneration in example 1 of an electrolyte for regenerative reduction of a single flow battery of the present invention;
fig. 2 is a comparative example of coulombic efficiency and energy efficiency before and after regeneration of short circuit failure in example 1 of the electrolyte for regenerative reduction of a single flow battery according to the present invention.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
Example 1
The invention relates to a preparation method of electrolyte for regenerative reduction of a single flow battery, which is implemented according to the following steps:
the first technical scheme adopted by the invention is that the reducible and renewable electrolyte of the single flow battery comprises the following components: lead trifluoromethanesulfonate, trifluoromethanesulfonic acid, deionized water and additives.
The concentration of the lead trifluoromethanesulfonate in the electrolyte which can be reduced and regenerated by the single flow battery is 2mol/L, and the concentration of the trifluoromethanesulfonic acid is 0mol/L.
The additive consists of sodium fluoride and stannous oxide, wherein the molar ratio of the sodium fluoride to the stannous oxide is 10:1, the concentration of sodium fluoride in electrolyte which can be reduced and regenerated by the single flow battery is 0.01mol/L, and the concentration of stannous oxide is 0.001mol/L.
The invention adopts another technical scheme that a preparation method of reducible and renewable electrolyte of a single flow battery is implemented according to the following steps:
step 1, preparing a new electrolyte containing lead trifluoromethanesulfonate and trifluoromethanesulfonic acid;
and 2, adding an additive into the new electrolyte obtained in the step 1, and performing constant volume to obtain 0.1L of electrolyte with stable performance of the single flow battery.
The step 1 is implemented according to the following steps:
step 1.1, dissolving lead trifluoromethanesulfonate in deionized water, and stirring until the solution is clear to obtain an electrolyte;
and step 1.2, adding trifluoromethanesulfonic acid into the electrolyte obtained in step 1.1, stirring for 5 minutes, and clarifying the solution to obtain a new electrolyte.
In the step 1.2, the concentration of the lead trifluoromethanesulfonate in the new electrolyte is 2mol/L, and the concentration of the trifluoromethanesulfonic acid is 0mol/L.
In the step 1, the additive consists of sodium fluoride and stannous oxide, and the molar ratio of the sodium fluoride to the stannous oxide is 10:1, the concentration of sodium fluoride in electrolyte which can be reduced and regenerated by the single flow battery is 0.1mol/L, and the concentration of stannous oxide is 0.01mol/L.
According to the preparation method of the electrolyte capable of being regenerated and reduced by the single flow battery, all the used chemicals are analytically pure.
Carrying out charge and discharge tests on the single flow battery applying the renewable reduction electrolyte at room temperature, wherein the test temperature is 20 ℃, and the parameters of the charge and discharge tests are set as follows: the charge-discharge current density is 30mA/cm 2 The charging time is 2h, the discharge cut-off voltage is 1.1V, and the linear flow velocity of the electrolyte in the battery is 0.5cm/s.
And (3) testing results: the coulombic efficiency of the battery before short circuit failure is 94-97%, the energy efficiency is 80-83%, the short circuit failure occurs after 480 times of circulation, the coulombic efficiency after hydrogen peroxide reduction regeneration is 94-97%, the energy efficiency is 80-83%, and no PbSO exists in the regeneration process 4 And (4) generating. The curve of the voltage (current) before and after the regeneration of the short circuit failure along with the charging and discharging time is shown in fig. 1, and the coulombic efficiency and the energy efficiency before and after the regeneration of the short circuit failure are correspondingly compared, as shown in fig. 2.
Example 2
The invention relates to a preparation method of electrolyte for regenerative reduction of a single flow battery, which is implemented according to the following steps:
the first technical scheme adopted by the invention is that the reducible and renewable electrolyte of the single flow battery comprises the following components: lead trifluoromethanesulfonate, trifluoromethanesulfonic acid, deionized water and additives.
The concentration of the lead trifluoromethanesulfonate in the electrolyte which can be reduced and regenerated by the single flow battery is 2.5mol/L, and the concentration of the trifluoromethanesulfonic acid is 0.5mol/L.
The additive consists of sodium fluoride and stannous oxide, wherein the molar ratio of the sodium fluoride to the stannous oxide is 10:1, the concentration of sodium fluoride in electrolyte which can be reduced and regenerated by the single flow battery is 0.05mol/L, and the concentration of stannous oxide is 0.005mol/L.
The invention adopts another technical scheme that a preparation method of reducible and renewable electrolyte of a single flow battery is implemented according to the following steps:
step 1, preparing a new electrolyte containing lead trifluoromethanesulfonate and trifluoromethanesulfonic acid;
and 2, adding an additive into the new electrolyte obtained in the step 1, and performing constant volume to obtain 0.1L of electrolyte with stable performance of the single flow battery.
The step 1 is implemented according to the following steps:
step 1.1, dissolving lead trifluoromethanesulfonate in deionized water, and stirring until the solution is clear to obtain an electrolyte;
and step 1.2, adding trifluoromethanesulfonic acid into the electrolyte obtained in step 1.1, stirring for 10 minutes, and clarifying the solution to obtain a new electrolyte.
In the step 1.2, the concentration of the lead trifluoromethanesulfonate in the new electrolyte is 2mol/L, and the concentration of the trifluoromethanesulfonic acid is 0.1mol/L.
In the step 1, the additive consists of sodium fluoride and stannous oxide, and the molar ratio of the sodium fluoride to the stannous oxide is 10:1, the concentration of sodium fluoride in electrolyte which can be reduced and regenerated by the single flow battery is 0.05mol/L, and the concentration of stannous oxide is 0.005mol/L.
According to the preparation method of the electrolyte capable of being regenerated and reduced by the single flow battery, all the used chemicals are analytically pure.
The single flow battery using the renewable reduction electrolyte is subjected to charge and discharge tests at room temperature, wherein the test temperature is 20 DEG CSetting parameters of charge and discharge tests: the charge-discharge current density is 20mA/cm 2 The charging time is 4h, the discharge cut-off voltage is 1.1V, and the linear flow velocity of the electrolyte in the battery is 0.5cm/s.
And (3) testing results: the coulomb efficiency of the battery is 93-95%, and the energy efficiency is 78-80%. Short circuit failure occurs after 530 times of circulation, the coulombic efficiency after hydrogen peroxide reduction regeneration is 93-95%, the energy efficiency is 78-80%, and no PbSO is generated in the regeneration process 4 And (4) generating.
Example 3
The first technical scheme adopted by the invention is that the reducible and renewable electrolyte of the single flow battery comprises the following components: lead trifluoromethanesulfonate, trifluoromethanesulfonic acid, deionized water and an additive.
The concentration of the lead trifluoromethanesulfonate in the electrolyte which can be reduced and regenerated by the single flow battery is 2.2mol/L, and the concentration of the trifluoromethanesulfonic acid is 0.7mol/L.
The additive consists of sodium fluoride and stannous oxide, wherein the molar ratio of the sodium fluoride to the stannous oxide is 10:1, the concentration of sodium fluoride in electrolyte which can be reduced and regenerated by the single flow battery is 0.03mol/L, and the concentration of stannous oxide is 0.003mol/L.
The invention adopts another technical scheme that a preparation method of reducible and renewable electrolyte of a single flow battery is implemented according to the following steps:
step 1, preparing a new electrolyte containing lead trifluoromethanesulfonate and trifluoromethanesulfonic acid;
and 2, adding an additive into the new electrolyte obtained in the step 1, and performing constant volume to obtain 0.1L of electrolyte with stable performance of the single flow battery.
The step 1 is implemented according to the following steps:
step 1.1, dissolving lead trifluoromethanesulfonate in deionized water, and stirring until the solution is clear to obtain an electrolyte;
and step 1.2, adding trifluoromethanesulfonic acid into the electrolyte obtained in step 1.1, stirring for 8 minutes, and clarifying the solution to obtain a new electrolyte.
In the step 1.2, the concentration of the lead trifluoromethanesulfonate in the new electrolyte is 2.2mol/L, and the concentration of the trifluoromethanesulfonic acid is 0.7mol/L.
In the step 1, the additive consists of sodium fluoride and stannous oxide, and the molar ratio of the sodium fluoride to the stannous oxide is 10:1, the concentration of sodium fluoride in electrolyte which can be reduced and regenerated by the single flow battery is 0.03mol/L, and the concentration of stannous oxide is 0.003mol/L.
According to the preparation method of the electrolyte for the renewable reduction of the single flow battery, all the used chemicals are analytically pure.
Example 4
The first technical scheme adopted by the invention is that the reducible and renewable electrolyte of the single flow battery comprises the following components: lead trifluoromethanesulfonate, trifluoromethanesulfonic acid, deionized water and an additive.
The concentration of the lead trifluoromethanesulfonate in the electrolyte capable of being reduced and regenerated by the single flow battery is 2.7mol/L, and the concentration of the trifluoromethanesulfonic acid is 0.4mol/L.
The additive consists of sodium fluoride and stannous oxide, wherein the molar ratio of the sodium fluoride to the stannous oxide is 10:1, the concentration of sodium fluoride in electrolyte which can be reduced and regenerated by the single flow battery is 0.07mol/L, and the concentration of stannous oxide is 0.007mol/L.
The invention adopts another technical scheme that a preparation method of reducible and renewable electrolyte of a single flow battery is implemented according to the following steps:
step 1, preparing a new electrolyte containing lead trifluoromethanesulfonate and trifluoromethanesulfonic acid;
and 2, adding an additive into the new electrolyte obtained in the step 1, and performing constant volume to obtain 0.1L of electrolyte with stable performance of the single flow battery.
The step 1 is implemented according to the following steps:
step 1.1, dissolving lead trifluoromethanesulfonate in deionized water, and stirring until the solution is clear to obtain an electrolyte;
and step 1.2, adding trifluoromethanesulfonic acid into the electrolyte obtained in step 1.1, stirring for 6 minutes, and clarifying the solution to obtain a new electrolyte.
In the step 1.2, the concentration of the lead trifluoromethanesulfonate in the new electrolyte is 2.7mol/L, and the concentration of the trifluoromethanesulfonic acid is 0.4mol/L.
In the step 1, the additive consists of sodium fluoride and stannous oxide, and the molar ratio of the sodium fluoride to the stannous oxide is 10:1, the concentration of sodium fluoride in electrolyte which can be reduced and regenerated by the single flow battery is 0.07mol/L, and the concentration of stannous oxide is 0.007mol/L.
According to the preparation method of the electrolyte for the renewable reduction of the single flow battery, all the used chemicals are analytically pure.
Carrying out charge and discharge tests on the single flow battery using the reducible and renewable electrolyte at room temperature, wherein the test temperature is 20 ℃, and the parameters of the charge and discharge tests are set as follows: the charge-discharge current density is 15mA/cm 2 The charging time is 6h, the discharge cut-off voltage is 1.1V, and the linear flow velocity of the electrolyte in the battery is 0.5cm/s.
And (3) testing results: the coulombic efficiency of the battery is more than 92-93%, the energy efficiency is 76-83%, short circuit failure occurs after 522 times of circulation, the coulombic efficiency after hydrogen peroxide reduction regeneration is 92-93%, the energy efficiency is 76-83%, and no PbSO exists in the regeneration process 4 And (4) generating.
Example 5
The first technical scheme adopted by the invention is that the reducible and renewable electrolyte of the single flow battery comprises the following components: lead trifluoromethanesulfonate, trifluoromethanesulfonic acid, deionized water and an additive.
The concentration of the lead trifluoromethanesulfonate in the electrolyte which can be reduced and regenerated by the single flow battery is 3mol/L, and the concentration of the trifluoromethanesulfonic acid is 1mol/L.
The additive consists of sodium fluoride and stannous oxide, wherein the molar ratio of the sodium fluoride to the stannous oxide is 10:1, the concentration of sodium fluoride in electrolyte which can be reduced and regenerated by the single flow battery is 0.1mol/L, and the concentration of stannous oxide is 0.01mol/L.
The invention adopts another technical scheme that a preparation method of reducible and renewable electrolyte of a single flow battery is implemented according to the following steps:
step 1, preparing a new electrolyte containing lead trifluoromethanesulfonate and trifluoromethanesulfonic acid;
and 2, adding an additive into the new electrolyte obtained in the step 1, and performing constant volume to obtain 0.1L of electrolyte with stable performance of the single flow battery.
The step 1 is implemented according to the following steps:
step 1.1, dissolving lead trifluoromethanesulfonate in deionized water, and stirring until the solution is clear to obtain an electrolyte;
and step 1.2, adding trifluoromethanesulfonic acid into the electrolyte obtained in step 1.1, stirring for 10 minutes, and clarifying the solution to obtain a new electrolyte.
In the step 1.2, the concentration of the lead trifluoromethanesulfonate in the new electrolyte is 3mol/L, and the concentration of the trifluoromethanesulfonic acid is 1mol/L.
In the step 1, the additive consists of sodium fluoride and stannous oxide, and the molar ratio of the sodium fluoride to the stannous oxide is 10:1, the concentration of sodium fluoride in electrolyte which can be reduced and regenerated by the single flow battery is 0.1mol/L, and the concentration of stannous oxide is 0.01mol/L.
According to the preparation method of the electrolyte for the renewable reduction of the single flow battery, all the used chemicals are analytically pure.
Carrying out charge and discharge tests on the single flow battery using the reducible and renewable electrolyte at room temperature, wherein the test temperature is 20 ℃, and the parameters of the charge and discharge tests are set as follows: the charge-discharge current density is 25mA/cm 2 The charging time is 4h, the discharge cut-off voltage is 1.1V, and the linear flow velocity of the electrolyte in the battery is 0.5cm/s.
And (3) testing results: the coulombic efficiency of the battery is more than 90-92%, the energy efficiency is 70-75%, short circuit failure occurs after the battery is cycled for 510 times, the coulombic efficiency after hydrogen peroxide reduction regeneration is 90-92%, the energy efficiency is 70-75%, and no PbSO exists in the regeneration process 4 And (4) generating.
TABLE 1
Figure BDA0002377337880000111
As can be seen from table 1: examples 1-5 Coulomb efficiency and energy efficiency of the cells before and after hydrogen peroxide reduction regeneration were consistent, with no white PbSO being present during regeneration 4 The coulombic efficiency of the lead methylsulfonate single flow battery is 90 percent and the energy efficiency is 60 to 70 percent, which are achieved and are superior to those of the lead methylsulfonate single flow battery reported in the prior literature.

Claims (2)

1. The electrolyte capable of being reduced and regenerated for the single flow battery is characterized by comprising the following components: lead trifluoromethanesulfonate, trifluoromethanesulfonic acid, deionized water and an additive;
the concentration of lead trifluoromethanesulfonate in the electrolyte which can be reduced and regenerated by the single flow battery is 2-3mol/L, and the concentration of trifluoromethanesulfonic acid is 0-1mol/L;
the additive consists of sodium fluoride and stannous oxide, wherein the molar ratio of the sodium fluoride to the stannous oxide is 10:1, the concentration of sodium fluoride in electrolyte which can be reduced and regenerated by the single flow battery is 0.01-0.1mol/L, and the concentration of stannous oxide is 0.001-0.01mol/L.
2. A preparation method of electrolyte capable of being reduced and regenerated for a single flow battery is characterized by comprising the following steps:
step 1, preparing a new electrolyte containing lead trifluoromethanesulfonate and trifluoromethanesulfonic acid;
step 1.1, dissolving lead trifluoromethanesulfonate in deionized water, and stirring until the solution is clear to obtain an electrolyte;
step 1.2, adding trifluoromethanesulfonic acid into the electrolyte obtained in step 1.1, stirring for 5-10 minutes, and clarifying the solution to obtain a new electrolyte;
the concentration of the lead trifluoromethanesulfonate of the new electrolyte in the step 1.2 is 2-3mol/L, and the concentration of the trifluoromethanesulfonic acid is 0-1mol/L;
step 2, adding an additive into the new electrolyte obtained in the step 1, and performing constant volume to obtain a reducible regenerative electrolyte of the single flow battery;
the additive consists of sodium fluoride and stannous oxide, wherein the molar ratio of the sodium fluoride to the stannous oxide is 10:1, the concentration of sodium fluoride in electrolyte which can be reduced and regenerated by the single flow battery is 0.01-0.1mol/L, and the concentration of stannous oxide is 0.001-0.01mol/L.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010086935A (en) * 2008-09-03 2010-04-15 Sharp Corp Redox flow battery
CN101747240A (en) * 2008-12-11 2010-06-23 张家港市国泰华荣化工新材料有限公司 Method for preparing trifluoromethyl sulfonic acid CF3SO3H by electrochemical fluorination gas-phase product of methanesulfonyl fluoride CH3SO2F
CN101964421A (en) * 2010-09-16 2011-02-02 南京双登科技发展研究院有限公司 Super lead storage battery anode active substance for electric automobile
CN106328976A (en) * 2016-11-11 2017-01-11 攀钢集团攀枝花钢铁研究院有限公司 Full-vanadium oxidation reduction flow battery
CN108666500A (en) * 2018-04-23 2018-10-16 浙江工业大学 A kind of increasing hole and cathode liberation of hydrogen in situ inhibit the preparation method of difunctional lead carbon battery glass fibre separator
CN109873191A (en) * 2019-03-29 2019-06-11 西安理工大学 A kind of electrolyte and preparation method thereof of the resistance to season of lead flow battery
CN110247093A (en) * 2019-06-25 2019-09-17 西安理工大学 A kind of preparation method of lead liquid stream pile

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6986966B2 (en) * 2001-08-10 2006-01-17 Plurion Systems, Inc. Battery with bifunctional electrolyte
US11177497B2 (en) * 2018-03-12 2021-11-16 Washington University Redox flow battery

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010086935A (en) * 2008-09-03 2010-04-15 Sharp Corp Redox flow battery
CN101747240A (en) * 2008-12-11 2010-06-23 张家港市国泰华荣化工新材料有限公司 Method for preparing trifluoromethyl sulfonic acid CF3SO3H by electrochemical fluorination gas-phase product of methanesulfonyl fluoride CH3SO2F
CN101964421A (en) * 2010-09-16 2011-02-02 南京双登科技发展研究院有限公司 Super lead storage battery anode active substance for electric automobile
CN106328976A (en) * 2016-11-11 2017-01-11 攀钢集团攀枝花钢铁研究院有限公司 Full-vanadium oxidation reduction flow battery
CN108666500A (en) * 2018-04-23 2018-10-16 浙江工业大学 A kind of increasing hole and cathode liberation of hydrogen in situ inhibit the preparation method of difunctional lead carbon battery glass fibre separator
CN109873191A (en) * 2019-03-29 2019-06-11 西安理工大学 A kind of electrolyte and preparation method thereof of the resistance to season of lead flow battery
CN110247093A (en) * 2019-06-25 2019-09-17 西安理工大学 A kind of preparation method of lead liquid stream pile

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"添加剂对甲基磺酸铅液流电池负极枝晶形态影响的研究"，史静，《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅱ辑》，第C042-1365页；20180215;史静;《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅱ辑》;20180215;第2018年/卷(第02期);第C042-1365页 *

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