CN110718709A - Single-liquid film-free full-deposition type lead-acid flow battery device and working method thereof - Google Patents

Single-liquid film-free full-deposition type lead-acid flow battery device and working method thereof Download PDF

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Publication number
CN110718709A
CN110718709A CN201910992682.1A CN201910992682A CN110718709A CN 110718709 A CN110718709 A CN 110718709A CN 201910992682 A CN201910992682 A CN 201910992682A CN 110718709 A CN110718709 A CN 110718709A
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China
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electrolyte
liquid
reactor
stabilizer
flow battery
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CN201910992682.1A
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刘旭东
毕孝国
孙旭东
惠宇
那兆霖
王兴安
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Dalian University
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Dalian University
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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
    • 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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • 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

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)

Abstract

The invention discloses a single-liquid film-free full-deposition type lead-acid flow battery device and a working method thereof, wherein the single-liquid film-free full-deposition type lead-acid flow battery device comprises the following steps: the device comprises an inlet current stabilizer, a reactor, an alternating current-direct current converter, a load, an electric energy device, an outlet current stabilizer and a liquid storage tank, wherein the outlet of the liquid storage tank is connected with the inlet current stabilizer through a liquid conveying pipe; positive and negative electrode plates which are connected in parallel and are arranged alternately are arranged in the reactor, the positive electrode plates are connected with one end of the alternating current-direct current converter through leads, the negative electrode plates are connected with the other end of the alternating current-direct current converter through leads, and the alternating current-direct current converter is also connected with a load and an electric energy device respectively. The application avoids the problems of cross contamination of electrolyte and expensive ion exchange membranes; the flow resistance of the electrolyte between the electrode plates is reduced, and the requirement for improving the charge and discharge performance of the flow battery is met.

Description

Single-liquid film-free full-deposition type lead-acid flow battery device and working method thereof
Technical Field
The invention relates to a redox flow battery device, in particular to a single-liquid film-free full-deposition lead-acid flow battery device, belonging to the field of new energy and energy conservation of energy science and technology.
Background
The energy crisis and environmental pollution threaten the survival and development of human beings, and the large-scale development and application of carbon-free clean distributed energy have become the subjects of the current and future human social life. Among the carbon-free clean distributed energy sources, the most abundant and most promising in scale application are distributed energy sources such as solar energy and wind energy. However, the solar energy and wind energy in nature have low energy density, extremely uneven time and regional distribution, great volatility along with time and season and great regional difference, which are bottlenecks that limit the large-scale development and application of the solar energy and wind energy.
The redox flow battery as a novel electric storage energy storage device has a plurality of potential excellent performances, such as large energy storage capacity, ultra-deep discharge, long service life, small concentration polarization and the like, is not limited by geographical conditions, can be used as matched energy storage equipment of distributed clean energy such as solar energy, wind energy and the like, and can also be used as a peak regulation device of a power grid, so that the power transmission quality is improved, and the safety of the power grid is ensured.
The redox flow battery has different reaction mechanisms due to its different kinds. In conventional redox flow batteries such as all vanadium, sodium polysulfide/bromine and iron/chromium systems, there are two main disadvantages: one is a key component diaphragm, the performance of which is not very stable, and the diaphragm is expensive, which is a bottleneck in the development of the traditional liquid flow energy storage battery. The other needs two sets of infusion systems, so that the system is complex in structure and high in cost. The existing lead acid liquid flow battery is formed by fixing a positive plate and a negative plate together through threads, and electrolyte flows through a gap between the two electrode plates. The battery has lower capacity, and the flow resistance of the electrolyte in a narrow gap is higher, so that the internal resistance of the battery is higher, the energy consumption of the battery is higher, the efficiency is lower, and the electrode plate is troublesome to replace in the use process of the battery.
Therefore, the reactor suitable for stable charge and discharge of the flow battery is designed, influence factors of the quantity and the distance of electrode plates and the flow resistance of electrolyte on the performance of the flow battery in the charge and discharge processes are eliminated, and the reactor is very necessary for the full-deposition type lead-acid flow battery and other single-liquid film-free redox flow batteries.
Disclosure of Invention
Aiming at the problems in the prior art, the application provides a single-liquid film-free full-deposition type lead-acid flow battery device and a working method thereof, which avoid the problems of cross contamination of electrolyte and expensive ion exchange membranes; the flow resistance of the electrolyte between the electrode plates is reduced, and the requirement for improving the charge and discharge performance of the flow battery is met.
In order to achieve the purpose, the technical scheme of the application is as follows: a single-liquid film-free full-deposition type lead-acid flow battery device comprises: the device comprises an inlet current stabilizer, a reactor, an alternating current-direct current converter, a load, an electric energy device, an outlet current stabilizer and a liquid storage tank, wherein the outlet of the liquid storage tank is connected with the inlet current stabilizer through a liquid conveying pipe; positive and negative electrode plates which are connected in parallel and are arranged alternately are arranged in the reactor, the positive electrode plates are connected with one end of the alternating current-direct current converter through leads, the negative electrode plates are connected with the other end of the alternating current-direct current converter through leads, and the alternating current-direct current converter is also connected with a load and an electric energy device respectively.
Furthermore, the positive and negative electrode plates are connected with the reactor in a plug-in manner.
Furthermore, the liquid storage tank is filled with a mixed liquid of 1.5mol/L lead methylsulfonate and 0.9mol/L methanesulfonic acid.
Furthermore, a circulating pump and a flowmeter are sequentially arranged on the infusion tube between the outlet of the liquid storage tank and the inlet current stabilizer.
The application also provides a working method of the single-liquid film-free full-deposition type lead-acid flow battery device, which specifically comprises the following steps: the circulating pump flows the electrolyte in the liquid storage tank into the inlet stabilizer through the liquid conveying pipe, the electrolyte is stabilized in the inlet stabilizer and then shunted into the reactor, the liquid level of the electrolyte in the reactor continuously rises to reach the outlet and flows into the outlet stabilizer from the reactor, and then the electrolyte flows into the liquid storage tank through the liquid conveying pipe to realize the circulating flow of the electrolyte;
during charging, the gear in the alternating current-direct current converter is adjusted to a charging gear; at this time, current is passed through the lead into the electrode plate, and Pb ions in the electrolyte undergo redox reaction to deposit PbO on the positive electrode plate under the condition that current is passed2And depositing Pb on the negative plate; during discharging, the gear in the alternating current-direct current converter is adjusted to a discharging gear; at this time, PbO on positive and negative plates2And Pb deposits are subjected to redox reaction to generate Pb ions which are dissolved into the electrolyte, and current is generated on the whole loop and is transmitted to a load. During the charging and discharging process, the flow of the electrolyte is required to be adjusted by a flowmeter according to the charging and discharging current and voltage or the number of electrode plates in the reactor.
Due to the adoption of the technical scheme, the invention can obtain the following technical effects:
1. the positive and negative electrodes are connected in parallel and arranged alternately, the number of the positive and negative electrode plates can be adjusted according to the capacity of the battery, the flow battery reactor is ensured to have larger unit volume electrode reaction area in the charging and discharging process, and the unit volume capacity of the full-deposition type lead-acid flow battery is improved.
2. The flow stabilizers are respectively added before and after the electrolyte flows through the reactor, so that the effects of stability and shunt are achieved in the flowing process of the electrolyte, the flowing stability and uniformity of the electrolyte between the positive electrode and the negative electrode in the reactor can be improved in the charging and discharging process of the battery, the uniformity of electrode current distribution is improved, and the charging and discharging performance of the battery is improved.
3. Through the improvement to the redox flow battery reactor, can design positive, negative electrode plate for plug-in structure, can adjust the capacity of battery in real time, also can change the plate electrode in real time simultaneously, and then improve the stability and the maintainability of battery.
4. The same liquid is used for the positive electrode and the negative electrode, and the mixed liquid of the methanesulfonic acid and the lead methylsulfonate is used as the electrolyte, so that the problems of cross contamination of the electrolyte and an expensive ion exchange membrane are solved.
Drawings
FIG. 1 is a schematic structural diagram of a single-liquid film-free fully-deposited lead-acid flow battery device;
the sequence numbers in the figures illustrate: 1. a circulation pump; 2. a flow meter; 3. a transfusion tube; 4. an inlet flow stabilizer; 5. a reactor; 6. a negative electrode plate; 7. an AC-DC converter; 8. a load; 9. an electrical energy device; 10. a positive electrode plate; 11. an outlet flow stabilizer; 12. a liquid storage tank.
Detailed Description
The embodiments of the present invention are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of the present invention is not limited to the following embodiments.
Example 1
The embodiment provides a single-liquid film-free full-deposition type lead-acid flow battery device, which comprises a circulating pump 1, a flowmeter 2, a liquid conveying pipe 3, an inlet current stabilizer 4, a reactor 5, a negative electrode plate 6, an alternating current-direct current converter 7, a load 8, an electric energy device 9, a positive electrode plate 10, an outlet current stabilizer 11 and a liquid storage tank 12. The circulating pump 1 has excellent strong acid corrosion resistance, the maximum flow rate is 20L/min, and the maximum flow rate of the circulating pump can also be changed according to the capacity and performance requirements of the battery. The flowmeter 2 has excellent strong acid corrosion resistance, the measuring range is 0.1L/min-20L/min, and the measuring range of the flowmeter 2 can also be changed according to the battery capacity and the performance requirement. An inlet current stabilizer 4 and an outlet current stabilizer 11 which can play a role in stabilizing and shunting are respectively added before and after the electrolyte flows through the reactor, so that the uniformity of electrode current distribution and the charge and discharge performance of the battery are improved. The positive and negative electrode plates in the reactor 5 are connected in parallel and are arranged alternately, and the number of the positive and negative electrode plates can be determined by the capacity of the battery. The positive and negative electrode plates in the reactor 5 can be designed into a plug-in structure, and the number of the electrode plates can be adjusted and the electrode plates can be replaced in real time. The volume of the liquid storage tank 12 is 10L, and the liquid storage tank stores a mixed liquid of 1.5mol/L lead methylsulfonate and 0.9mol/L methanesulfonic acid.
The device makes full use of the principles of fluid flow, chemical reaction, electrolyte deposition, dissolution and the like, realizes the adjustability of the number of the positive and negative electrode plates, ensures that the flow battery has larger electrode reaction area per unit volume in the charging and discharging process, and improves the capacitance per unit volume of the battery. The flow stabilizers are respectively added before and after the electrolyte flows through the reactor, so that the electrolyte flow process plays a role in stable and uniform flow division, the flow stability and uniformity of the electrolyte between the positive electrode and the negative electrode in the reactor can be improved in the charge and discharge process of the battery, the uniformity of electrode current distribution is improved, and the charge and discharge performance of the battery is improved.
Example 2
The single-liquid film-free full-deposition type lead-acid flow battery device provided by the embodiment is tried on a small solar power generation device and is installed at a power utilization part of the solar power generation device. The electrolyte is a mixed solution of 1.5mol/L lead methylsulfonate and 0.9mol/L methanesulfonic acid; the volume of the liquid storage tank is 10L, and the flow rate of the electrolyte is 2L/min; the number of the electrode plates is 50, wherein the positive electrode plate and the negative electrode plate are respectively 25; the charge-discharge current was 20A and the charge-discharge time was 10 h.
The battery device runs 100 charge-discharge cycles, runs stably and reliably in the charge-discharge process, and does not have the phenomenon of open circuit or short circuit caused by falling off of sediments or adhesion of sediments in the running process. After the charging and discharging are stopped, the sediments on the electrode plate are more compact and uniform, which shows that the flow field distribution of the electrolyte in the reactor is very uniform and the contact between the electrolyte and the electrode plate is very sufficient under the conditions of the electrolyte flow and the reactor structure design of the flow cell energy storage device of the invention, so that the flow cell energy storage device has stable charging and discharging performance.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.

Claims (5)

1. A single-liquid film-free full-deposition type lead-acid flow battery device is characterized by comprising: the device comprises an inlet current stabilizer, a reactor, an alternating current-direct current converter, a load, an electric energy device, an outlet current stabilizer and a liquid storage tank, wherein the outlet of the liquid storage tank is connected with the inlet current stabilizer through a liquid conveying pipe; positive and negative electrode plates which are connected in parallel and are arranged alternately are arranged in the reactor, the positive electrode plates are connected with one end of the alternating current-direct current converter through leads, the negative electrode plates are connected with the other end of the alternating current-direct current converter through leads, and the alternating current-direct current converter is also connected with a load and an electric energy device respectively.
2. The single-liquid film-free fully-deposited lead-acid flow battery device according to claim 1, wherein the positive and negative electrode plates are connected with the reactor in a plug-in manner.
3. The single-liquid film-free fully-deposited lead-acid flow battery device according to claim 1, wherein the liquid storage tank is a mixed solution of 1.5mol/L lead methylsulfonate and 0.9mol/L methanesulfonic acid.
4. The single-liquid film-free fully-deposited lead-acid flow battery device according to claim 1, wherein a circulating pump and a flow meter are sequentially arranged on a liquid transfer pipe between the outlet of the liquid storage tank and the inlet flow stabilizer.
5. A working method of a single-liquid film-free full-deposition type lead-acid flow battery device is characterized by specifically comprising the following steps: the circulating pump flows the electrolyte in the liquid storage tank into the inlet stabilizer through the liquid conveying pipe, the electrolyte is stabilized in the inlet stabilizer and then shunted into the reactor, the liquid level of the electrolyte in the reactor continuously rises to reach the outlet and flows into the outlet stabilizer from the reactor, and then the electrolyte flows into the liquid storage tank through the liquid conveying pipe to realize the circulating flow of the electrolyte;
during charging, the gear in the alternating current-direct current converter is adjusted to a charging gear; at this time, current is passed through the lead into the electrode plate, and Pb ions in the electrolyte undergo redox reaction to deposit PbO on the positive electrode plate under the condition that current is passed2And depositing Pb on the negative plate; during discharging, the gear in the alternating current-direct current converter is adjusted to a discharging gear; at this time, PbO on positive and negative plates2And Pb deposits are subjected to redox reaction to generate Pb ions which are dissolved into the electrolyte, and current is generated on the whole loop and is transmitted to a load.
CN201910992682.1A 2019-10-18 2019-10-18 Single-liquid film-free full-deposition type lead-acid flow battery device and working method thereof Pending CN110718709A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104078695A (en) * 2014-07-22 2014-10-01 沈阳工程学院 Full-sedimentary type lead acid liquid current battery energy storing device
CN109065932A (en) * 2018-08-09 2018-12-21 中南大学 Appositional pattern flow battery

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104078695A (en) * 2014-07-22 2014-10-01 沈阳工程学院 Full-sedimentary type lead acid liquid current battery energy storing device
CN109065932A (en) * 2018-08-09 2018-12-21 中南大学 Appositional pattern flow battery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
林仁荣等: ""无膜单液铅酸液流电池的制备与性能研究"", 《沈阳工程学院（自然科学版）》 *

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Application publication date: 20200121