CN108598529B - Pressure balancing device for positive and negative electrode systems of all-vanadium redox flow battery - Google Patents
Pressure balancing device for positive and negative electrode systems of all-vanadium redox flow battery Download PDFInfo
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- CN108598529B CN108598529B CN201810434053.2A CN201810434053A CN108598529B CN 108598529 B CN108598529 B CN 108598529B CN 201810434053 A CN201810434053 A CN 201810434053A CN 108598529 B CN108598529 B CN 108598529B
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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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/0438—Pressure; Ambient pressure; Flow
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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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
- H01M8/04746—Pressure; Flow
- H01M8/04761—Pressure; Flow of fuel cell exhausts
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a pressure balancing device for a positive and negative electrode system of an all-vanadium redox flow battery, which comprises a communicating pipeline for connecting a negative electrolyte storage tank and a positive electrolyte storage tank, wherein a deaerator is connected in series on the communicating pipeline, and a breather valve is also communicated on the communicating pipeline; the deaerator is filled with deaerator, and the deaerator is prepared by adopting an impregnation method, namely the carrier is prepared by impregnating with an adsorbent solution; the carrier is one or more of alumina, silica gel, activated carbon, carbon fiber, molecular sieve and silicon dioxide; the adsorbent is a reducing agent that can undergo a color reaction. The pressure balancing device for the positive and negative electrode systems of the all-vanadium redox flow battery, provided by the invention, replaces an inert gas sealing/water sealing system as the pressure balancing device for the positive and negative electrodes of the vanadium redox flow battery system, has the effects of detecting the overcharge phenomenon of the positive electrode and absorbing oxygen to protect negative electrode electrolyte, greatly reduces the cost investment of a peripheral system, has better practicability and simple operation, and can effectively reduce the pressure risk factors of the system.
Description
Technical Field
The invention relates to the technical field of vanadium redox batteries, in particular to a pressure balancing device for a positive and negative electrode system of an all-vanadium redox flow battery.
Background
The all-vanadium redox flow battery has the advantages of high energy conversion efficiency, adjustable capacity, long service life, high safety, environmental friendliness and the like, and is mainly used for matching energy storage equipment with a power generation system of renewable energy sources such as solar energy, wind energy and the like, a peak and valley regulation device of a power grid, an uninterruptible power supply and an emergency power supply system.
As an electrochemical system, a vanadium battery stores energy in electrolyte containing vanadium ion redox couples with different valence states, the electrolyte with different redox couples respectively forms anode electrolyte and cathode electrolyte of the battery, the anode electrolyte and the cathode electrolyte are separated by an ion exchange membrane, the solution is pressed into a battery stack body from a liquid storage tank through an external pump to complete electrochemical reaction, the solution returns to the liquid storage tank after reaction, and active substances continuously and circularly flow, so that charging and discharging are completed. The all-vanadium redox flow battery realizes the storage and release of electric energy through the interconversion of vanadium ions with different valence states. The positive and negative electrolytes are respectively sulfuric acid electrolytes V (IV) and V (III). As the positive and negative electrolytes are all the same elements, the cross contamination caused by the mutual permeation of different active substances between the positive and negative electrodes of the battery is avoided in principle.
When the all-vanadium redox flow battery is charged, electric energy is converted into chemical energy to be stored in vanadium ions with different valence states. At this time, positive electrode VO2+Oxidation to VO2 +In the negative electrode V3+Reduction to V2+(ii) a During discharging, chemical energy is converted into electric energy to discharge, and at the moment, the positive electrode VO2 +Conversion to VO2+In the negative electrode V2+Conversion to V3+The charge and discharge reaction is as follows:
and (3) positive electrode:
negative electrode:
the pressure balancing device is an important component of a peripheral pipeline system of the all-vanadium redox flow battery, and has the functions of controlling the pressure of the pipeline in the system, maintaining the pressure balance of the anode system and the cathode system and relieving the migration of the electrolyte. During the operation of the vanadium battery system, the phenomenon of unbalanced positive and negative pressure often occurs due to vanadium ion migration, pressure loss difference of pipelines and the like. The imbalance of the pressures of the anode and the cathode easily causes the phenomenon of vanadium ion migration to be aggravated, the concentration difference of the electrolyte of the anode and the cathode is continuously enlarged along with the continuous migration of the vanadium ions, and the electrolyte of the anode and the cathode is increasingly mismatched, so that the capacity is rapidly attenuated, and the service life of the battery is shortened; on the other hand, the positive electrode is easy to generate over-charging oxygen evolution, the phenomenon of pressure imbalance is aggravated, and a vicious circle is formed.
At present, the pressure control mode of the vanadium redox battery system is mainly to use water seal or inert gas seal for pressure regulation. The water seal device adopts a water seal buffer tank to automatically adjust air pressure balance, and has the defects that the phenomenon of water suck-back or ejection in the buffer tank is easily caused due to large instantaneous pressure change when a pump is started or closed, and the internal pressure balance of the two storage tanks cannot be ensured due to the independent arrangement of the water seals on the positive and negative storage tanks. An inert gas sealing device is adopted in patent application CN105428680A, the device comprises a pressure balance device filled with inert gas, one end of the pressure balance device is connected with a positive electrolyte storage tank, the other end is connected with a negative electrolyte storage tank, and a pressure sensing switch is used for maintaining the pressure in the storage tank at a certain value. The disadvantages mainly include: the sealing performance of the inert gas sealing system is poor, and reactive loss of inert gas is easily caused; the purchase cost is high, and certain requirements are made on installation space; the system has large internal pressure and reduces the safety degree of the system. Utility model patent CN202996968U adopts a simple and easy atmospheric pressure balancing unit, and the device will just, negative pole storage tank upper space intercommunication, and inside expert has inert gas, and the storage tank is sealed completely with the outside, stops the outside air admission. Although the device can ensure the pressure of the upper layer of the positive and negative storage tanks to be consistent, the oxidation of external oxygen to the electrolyte is avoided, and the oxidation of oxygen separated out due to the overcharge of the positive electrode to the negative electrolyte cannot be prevented. The technologies can not detect whether the anode solution has an oxygen evolution phenomenon or not, and can not absorb or eliminate the oxygen evolution phenomenon, so that once the oxygen evolution phenomenon occurs, the mismatching of the vanadium battery electrolyte is aggravated, and the service life of the battery is shortened.
Disclosure of Invention
The invention mainly solves the technical problem of providing a pressure balancing device for a positive and negative electrode system of an all-vanadium redox flow battery, which consists of a breather valve, a deaerator and related connecting pipelines, replaces an inert gas sealing/water sealing system to be used as the pressure balancing device for the positive and negative electrodes of the vanadium battery system, has the functions of detecting the positive electrode overcharge phenomenon and absorbing oxygen to protect negative electrode electrolyte, greatly reduces the cost input of a peripheral system, has better practicability and simple operation, and can effectively reduce the dangerous factors of the system pressure.
The technical scheme adopted by the invention is as follows: a pressure balancing device for a positive-negative electrode system of an all-vanadium redox flow battery comprises a communicating pipeline for connecting a negative electrolyte storage tank and a positive electrolyte storage tank, wherein a deaerator is connected in series on the communicating pipeline, and a breather valve is also communicated on the communicating pipeline;
the deaerator is filled with a deaerator, and the deaerator is prepared by adopting an impregnation method, namely the carrier is prepared by impregnating an adsorbent solution; the carrier is one or more of alumina, silica gel, activated carbon, carbon fiber, molecular sieve and silicon dioxide; the adsorbent is a reducing agent capable of performing a color reaction, and can be one or more of ferrous salt, iodide salt, citric acid, sodium citrate, 2-hydroxysuccinic acid, hydroxylamine hydrochloride and phenol. The reducing agent capable of generating the color reaction is used as the adsorbent, the oxygen evolution condition of the anode can be visually monitored through the color reaction in the working process, and the evolved oxygen is absorbed to prevent the cathode electrolyte from being oxidized by the evolved oxygen.
Preferably, the deaerator includes the cylinder casing that transparent corrosion resistant material made, the both ends mouth of cylinder casing seals and is equipped with the filter screen the oxygen-eliminating agent is filled in between two filter screens in the cylinder casing be provided with the screw thread section on the outer wall that is located both ends of cylinder casing, install the loose joint on the screw thread section, the deaerator through the loose joint at both ends with the intercommunication pipeline concatenates, the vertical installation of deaerator. The movable joints are adopted for connection, so that the regenerated deoxidant can be replaced or treated conveniently after being detached. The deaerator has the main function of absorbing oxygen entering the system when the breather valve is opened and oxygen separated out when the vanadium battery anode side reaction or overcharge occurs, and preventing the oxygen from entering the cathode system and oxidizing cathode electrolyte.
A loose joint sealing ring is installed in the loose joint, and the loose joint sealing ring is made of corrosion-resistant and elastic materials.
The communicating pipeline is made of polyethylene, polypropylene, polyvinyl chloride or polytetrafluoroethylene high-molecular acid-resistant materials.
The main body and the sealing element of the breather valve are made of polypropylene, polyethylene, polyvinyl chloride or polytetrafluoroethylene high-molecular acid-resistant materials.
The breather valve is vertically arranged and communicated with the communicating pipeline.
Further, the breather valve is vertically installed above the communication pipeline. Or the breather valve is vertically arranged at the top end of the positive electrolyte storage tank and is communicated with the communicating pipeline through a tee joint. The breather valve is mainly used for controlling the pressure of the pipeline system. The breather valve is vertically arranged at the highest point of the gas phase space of the storage tank, so that the pressure in the tank is ensured to be in a normal state, the storage tank is prevented from being damaged due to overpressure or super vacuum in the tank, and the volatilization loss of liquid in the tank can be reduced. The breather valve should periodically check and clean if the valve disc and valve seat become stuck, clogged, etc., or otherwise malfunctioning.
The invention provides a pressure balancing device of a positive-negative system for a vanadium redox battery, which consists of a breather valve, a deaerator and related pipelines, wherein the deaerator adopts a reductive adsorbent capable of generating a color reaction to load on a carrier and is filled in the deaerator to form a filter element. The positive and negative system pressure balancing device for the vanadium redox battery mainly has the functions of balancing the pressure of the positive and negative systems, and can detect and absorb oxygen precipitated from a positive electrolyte and oxygen in air entering a system when a breather valve is opened through a color reaction. The method has the effects of balancing the pressure of the anode and the cathode, detecting and absorbing the oxygen evolution of the anode and preventing the cathode electrolyte from being oxidized, and is easy to operate, low in cost and environment-friendly.
Drawings
Fig. 1 is a schematic structural diagram of an embodiment of a pressure balancing device for a positive-negative electrode system of an all-vanadium redox flow battery provided by the invention;
fig. 2 is a schematic structural diagram of the deaerator 2 in fig. 1.
Detailed Description
The technical scheme of the invention is explained in detail in the following with the accompanying drawings.
As shown in fig. 1 and fig. 2, the pressure balancing device 30 for the positive-negative electrode system of the all-vanadium redox flow battery comprises a communicating pipeline 40, one end of the communicating pipeline 40 is communicated with the top end of the negative electrolyte storage tank 10, the other end of the communicating pipeline 40 is communicated with the top end of the positive electrolyte storage tank 20, a deaerator 2 is connected in series on the communicating pipeline 40, and the communicating pipeline 40 is also communicated with a breather valve 1;
the connecting channel 40 is made of an acid-resistant polymer material, such as polyethylene, polypropylene, polyvinyl chloride, or polytetrafluoroethylene.
The deaerator 2 comprises a cylindrical shell 6 made of transparent corrosion-resistant materials, two ports of the cylindrical shell 6 are sealed with filter screens 4, a deaerator 5 is filled between the two filter screens 4 in the cylindrical shell 6, threaded sections are arranged on the outer wall surfaces of the cylindrical shell 6, which are located at two ends, loose joints 3 are installed on the threaded sections, the deaerator 2 is connected in series with a communication pipeline 40 through the loose joints 3 at two ends, and the deaerator 2 needs to be installed vertically. A loose joint sealing ring is arranged in the loose joint 3, and the loose joint sealing ring is made of corrosion-resistant and elastic material. The cylindrical shell 6 can be made of transparent PVC pipe.
The deoxidant 5 filled in the deaerator 2 is prepared by adopting an impregnation method, namely the carrier is prepared by impregnating the carrier with an adsorbent solution. The carrier can be one or more of alumina, silica gel, activated carbon, carbon fiber, molecular sieve and silicon dioxide. The adsorbent is selected to be a reducing agent that can undergo a color reaction. The adsorbent can be one or more of ferrous salt, iodide salt, citric acid, sodium citrate, 2-hydroxysuccinic acid, hydroxylamine hydrochloride and phenol.
The main body and the sealing element of the breather valve 1 are made of polypropylene, polyethylene, polyvinyl chloride or polytetrafluoroethylene high-molecular acid-resistant materials. The breather valve 1 needs to be vertically installed and communicate with the communication duct 40. Specifically, the breather valve 1 may be vertically installed above the communication duct 40, and communicate with the communication duct 40 through a flange. Alternatively, the breather valve 1 may be vertically installed at the top end of the positive electrolyte reservoir 20 and communicated with the communication pipe 40 through a tee.
The above-mentioned pressure balance device that this embodiment provided not only has the effect of balanced positive negative pole system pressure, can absorb the anodal oxygen that appears moreover, and the color reaction through the oxygen-eliminating device can the audio-visual monitoring anodal oxygen evolution condition to the oxygen absorption that will appear prevents that the negative pole electrolyte from being oxidized by the oxygen that appears.
The inventive concept has been described in detail above with reference to specific embodiments. Those of ordinary skill in the art, having access to the teachings set forth above, may readily modify any of the above-described embodiments to achieve the same or similar results without undue experimentation, and such modifications are intended to be within the scope of the present invention as defined by the following claims.
Claims (9)
1. The pressure balancing device for the positive and negative electrode systems of the all-vanadium redox flow battery is characterized by comprising a communicating pipeline for connecting a negative electrolyte storage tank and a positive electrolyte storage tank, wherein a deaerator is connected in series on the communicating pipeline, and a breather valve is also communicated on the communicating pipeline;
the deaerator is filled with a deaerator, and the deaerator is prepared by adopting an impregnation method, namely the carrier is prepared by impregnating an adsorbent solution; the carrier is one or more of alumina, silica gel, activated carbon, carbon fiber, molecular sieve and silicon dioxide; the adsorbent is a reducing agent capable of developing a color reaction.
2. The pressure balancing device for the positive-negative electrode system of the all-vanadium flow battery is characterized in that the deaerator comprises a cylindrical shell made of a transparent corrosion-resistant material, filter screens are sealed at two end openings of the cylindrical shell, the deaerator is filled between the two filter screens in the cylindrical shell, threaded sections are arranged on the outer wall surfaces of the cylindrical shell, located at two end portions, of the cylindrical shell, loose joints are mounted on the threaded sections, the deaerator is connected with the communication pipeline in series through the loose joints at the two ends, and the deaerator is vertically mounted.
3. The pressure balancing device for the positive and negative electrode systems of the all-vanadium redox flow battery of claim 1, wherein the adsorbent is one or more of ferrite, iodide salt, citric acid, sodium citrate, 2-hydroxysuccinic acid, hydroxylamine hydrochloride and phenol.
4. The pressure balancing device for the positive-negative electrode system of the all-vanadium redox flow battery of claim 2, wherein a loose joint sealing ring is installed in the loose joint, and the loose joint sealing ring is made of a corrosion-resistant and elastic material.
5. The pressure balancing device for the positive-negative electrode system of the all-vanadium redox flow battery as claimed in claim 1, wherein the communication pipeline is made of polyethylene, polypropylene, polyvinyl chloride or polytetrafluoroethylene polymer acid-resistant material.
6. The pressure balancing device for the positive-negative electrode system of the all-vanadium flow battery as claimed in claim 1, wherein the main body and the sealing member of the breather valve are made of polypropylene, polyethylene, polyvinyl chloride or polytetrafluoroethylene polymer acid-resistant material.
7. The pressure balancing device for the positive-negative electrode system of the all-vanadium redox flow battery as claimed in claim 6, wherein the breather valve is vertically installed on the surface of the communication pipeline or the surface of the positive electrolyte storage tank and is communicated with the communication pipeline.
8. The all-vanadium redox flow battery positive-negative electrode system pressure balancing device of claim 7, wherein the breather valve is vertically installed above the communication pipe.
9. The pressure balancing device for the positive-negative electrode system of the all-vanadium redox flow battery as claimed in claim 7, wherein the breather valve is vertically installed at the top end of the positive electrolyte storage tank and is communicated with the communication pipeline through a tee joint.
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| CN201810434053.2A CN108598529B (en) | 2018-05-08 | 2018-05-08 | Pressure balancing device for positive and negative electrode systems of all-vanadium redox flow battery |
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| CN201810434053.2A CN108598529B (en) | 2018-05-08 | 2018-05-08 | Pressure balancing device for positive and negative electrode systems of all-vanadium redox flow battery |
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| CN108598529B true CN108598529B (en) | 2020-06-09 |
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| CN111710889A (en) * | 2020-06-29 | 2020-09-25 | 上海电气集团股份有限公司 | Electrolyte storage tank and flow battery energy storage system |
| CN113594492B (en) * | 2021-06-16 | 2022-08-09 | 东风汽车集团股份有限公司 | Fuel cell cooling system, fuel cell system, control method, and control device |
| CN114243127A (en) * | 2022-02-21 | 2022-03-25 | 浙江金羽新能源科技有限公司 | Aqueous electrolyte with low dissolved oxygen, preparation method thereof and aqueous ion battery |
| CN217822889U (en) * | 2022-08-10 | 2022-11-15 | 寰泰储能科技股份有限公司 | Non-flat-layer arranged all-vanadium redox flow battery |
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| CN202996968U (en) * | 2012-12-25 | 2013-06-12 | 中国东方电气集团有限公司 | Storage system for vanadium battery electrolyte |
| CN103515642A (en) * | 2012-06-25 | 2014-01-15 | 中国人民解放军63971部队 | Preparation method of vanadium battery electrolyte solution with high purity and high concentration |
| CN105428680A (en) * | 2014-09-23 | 2016-03-23 | 周汉涛 | Vanadium cell electrolyte solution storage apparatus |
| CN105609796A (en) * | 2016-01-21 | 2016-05-25 | 湖南农业大学 | Modification method of electrode material for all-vanadium redox flow battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102055000B (en) * | 2009-10-29 | 2015-04-22 | 北京普能世纪科技有限公司 | Redox flow battery and method for enabling battery to operate continuously for long time |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103515642A (en) * | 2012-06-25 | 2014-01-15 | 中国人民解放军63971部队 | Preparation method of vanadium battery electrolyte solution with high purity and high concentration |
| CN202996968U (en) * | 2012-12-25 | 2013-06-12 | 中国东方电气集团有限公司 | Storage system for vanadium battery electrolyte |
| CN105428680A (en) * | 2014-09-23 | 2016-03-23 | 周汉涛 | Vanadium cell electrolyte solution storage apparatus |
| CN105609796A (en) * | 2016-01-21 | 2016-05-25 | 湖南农业大学 | Modification method of electrode material for all-vanadium redox flow battery |
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