CN110010934B - Method for measuring resistance of electrolyte of flow battery on line - Google Patents
Method for measuring resistance of electrolyte of flow battery on line Download PDFInfo
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- CN110010934B CN110010934B CN201910316050.3A CN201910316050A CN110010934B CN 110010934 B CN110010934 B CN 110010934B CN 201910316050 A CN201910316050 A CN 201910316050A CN 110010934 B CN110010934 B CN 110010934B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/06—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a liquid
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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
- H01M8/04537—Electric variables
- H01M8/04634—Other electric variables, e.g. resistance or impedance
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a method for measuring the resistance of electrolyte of a flow battery on line, and particularly relates to the field of resistance measurement methods of flow batteries. According to the invention, two graphite electrodes are connected to two ends of an electrolyte pipeline, a resistance measurement loop is formed by the two graphite electrodes, the electrolyte and an electrochemical analyzer which are conveyed in the electrolyte pipeline, the length of the electrolyte between the two electrodes is adjusted according to the movement of an electric cylinder, the resistance of the electrolyte is measured, the cross section area of the electrolyte is calculated according to the value measured by a flowmeter, the resistivity of the electrolyte is calculated by using a resistivity formula, the resistance value of each part of the electrolyte loop in a pile is further obtained, and finally the cut-off voltage of a flow battery is controlled and adjusted according to the discharge duration and the resistance, so that the phenomenon that the overcharge and over-discharge are caused and the service life of the battery is shortened when the self-discharge and the output characteristics of the battery are influenced by the temperature and the concentration change of the resistance of the electrolyte is avoided.
Description
Technical Field
The invention relates to the technical field of a flow battery resistance measuring method, in particular to a method for measuring the resistance of electrolyte of a flow battery on line.
Background
The pile of all-Vanadium Redox Flow Battery (VRFB) is generally formed by connecting dozens of single cells in series, the single cells are connected by bipolar plates, electrolyte is distributed to the single cells in parallel through a common infusion header pipe, and the electrolyte in the positive and negative storage tanks is respectively delivered into the pile by a pump for circulation. Therefore, when a liquid circuit in the galvanic pile forms a closed loop and a potential difference exists, directional migration of ions can form bypass current, so that charge loss, reduction of current efficiency and reduction of energy efficiency are caused;
the existing device can not measure the resistance of the electrolyte, the temperature and the concentration of the electrolyte change along with charging or discharging, the resistance of the electrolyte changes, the resistance of the electrolyte influences the self-discharging of the battery and the output characteristic of the battery, and therefore, the resistance of the electrolyte needs to be measured on line, the charging and discharging degree of the battery is tracked, and the cut-off voltage of the charging and discharging is adjusted.
Disclosure of Invention
In order to overcome the above-mentioned defects of the prior art, embodiments of the present invention provide a method for online measurement of electrolyte resistance of a flow battery, two graphite electrodes are connected with two ends of an electrolyte pipeline to form a resistance measuring loop together with electrolyte conveyed in the electrolyte pipeline and an electrochemical analyzer, and the length of the electrolyte between the two electrodes is adjusted according to the movement of the electric cylinder, the resistance of the electrolyte is measured, the cross-sectional area of the electrolyte is calculated according to the value measured by the flowmeter, and finally, adjusting the cut-off voltage of the flow battery according to the discharge time and resistance control, and avoiding overcharge and overdischarge and shortening the service life of the battery when the self-discharge of the battery and the output characteristic of the battery are influenced by the resistance of the electrolyte due to the temperature and concentration change.
In order to achieve the purpose, the invention provides the following technical scheme: the method for measuring the resistance of the electrolyte of the flow battery on line comprises a measuring device, wherein the measuring device comprises an electrolyte storage tank, an electrolyte pipeline, an electrochemical analyzer, graphite electrodes and recording equipment, two ends of the electrolyte pipeline are respectively connected with the electrolyte storage tank to form an electrolyte loop, the graphite electrodes are arranged in two ends of one electrolyte pipeline which is arranged outside the flow battery respectively, the graphite electrodes are connected with the electrochemical analyzer through leads, one end of each graphite electrode, far away from the electrolyte pipeline, is fixedly connected with an electric cylinder, a flowmeter is arranged in the electrolyte pipeline, and the electrolyte pipeline is connected with a pressure pump;
the specific method of use of the measuring device is as follows:
step S1, laying a line; firstly, respectively leading out electrolyte pipelines from a positive electrolyte storage tank and a negative electrolyte storage tank of the flow battery, connecting graphite electrodes with an electric cylinder, leading out the positive electrolyte storage tank and the negative electrolyte storage tank to two electrolyte pipelines outside the flow battery, respectively installing the graphite electrodes and the electric cylinder at two ends, respectively connecting two groups of graphite electrodes with an electrochemical analyzer through leads, and then respectively connecting the electric cylinder, a flowmeter and a pressure pump with recording equipment;
step S2 measuring resistance; respectively measuring the resistance and calculating the resistivity of the positive electrolyte and the negative electrolyte in real time, and specifically comprising the following steps:
s2.1, controlling the pressure pump to work by the recording equipment, and conveying the electrolyte in the electrolyte storage tank into each single battery in the flow battery through an electrolyte pipeline so as to enable the flow battery to perform charging and discharging work;
s2.2, electrifying the two graphite electrodes, forming a resistance measurement loop with the electrolyte conveyed in the electrolyte pipeline and the electrochemical analyzer, measuring by the electrochemical analyzer to obtain the resistance of the electrolyte, and sending the measurement result to a recording device for storage;
s2.3, after the length of the electrolyte passing between the two graphite electrodes is determined, the flow meter monitors the flow of the electrolyte in real time, sends the flow value to a recording device, calculates the cross section area of the electrolyte, and the recording device calculates the resistivity according to the resistance of the electrolyte obtained in the step, wherein the calculation formula is as follows:
wherein R represents resistance, rho represents resistivity, L represents the length of the electrolyte passing between the two graphite electrodes, and S represents the cross-sectional area of the electrolyte passing between the two graphite electrodes;
and S2.4, after the recording equipment obtains the initial resistance value, controlling the electric cylinder to perform telescopic work, driving the two graphite electrodes to move back and forth by the electric cylinder so as to change the length of the electrolyte passing between the two graphite electrodes, changing the length measurement resistance for multiple times, calculating the resistivity, further obtaining the resistance value of each part of the electrolyte loop in the galvanic pile, and finally controlling and adjusting the cut-off voltage of the flow battery according to the discharge time and the resistance.
In a preferred embodiment, both ends of each single cell inside the flow battery are connected with an electrolyte pipeline through a common liquid feeding main pipe.
In a preferred embodiment, the electrochemical analyzer is in signal connection with a recording device, in particular a computer, via a data line.
In a preferred embodiment, the transmission of electric cylinder one end is connected with the push rod, push rod one end runs through electrolyte pipeline outer wall and extends to inside and graphite electrode fixed connection of electrolyte pipeline, push rod and electrolyte pipeline activity joint.
In a preferred embodiment, a cavity is arranged inside one end of the push rod close to the graphite electrode, through holes are arranged at the top end of the cavity and on the end surface of the push rod connected with the graphite electrode, the lead is arranged inside the cavity, one end of the lead penetrates through the through hole on the end surface of the push rod and is connected with the graphite electrode, and the other end of the lead penetrates through the through hole at the top end of the push rod and is connected with the electrochemical analyzer.
In a preferred embodiment, the flow meter is connected via an a/D converter to a recording device, which is connected via a D/a converter to a pressure pump and an electric cylinder.
The invention has the technical effects and advantages that:
1. according to the invention, two graphite electrodes are connected to two ends of an electrolyte pipeline, a resistance measurement loop is formed by the two graphite electrodes, the electrolyte and an electrochemical analyzer which are conveyed in the electrolyte pipeline, the length of the electrolyte between the two electrodes is adjusted according to the movement of an electric cylinder, the resistance of the electrolyte is measured, the cross section area of the electrolyte is calculated according to the value measured by a flowmeter, the resistivity of the electrolyte is calculated by using a resistivity formula, the resistance value of each part of the electrolyte loop in a pile is further obtained, and finally the cut-off voltage of a flow battery is controlled and adjusted according to the discharge duration and the resistance, so that the phenomenon that the overcharge and over-discharge are caused and the service life of the battery is shortened when the self-discharge of the battery and the output characteristic of the battery are influenced by the temperature and concentration change of the resistance of the electrolyte is avoided;
2. when the battery is charged/discharged, the concentration of each component in the electrolyte and the temperature of the electrolyte are changed, the resistance of the electrolyte can be measured in real time by the measuring method, and the problems that the resistance change of the electrolyte caused by the temperature and concentration change of the electrolyte in the charging/discharging process cannot be monitored in time, the overcharge and the overdischarge are caused, and the service life of the battery is shortened are solved.
Drawings
FIG. 1 is a wiring diagram of the overall measurement of electrolyte resistance according to the present invention.
FIG. 2 is a diagram of an overall resistance measurement circuit of the present invention.
Fig. 3 is a schematic view of a connection structure of an electrolyte pipeline and an electric cylinder according to the present invention.
Fig. 4 is a sectional view showing the connection of an electrolyte pipe with an electric cylinder according to the present invention.
FIG. 5 is a schematic diagram of the system of the present invention.
The reference signs are: the device comprises an electrolyte storage tank 1, an electrolyte pipeline 2, an electrochemical analyzer 3, a graphite electrode 4, a recording device 5, a lead 6, an electric cylinder 7, a flowmeter 8, a pressure pump 9, a push rod 10, a cavity 11 and a through hole 12.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The method for measuring the resistance of the electrolyte of the flow battery on line according to the drawings 1 and 2 comprises a measuring device, wherein the measuring device comprises an electrolyte storage tank 1, an electrolyte pipeline 2, an electrochemical analyzer 3, a graphite electrode 4 and a recording device 5, two ends of the electrolyte pipeline 2 are respectively connected with the electrolyte storage tank 1 to form an electrolyte loop, two graphite electrodes 4 are arranged inside two ends of one electrolyte pipeline 2 outside the flow battery, the graphite electrode 4 is connected with the electrochemical analyzer 3 through a lead 6, one end of the graphite electrode 4, far away from the electrolyte pipeline 2, is fixedly connected with an electric cylinder 7, a flowmeter 8 is arranged inside the electrolyte pipeline 2, and the electrolyte pipeline 2 is connected with a pressure pump 9;
two ends of each single cell in the flow battery are connected with the electrolyte pipeline 2 through a common main liquid conveying pipe;
the electrochemical analyzer 3 is in signal connection with a recording device 5 through a data line, and the recording device 5 is a computer;
the specific method of use of the measuring device is as follows:
step S1, laying a line; firstly, respectively leading out electrolyte pipelines 2 from a positive electrolyte storage tank 1 and a negative electrolyte storage tank 1 of a flow battery, connecting a graphite electrode 4 with an electric cylinder 7, leading out the positive electrolyte storage tank 1 and the negative electrolyte storage tank 1 to two electrolyte pipelines 2 outside the flow battery, respectively installing the graphite electrode 4 and the electric cylinder 7 at two ends, respectively connecting two groups of graphite electrodes 4 with an electrochemical analyzer 3 through leads 6, and then respectively connecting the electric cylinder 7, a flowmeter 8 and a pressure pump 9 with a recording device 5;
step S2, measuring resistance; respectively measuring the resistance and calculating the resistivity of the positive electrolyte and the negative electrolyte in real time, and specifically comprising the following steps:
s2.1, controlling the pressure pump 9 to work by the recording equipment 5, and conveying the electrolyte in the electrolyte storage tank 1 into each single battery in the flow battery through the electrolyte pipeline 2 so as to enable the flow battery to perform charging and discharging work;
s2.2, electrifying the two graphite electrodes 4, forming a resistance measurement loop with the electrolyte conveyed in the electrolyte pipeline 2 and the electrochemical analyzer 3, measuring by the electrochemical analyzer 3 to obtain the electrolyte resistance, and sending the measurement result to the recording equipment 5 for storage;
step S2.3, after the length of the electrolyte passing between the two graphite electrodes 4 is determined, the flow meter 8 monitors the flow of the electrolyte in real time, sends the flow value to the recording equipment 5, calculates the cross-sectional area of the electrolyte, and the recording equipment 5 calculates the resistivity according to the resistance of the electrolyte obtained in the step, wherein the calculation formula is as follows:
wherein R represents resistance, ρ represents resistivity, L represents the length of the electrolyte passing between the two graphite electrodes 4, and S represents the cross-sectional area of the electrolyte passing between the two graphite electrodes 4;
and S2.4, after the recording equipment 5 obtains the initial resistance value, obtaining the resistance of each part of the electrolyte loop in the galvanic pile, controlling the electric cylinder 7 to perform telescopic work, driving the two graphite electrodes 4 to move back and forth by the electric cylinder 7, changing the length of the electrolyte passing between the two graphite electrodes 4, changing the length measurement resistance for multiple times, calculating the resistivity, obtaining the resistance value of each part of the electrolyte loop in the galvanic pile, and finally regulating the cut-off voltage of the flow battery (the voltage is reduced to the lowest working voltage value at which the battery is not suitable for continuous discharge) according to the discharge time length and the resistance control.
According to the method for measuring the electrolyte resistance of the flow battery on line shown in fig. 3 to 5, one end of the electric cylinder 7 is in transmission connection with a push rod 10, one end of the push rod 10 penetrates through the outer wall of the electrolyte pipeline 2 and extends into the electrolyte pipeline 2 to be fixedly connected with the graphite electrode 4, and the push rod 10 is movably clamped with the electrolyte pipeline 2;
a cavity 11 is arranged in one end of the push rod 10 close to the graphite electrode 4, through holes 12 are formed in the top end of the cavity 11 and the end face of the push rod 10 connected with the graphite electrode 4, the lead 6 is arranged in the cavity 11, one end of the lead 6 penetrates through the through hole 12 in the end face of the push rod 10 to be connected with the graphite electrode 4, and the other end of the lead 6 penetrates through the through hole 12 in the top end of the push rod 10 to be connected with the electrochemical analyzer 3;
the flowmeter 8 is connected with the recording device 5 through an A/D converter, and the recording device 5 is connected with the pressure pump 9 and the electric cylinder 7 through a D/A converter;
the implementation mode is specifically as follows: the electric cylinder 7 drives the graphite electrodes 4 to move in the electrolyte pipeline 2, the length of electrolyte between the two graphite electrodes 4 can be changed, so that the resistivity of a plurality of groups of electrolytes can be measured, the accuracy of the resistivity is ensured, in addition, the wiring can be facilitated through the distribution of the wires 6 in the cavity 11, the problem that the wiring in the electrolyte pipeline 2 is not good is avoided, and the installation is facilitated;
the flowmeter 8 measures the flow of the electrolyte inside the electrolyte pipeline 2, so that the cross-sectional area of the electrolyte in the pipeline can be calculated, the resistance value can be calculated conveniently, the recording equipment 5 can intelligently control the working efficiency of the pressure pump 9 according to the flow value, the extraction cross-sectional area of the electrolyte is controlled, and the charging and discharging efficiency of the battery is controlled.
The points to be finally explained are: first, in the description of the present application, it should be noted that, unless otherwise specified and limited, the terms "mounted," "connected," and "connected" should be understood broadly, and may be a mechanical connection or an electrical connection, or a communication between two elements, and may be a direct connection, and "upper," "lower," "left," and "right" are only used to indicate a relative positional relationship, and when the absolute position of the object to be described is changed, the relative positional relationship may be changed;
secondly, the method comprises the following steps: in the drawings of the disclosed embodiments of the invention, only the structures related to the disclosed embodiments are referred to, other structures can refer to common designs, and the same embodiment and different embodiments of the invention can be combined with each other without conflict;
and finally: the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention are intended to be included in the scope of the present invention.
Claims (4)
1. A method for measuring the resistance of the electrolyte of a flow battery on line is characterized in that: the device comprises a measuring device, wherein the measuring device comprises an electrolyte storage tank (1), an electrolyte pipeline (2), an electrochemical analyzer (3), a graphite electrode (4) and recording equipment (5), two ends of the electrolyte pipeline (2) are respectively connected with the electrolyte storage tank (1) to form an electrolyte loop, the graphite electrode (4) is arranged in two and is respectively arranged inside two ends of one electrolyte pipeline (2) outside a flow battery, the graphite electrode (4) is connected with the electrochemical analyzer (3) through a lead (6), one end, far away from the electrolyte pipeline (2), of the graphite electrode (4) is fixedly connected with an electric cylinder (7), a flowmeter (8) is arranged inside the electrolyte pipeline (2), and the electrolyte pipeline (2) is connected with a pressure pump (9);
one end of the electric cylinder (7) is in transmission connection with a push rod (10), one end of the push rod (10) penetrates through the outer wall of the electrolyte pipeline (2) and extends to the inside of the electrolyte pipeline (2) to be fixedly connected with the graphite electrode (4), the push rod (10) is movably clamped with the electrolyte pipeline (2), a cavity (11) is arranged inside one end, close to the graphite electrode (4), of the push rod (10), through holes (12) are formed in the top end of the cavity (11) and the connection end face of the push rod (10) and the graphite electrode (4), the lead (6) is arranged inside the cavity (11), one end of the lead (6) penetrates through the through hole (12) in the end face of the push rod (10) to be connected with the graphite electrode (4), and the other end of the lead (6) penetrates through the through hole (12) in the top end of the push rod (10) to be connected with the electrochemical analyzer (3);
the specific method of use of the measuring device is as follows:
step S1, laying a line; firstly, respectively leading out electrolyte pipelines (2) from a positive electrolyte storage tank (1) and a negative electrolyte storage tank (1) of a flow battery, connecting a graphite electrode (4) with an electric cylinder (7), leading out the positive electrolyte storage tank (1) and the negative electrolyte storage tank (1) to two electrolyte pipelines (2) outside the flow battery, respectively installing the graphite electrode (4) and the electric cylinder (7) at two ends, respectively connecting two groups of graphite electrodes (4) with an electrochemical analyzer (3) through leads (6), and then respectively connecting the electric cylinder (7), a flowmeter (8) and a pressure pump (9) with recording equipment (5);
step S2, measuring resistance; respectively measuring the resistance and the resistivity of the positive electrolyte and the negative electrolyte in real time, and specifically comprising the following steps:
s2.1, controlling a pressure pump (9) to work by the recording equipment (5), and conveying the electrolyte in an electrolyte storage tank (1) into each single battery in the flow battery through an electrolyte pipeline (2) so as to enable the flow battery to perform charging and discharging work;
s2.2, electrifying the two graphite electrodes (4), forming a resistivity measurement loop with the electrolyte conveyed in the electrolyte pipeline (2) and the electrochemical analyzer (3), obtaining the resistivity of the electrolyte after the electrochemical analyzer (3) measures the resistivity, and sending a measurement result to the recording equipment (5) for storage;
s2.3, after the length of the electrolyte passing between the two graphite electrodes (4) is determined, the flow meter (8) monitors the flow of the electrolyte in real time, sends the flow value to the recording equipment (5), calculates the cross-sectional area of the electrolyte, and the recording equipment (5) calculates the resistance of the electrolyte according to the resistivity of the electrolyte obtained in the step and a resistance calculation formula, wherein the resistance calculation formula is as follows:
wherein R represents resistance, rho represents resistivity, L represents the length of the electrolyte passing between the two graphite electrodes (4), and S represents the cross-sectional area of the electrolyte passing between the two graphite electrodes (4);
s2.4, after the initial resistance value is obtained by the recording equipment (5), the electric cylinder (7) is controlled to perform telescopic work, the electric cylinder (7) drives the two graphite electrodes (4) to move back and forth to work, so that the length of electrolyte passing between the two graphite electrodes (4) is changed, the length measurement resistivity is changed for multiple times, the accurate resistivity is measured, then the resistance value of the electrolyte is obtained, and finally the cut-off voltage of the flow battery is controlled and adjusted according to the discharge time length and the resistance.
2. The method for on-line measuring the electrolyte resistance of the flow battery according to claim 1, wherein the method comprises the following steps: and two ends of each single cell in the flow battery are connected with the electrolyte pipeline (2) through pipelines.
3. The method for on-line measuring the electrolyte resistance of the flow battery according to claim 1, wherein the method comprises the following steps: the electrochemical analyzer (3) is in signal connection with a recording device (5) through a data line, and the recording device (5) is a computer.
4. The method for on-line measuring the electrolyte resistance of the flow battery according to claim 1, wherein the method comprises the following steps: the flowmeter (8) is connected with a recording device (5) through an A/D converter, and the recording device (5) is connected with a pressure pump (9) and an electric cylinder (7) through a D/A converter.
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| CN111273182B (en) * | 2020-02-24 | 2022-02-01 | 山东科技大学 | Flow battery bipolar plate structure and method for measuring current distribution |
| CN111397752A (en) * | 2020-04-16 | 2020-07-10 | 德州尧鼎光电科技有限公司 | Liquid conductance adjustable temperature sensor |
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| JP2003173812A (en) * | 2001-12-04 | 2003-06-20 | Sumitomo Electric Ind Ltd | Capacity drop detection method of redox flow battery |
| CN103344840A (en) * | 2013-07-03 | 2013-10-09 | 东北大学 | Method and device for conducting absolute measurement on electrical conductivity of solution and high-temperature melt |
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