CN114420982A - System and method for monitoring charge state of flow battery on line - Google Patents
System and method for monitoring charge state of flow battery on line Download PDFInfo
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Abstract
The application discloses a flow battery charge state on-line monitoring system and a method, which relate to the technical field of battery protection and comprise the steps of transmitting laser signals with preset frequency into positive and negative liquid storage tanks, collecting emergent scattered light signals, splitting the light signals to obtain first optical signals and second optical signals, filtering the first optical signals to obtain third optical signals which do not contain the preset frequency, and performing photoelectric conversion on the third optical signals and the second optical signals to obtain first electric signals and second electric signals. The temperature correction coefficient is obtained by processing the first electric signal, the charge states of the positive single battery and the negative single battery are obtained by processing the second electric signal, and the charge states of the flow battery are obtained by combining the first electric signal and the second electric signal and then output on line. The on-line monitoring method and the on-line monitoring system have the advantages that the charged state is determined directly by analyzing the reactant, the temperature correction coefficient is introduced, the monitoring accuracy, the monitoring efficiency and the sustainability are improved, and the charged state is monitored on line through on-line output.
Description
Technical Field
The application relates to the technical field of battery protection, in particular to a system and a method for monitoring the charge state of a flow battery on line.
Background
With the continuous construction of new energy, large-scale battery energy storage technology is also developing vigorously. The flow battery is one of the most promising large-scale energy storage technologies which occupies a large share in renewable energy power generation at present. The State of Charge (SOC) of a battery is the ratio of the remaining capacity of the battery to its full Charge capacity, and accurate prediction thereof directly concerns the Charge and discharge safety of the battery and affects the cycle life of the battery. Therefore, the charge state of the flow battery needs to be continuously monitored on line, so that damage caused by overcharge or overdischarge is avoided, the safe and stable operation of the flow battery is ensured, and the large-scale engineering application of battery energy storage is promoted.
At present, the mainstream battery state of charge monitoring methods comprise an open-circuit voltage method, an ampere-hour integration method, a neural network method and the like, but the methods all have great problems. The open-circuit voltage method needs to acquire the open-circuit voltage at two ends of the battery pack, look up a table to obtain the state of charge of the battery at the moment, and cannot perform online monitoring. The ampere-hour integration method is extremely dependent on the setting of the initial value of the state of charge, the accuracy of current collection is greatly influenced by the ambient temperature, and errors are easy to accumulate. The neural network method needs a large amount of known data for driving, has slow calculation speed and cannot be put into engineering application.
In addition, the current mainstream battery state of charge monitoring method cannot directly monitor factors such as electrolyte concentration and electrolyte temperature which affect the state of charge, and needs to depend on external parameters, so that the precision is low. Or require a large amount of known data resulting in inefficiency. Or direct contact with corrosive electrolytes is required, resulting in low sustainability.
Therefore, the accuracy, efficiency and sustainability of the existing battery state of charge monitoring method cannot meet the user requirements.
Disclosure of Invention
Aiming at the defects in the prior art, the application aims to provide an online monitoring system for the charge state of a flow battery, which directly analyzes reactants in electrolyte to determine the charge state, introduces a temperature correction coefficient, improves monitoring accuracy, monitoring efficiency and sustainability, and realizes online output of the charge state.
In order to achieve the above purposes, the technical scheme is as follows:
the first aspect of the present application provides a flow battery state of charge on-line monitoring system, including:
the light source module is used for emitting laser signals with preset frequency into the positive and negative liquid storage tanks of the redox flow battery, and the laser signals are emitted from the positive and negative liquid storage tanks in the form of scattered light signals after being scattered by positive and negative electrolytes in the positive and negative liquid storage tanks;
the optical acquisition module is used for acquiring the scattered light signals, splitting the scattered light signals into beams to obtain first optical signals and second optical signals, and filtering the first optical signals to obtain third optical signals which do not contain the preset frequency, and then respectively performing photoelectric conversion on the third optical signals and the second optical signals to obtain first electric signals and second electric signals;
the optical analysis module is connected with the optical acquisition module, and is used for acquiring the first electric signal and the second electric signal, processing the first electric signal to obtain the current temperature and the corresponding temperature correction coefficient, processing the second electric signal to obtain the charge states of the positive and negative single cells, and correcting the charge states of the positive and negative single cells according to the temperature correction coefficient to obtain the charge state of the flow battery;
and the communication module is connected with the optical analysis module and used for collecting the charge state of the flow battery and sending the charge state to the controller of the flow battery.
In some embodiments, the light collection module is integrated within a light collection device that is transparent to a light receiving surface of the optical signal exit region, and the light receiving surface is shaped to mate with the optical signal exit region to enclose the optical signal exit region.
In some embodiments, the light collection module comprises:
the lens unit is used for receiving the scattered light signals, converging the scattered light signals and outputting the converged scattered light signals;
the light splitting unit is connected with the lens unit and used for receiving the converged scattered light signals, splitting the scattered light signals into a first light signal and a second light signal and outputting the first light signal and the second light signal;
the filtering unit is connected with the optical splitting unit and used for receiving the first optical signal, filtering the first optical signal to filter light with a preset frequency to obtain a third optical signal, and then outputting the third optical signal;
and the photoelectric conversion unit is connected with the light splitting unit and the filtering unit, and is used for receiving the third optical signal and the second optical signal, performing photoelectric conversion on the third optical signal and the second optical signal respectively to obtain a first electric signal and a second electric signal, and outputting the first electric signal and the second electric signal.
In some embodiments, the light collection module further comprises:
and the data temporary storage unit is connected with the photoelectric conversion unit, and is used for receiving and storing the first electric signal and the second electric signal, and sending the first electric signal and the second electric signal to the optical analysis module at a preset speed when receiving an acquisition request sent by the optical analysis module.
In some embodiments, the optical analysis module comprises:
the temperature identification unit is used for acquiring the first electric signal, obtaining the power ratio of the Stokes light and the anti-Stokes light according to the first electric signal, obtaining the current temperature according to the power ratio and obtaining a temperature correction coefficient according to the current temperature;
the electrolyte concentration identification unit is used for acquiring the second electric signal, processing the second electric signal to obtain the electrolyte concentrations of the positive and negative electrode electrolytes, and processing the electrolyte concentrations to obtain the charge states of the positive and negative single cells;
and the overall charge state calculation unit is connected with the temperature identification unit and the electrolyte concentration identification unit and is used for correcting the charge state of the positive and negative single cells according to the temperature correction coefficient to obtain the charge state of the flow battery.
In some embodiments, the temperature identification unit calculates the temperature correction coefficient by using the following formula:
wherein the content of the first and second substances,
eta represents the temperature correction coefficient of the positive and negative single cells;
t represents the current temperature of the positive and negative electrolytes.
In some embodiments, the electrolyte concentration identification unit calculates the electrolyte concentration by using the following formula:
wherein the content of the first and second substances,
l represents the optical path of the laser signal in the positive and negative electrolyte;
In some embodiments, the electrolyte concentration identification unit calculates the charge states of the positive and negative single cells by using the following formula:
wherein the content of the first and second substances,
In some embodiments, the overall state of charge calculation unit obtains the state of charge of the flow battery by using the following formula:
wherein the content of the first and second substances,
The second aspect of the present application provides an online monitoring method for a state of charge of a flow battery, including:
emitting laser signals with preset frequency into positive and negative liquid storage tanks of the redox flow battery, wherein the laser signals are emitted from the positive and negative liquid storage tanks in the form of scattered light signals after being scattered by positive and negative electrolytes in the positive and negative liquid storage tanks;
collecting the scattered light signals, splitting the scattered light signals to obtain first optical signals and second optical signals, filtering the first optical signals to obtain third optical signals which do not contain the preset frequency, and respectively carrying out photoelectric conversion on the third optical signals and the second optical signals to obtain first electric signals and second electric signals;
acquiring the first electric signal and the second electric signal, processing according to the first electric signal to obtain the current temperature and the corresponding temperature correction coefficient, processing according to the second electric signal to obtain the charge states of the positive and negative single cells, and correcting the charge states of the positive and negative single cells according to the temperature correction coefficient to obtain the charge state of the flow battery;
and collecting the charge state of the flow battery, and sending the charge state to a controller of the flow battery.
The beneficial effect that technical scheme that this application provided brought includes:
the online monitoring system and the online monitoring method are convenient to operate, the structure of the conventional flow battery is not required to be changed, and the online monitoring system is not in direct contact with corrosive electrolyte, so that the long-term effective online monitoring of the system is ensured.
The online monitoring system and the online monitoring method do not indirectly monitor external parameters such as current and voltage, but directly analyze reactants to determine the state of charge, improve the accuracy and efficiency of monitoring the state of charge of the flow battery, and effectively solve the problem that the overall state of charge of the battery is not uniform with the states of charge of positive and negative single batteries.
The online monitoring system and the online monitoring method can monitor the temperature of the electrolyte, and improve the online monitoring accuracy of the state of charge of the flow battery by introducing the temperature correction coefficient.
The online monitoring system and the online monitoring method can output the charge state of the flow battery to the battery controller of the flow battery in real time online, and the battery controller is convenient to control the charging and discharging process of the flow battery.
Drawings
Fig. 1 is a schematic overall structure diagram of an on-line monitoring system for the state of charge of a flow battery in an embodiment of the invention.
Fig. 2 is a functional module schematic diagram of an online monitoring system for the state of charge of a flow battery in an embodiment of the invention.
Fig. 3 is a flowchart of an online monitoring method for the state of charge of a flow battery according to an embodiment of the present invention.
Detailed Description
The present application will be described in further detail with reference to the accompanying drawings and examples.
As shown in fig. 1 and 2, the present invention provides an online monitoring system for a state of charge of a flow battery, including a light source module 1, an optical acquisition module 2, an optical analysis module 3, and a communication module 4, where the optical acquisition module 2 is connected to the optical analysis module 3. The outer walls of the positive and negative liquid storage tanks of the flow battery are provided with transparent inlets and outlets, and light rays can penetrate through the positive and negative liquid storage tanks through the inlets and outlets. The light source module 1 emits laser signals with preset frequency to the anode liquid storage tank and the cathode liquid storage tank of the cathode liquid storage tank 6. The light collection module 2 collects the emitted scattered light signals, splits the light signals to obtain first light signals and second light signals, filters the first light signals to obtain third light signals which do not contain preset frequency, and performs photoelectric conversion on the third light signals and the second light signals to obtain first electric signals and second electric signals. The optical analysis module 3 obtains the temperature correction coefficient through processing the first electric signal, obtains the charge state of the positive and negative single cells through processing the second electric signal, and obtains the charge state of the flow battery through combining the temperature correction coefficient and the charge state of the positive and negative single cells. The communication module 4 is connected with the optical analysis module 3, the optical analysis module 3 sends the state of charge of the flow battery to the optical analysis module 3, and the optical analysis module 4 sends the state of charge of the flow battery to the battery controller of the flow battery on line, so that the battery controller can conveniently control the charging and discharging processes of the flow battery, and overshoot and overdischarge of the battery are avoided.
In this embodiment, since the positive and negative electrolytes have a certain temperature, the laser signal is affected by the temperature to generate scattered light with a frequency different from the preset frequency, that is, the scattered light signal includes light with the same frequency as the preset frequency and light with a frequency different from the preset frequency, the temperature of the positive and negative electrolytes can be derived according to the light with the frequency different from the preset frequency included in the scattered light signal, and the electric quantity is corrected by setting a temperature correction coefficient according to the temperature of the positive and negative electrolytes, so that the electric quantity calculation accuracy can be improved.
The system does not need to change the structure of the existing redox flow battery, does not need to be in direct contact with corrosive electrolyte, does not need to indirectly monitor external parameters such as current and voltage, only needs to project laser signals from one side of the positive and negative liquid storage tanks to the inside of the positive and negative liquid storage tanks, receives scattered light signals emitted from the inside of the positive and negative liquid storage tanks from the other side of the positive and negative liquid storage tanks, generates corresponding scattered light signals by scattering of the laser signals in the positive and negative liquid storage tanks under the influence of electrolyte concentration, electrolyte temperature and the like, can directly analyze reactants in the electrolyte to determine the charge state by analyzing the laser signals and the scattered light signals, introduces a temperature correction coefficient, and can improve the monitoring accuracy. The charge state of the flow battery is transmitted to the battery pack balance controller in real time through the communication module 4 to control the running state of the flow battery and prevent overcharge and overdischarge of the flow battery.
Furthermore, each module of the flow battery state of charge on-line monitoring system comprises a communication unit (not shown in the figure), can communicate with each other to unify time sequences, and can be manually controlled by a background control system to ensure the flexibility of monitoring the state of charge of the battery.
Specifically, the flow battery comprises an anode liquid storage tank 5 and a cathode liquid storage tank 6 which are arranged side by side, anode electrolyte is contained in the anode liquid storage tank 5, cathode electrolyte is contained in the cathode liquid storage tank 6, one end of an anode electrode is positioned in the anode electrolyte, and one end of a cathode electrode is positioned in the cathode electrolyte. The positive liquid storage tank 5 and the negative liquid storage tank 6 are collectively called as positive and negative liquid storage tanks, and the positive electrolyte and the negative electrolyte are collectively called as positive and negative electrolytes.
The light source module 1 is used for emitting laser signals with preset frequency into positive and negative liquid storage tanks of the redox flow battery, and the laser signals are emitted from the positive and negative liquid storage tanks in the form of scattered light signals after being scattered by positive and negative electrolytes in the positive and negative liquid storage tanks. For example, the light source module 1 includes a positive laser source 7 for emitting a laser signal into the positive liquid storage tank 5 and a negative laser source 8 for emitting a laser signal into the negative liquid storage tank 6, the positive laser source 7 is connected to the positive liquid storage tank 5 through a positive optical fiber 9, and the negative laser source 8 is connected to the negative liquid storage tank 6 through a negative optical fiber 10. The positive liquid storage tank 5 and the negative liquid storage tank 6 are arranged side by side, and the positive laser source 7 and the negative laser source 8 are respectively positioned on the outer sides of the two liquid storage tanks and are respectively used for emitting laser signals in the horizontal direction into the two liquid storage tanks. The optical acquisition module 2 is located between the two reservoirs.
The optical acquisition module 2 acquires the scattered light signals, and splits the scattered light signals to obtain first optical signals and second optical signals, and is further configured to perform photoelectric conversion on the third optical signals and the second optical signals to obtain first electrical signals and second electrical signals respectively after filtering the first optical signals to obtain third optical signals that do not include the preset frequency. For example, the light collection module 2 is located between two fluid reservoirs. The light collection module 2 collects scattered light signals emitted by the positive liquid storage tank 5 and the negative liquid storage tank 6 respectively, and splits the two scattered light signals respectively to obtain two groups of first light signals and second light signals, the current temperature, temperature correction coefficient and charge state of the positive single electrode can be obtained through subsequent processing according to the first light signals and the second light signals emitted from the positive liquid storage tank 5, the current temperature, temperature correction coefficient and charge state of the negative single electrode can be obtained through subsequent processing according to the first light signals and the second light signals emitted from the negative liquid storage tank 6, and the charge state of the redox flow battery can be obtained through subsequent processing according to the temperature correction coefficient and charge state of the positive single electrode and the temperature correction coefficient and charge state of the negative single electrode.
The optical acquisition module 2 is used for acquiring the first electrical signal and the second electrical signal, processing the first electrical signal to obtain the current temperature and the corresponding temperature correction coefficient, processing the second electrical signal to obtain the charge states of the positive and negative single cells, and correcting the charge states of the positive and negative single cells according to the temperature correction coefficient to obtain the charge state of the flow battery.
In the embodiment, the electrolyte concentration is directly analyzed by analyzing the scattered light signals, so that the charge state of the flow battery is obtained, the monitoring precision of the charge state of the battery is improved, and the problem that the overall charge state of the flow battery is not uniform with the charge states of positive and negative single batteries is effectively solved. The temperature condition of the electrolyte of the flow battery is synchronously monitored, and a temperature correction coefficient is introduced, so that the accuracy of the charge state monitoring is further improved.
In a preferred embodiment, when the positive and negative liquid tanks are partially transparent, the outer wall of the positive and negative liquid tanks includes a transparent optical signal inlet region and an optical signal outlet region, the laser signal is incident into the positive and negative liquid tanks from the optical signal inlet region, and the scattered light signal is emitted out of the positive and negative liquid tanks from the optical signal outlet region.
When the anode liquid storage tank and the cathode liquid storage tank of the cathode liquid storage tank 6 are completely transparent, the shapes of the anode liquid storage tank and the cathode liquid storage tank can be transparent cylinders, transparent cubes or transparent polyhedrons. When the positive and negative liquid storage tanks are completely transparent, any one position can be selected manually as an optical signal inlet area, and the area opposite to the optical signal inlet area is set as an optical signal outlet area.
The light collection module 2 is integrated inside a specially-made light collection device A, a light receiving surface of the light collection device A facing to the light signal outlet area is transparent, and the shape of the light receiving surface is matched with that of the light signal outlet area so as to wrap the light signal outlet area, and therefore emitted scattered light signals are gathered and collected as much as possible.
For example, when the positive and negative liquid storage tanks are partially transparent cylinders, the light collection surface is a parabolic transparent surface, the shape of the parabolic transparent surface is matched with that of the optical signal outlet area, and the optical signal outlet areas of the positive and negative liquid storage tanks are embedded in the notches of the parabolic transparent surface and are attached to the inner walls of the notches of the parabolic transparent surface, so that the light collection surface collects scattered light signals as much as possible, and the detection precision is improved.
When the positive and negative liquid storage tanks are partially transparent square cylinders and the optical signal outlet area is rectangular, the light collection surface is a rectangular transparent surface, the shape of the rectangular transparent surface is matched with that of the optical signal outlet area, and the optical signal outlet areas of the positive and negative liquid storage tanks are attached to the rectangular transparent surface, so that the light collection surface collects scattered light signals as much as possible, and the detection precision is improved.
When the positive and negative liquid storage tanks are completely transparent cylinders, the light collection surface is a parabolic transparent surface, and the artificially selected light signal outlet area on the outer wall of the positive and negative liquid storage tanks is embedded in the notch of the parabolic transparent surface and is attached to the inner wall of the notch of the parabolic transparent surface, so that the light collection surface collects scattered light signals as much as possible, and the detection precision is improved.
When the positive and negative liquid storage tanks are completely transparent square cylinders and the artificially selected optical signal outlet area is rectangular, the light collection surface is a rectangular transparent surface, the shape of the rectangular transparent surface is matched with that of the last selected optical signal outlet area, and the optical signal outlet areas of the positive and negative liquid storage tanks are attached to the rectangular transparent surface, so that the light collection surface collects scattered light signals as much as possible, and the detection precision is improved. In a preferred embodiment, the light source module 1 includes a laser light source 11, a modulation unit 12, and an optical fiber unit 13, where the laser light source 11 is configured to generate laser light, and the modulation unit 12 is configured to modulate the laser light to obtain a laser signal with a preset frequency, and transmit the laser signal to the inside of the positive and negative liquid storage tanks through the optical fiber unit 13.
The laser light source 11 may be an HMS high-speed pulse light source, and the modulation unit 12 may be a pulse code modulator.
The laser light source 11 comprises an anode laser source 7 positioned outside the anode liquid storage tank 5 and a cathode laser source 8 positioned outside the cathode liquid storage tank 6, the optical fiber unit 13 comprises an anode optical fiber 9 connecting the anode laser source 7 and the anode liquid storage tank 5 and a cathode optical fiber 10 connecting the cathode laser source 8 and the cathode liquid storage tank 6,
after the modulated laser signals are input into the anode liquid storage tank 5 and the cathode liquid storage tank 6 in a laser mode, scattered light is generated under the action of the anode electrolyte and the cathode electrolyte respectively and is emitted from the anode liquid storage tank 5 and the cathode liquid storage tank 6 in the form of the scattered light signals.
In a preferred embodiment, the light collection module 2 includes a lens unit 21, an optical splitting unit 22, a filtering unit 23, and a photoelectric conversion unit 24, the lens unit 21 is connected to the optical splitting unit 22, the optical splitting unit 22 is connected to the filtering unit 23, and the photoelectric conversion unit 24 is connected to the optical splitting unit 22 and the filtering unit 23.
The lens unit 21 is used for receiving the scattered light signal, converging the scattered light signal and outputting the converged scattered light signal.
The optical splitting unit 22 is configured to receive the converged scattered light signal, split the converged scattered light signal into a first optical signal and a second optical signal, and output the first optical signal and the second optical signal.
The filtering unit 23 is configured to receive the first optical signal, filter the first optical signal to obtain a third optical signal, and output the third optical signal. The third optical signal is composed of stokes light and anti-stokes light.
The photoelectric conversion unit 24 is configured to receive the third optical signal and the second optical signal, perform photoelectric conversion on the third optical signal and the second optical signal respectively to obtain a first electrical signal and a second electrical signal, and output the first electrical signal and the second electrical signal.
The filtering unit 23 may use a grating filter sheet to distinguish the frequency of the transmitted and scattered light at the input photoelectric conversion unit 24. The photoelectric conversion unit 24 may employ a photomultiplier tube to convert an optical signal into an electrical signal while amplifying the signal.
In the present embodiment, the scattered light signal received by the lens unit 21 includes a scattered light signal emitted from the positive reservoir 5 and a scattered light signal emitted from the negative reservoir 6, and the lens unit 21 is, for example, a lens group, and converges the scattered light signals and outputs the converged signals to the light splitting unit 22. The light beam splitting unit 22 splits the scattered light signal emitted from the positive reservoir 5 into one set of the first light signal and the second light signal, and splits the scattered light signal emitted from the negative reservoir 6 into another set of the first light signal and the second light signal. The filtering unit 23 filters a preset frequency signal having the same frequency as the incident light frequency in the first light signal to obtain a third light signal, where the third light signal is composed of stokes light and anti-stokes light, and a corresponding electrolyte temperature can be obtained according to a ratio of the stokes light to the anti-stokes light.
In a preferred embodiment, the optical acquisition module 2 further includes a data temporary storage unit 25, connected to the photoelectric conversion unit 24, and configured to receive and store the first electrical signal and the second electrical signal, and send the first electrical signal and the second electrical signal to the optical analysis module 3 at a preset rate when receiving an acquisition request sent by the optical analysis module 3.
In this embodiment, the data temporary storage unit 25 may adopt a RAM (Random Access Memory, short for Random Access Memory) to temporarily store the first electrical signal and the second electrical signal, and the data temporary storage unit 25 transmits the signal to the optical analysis module 3 only when the optical analysis module 3 queries the optical acquisition module 2, so as to ensure timeliness of signal processing. The data temporary storage unit 25 can also preset a data transmission rate to control the data amount read each time, and the data transmission rate is matched with the signal processing speed for use, so that the processing efficiency is improved.
In a preferred embodiment, the optical analysis module 3 comprises a temperature identification unit 31, an electrolyte concentration identification unit 32, and a global state of charge calculation unit 33, the global state of charge calculation unit 33 being connected to the temperature identification unit 31 and the electrolyte concentration identification unit 32.
The temperature identification unit 31 is configured to obtain the first electrical signal, obtain a power ratio of the stokes light and the anti-stokes light according to the first electrical signal, obtain a current temperature according to the power ratio, and obtain a temperature correction coefficient according to the current temperature.
The electrolyte concentration identification unit 32 is configured to obtain the second electrical signal, process the second electrical signal to obtain electrolyte concentrations of the positive and negative electrodes of the electrolyte, and process the electrolyte concentrations to obtain charge states of the positive and negative single cells.
The overall state of charge calculation unit 33 is used for correcting the state of charge of the positive and negative single cells according to the temperature correction coefficient to obtain the state of charge of the flow battery.
The temperature identification unit 31 and the electrolyte concentration identification unit 32 may each include an oscilloscope, and power, light intensity, and the like may be obtained by detecting the first electrical signal and the second electrical signal with the oscilloscope.
Further, the temperature identification unit 31 calculates a temperature correction coefficient by using the following formula:
wherein eta represents the temperature correction coefficient of the positive and negative single cells,
the standard temperature of the positive and negative electrolytes is shown, and T represents the current temperature of the positive and negative electrolytes.
In this embodiment, after splitting a scattered light signal emitted from the anode liquid storage tank 5 to obtain a first light signal and a second light signal, filtering the first light signal to obtain a third light signal composed of stokes light and anti-stokes light, performing photoelectric conversion on the third light signal to obtain a first electrical signal, and obtaining the current temperature of the anode electrolyte in the anode liquid storage tank 5 according to the power ratio of the stokes light and the anti-stokes light in the first electrical signal. And (4) calculating the temperature correction coefficient of the corresponding positive electrode single electrode according to the formula (1).
After the scattered light signals emitted from the negative liquid storage tank 6 are subjected to beam splitting to obtain first light signals and second light signals, the first light signals are filtered to obtain third light signals formed by Stokes light and anti-Stokes light, the third light signals are subjected to photoelectric conversion to obtain first electric signals, and the current temperature of the negative electrolyte in the negative liquid storage tank 6 is obtained according to the power ratio of the Stokes light and the anti-Stokes light in the first electric signals. And (4) calculating the temperature correction coefficient corresponding to the negative single electrode according to the formula (1).
Further, the electrolyte concentration identification unit 32 calculates the electrolyte concentration by using the following formula:
wherein the content of the first and second substances,
indicating positive and negative polarityThe concentration of the electrolyte in the electrolyte solution,
showing the molar absorption coefficients of the positive electrolyte and the negative electrolyte, l showing the optical path of the laser signal in the positive electrolyte and the negative electrolyte,
the absorbance of the positive and negative electrode electrolytes is shown,
indicating the intensity of the scattered light signal exiting from the positive and negative electrolytes,
indicating the light intensity of the laser signal incident on the positive and negative electrolytes.
In the present embodiment, the electrolyte concentration corresponding to the positive electrolyte is calculated by using the above formula (2) according to the light intensity of the positive laser source 7 entering the positive liquid storage tank 5, the light intensity of the first light signal emitted from the positive liquid storage tank 5, the molar absorption coefficient of the positive electrolyte, and the optical length of the positive light source in the positive electrolyte.
And calculating the electrolyte concentration of the corresponding cathode electrolyte by using the formula (2) according to the light intensity of the cathode laser source 8 entering the cathode liquid storage tank 6, the light intensity of the first light signal emitted by the cathode liquid storage tank 6, the molar absorption coefficient of the cathode electrolyte and the optical path of the cathode light source in the cathode electrolyte.
Further, the electrolyte concentration identification unit 32 calculates the charge states of the positive and negative single cells by using the following formula:
wherein the content of the first and second substances,
indicating the state of charge of the positive and negative cells,
indicates the remaining capacity of the positive and negative single cells,
indicates the total amount of electricity of the positive and negative single cells,
represents the chemical equilibrium constant of the positive and negative single cells,
showing the electrolyte concentrations of the positive and negative electrode electrolytes,
the number of electrons in the electrolytes of both electrodes is shown.
In this embodiment, the state of charge of the positive single cell is calculated by using the above formula (3) based on the electrolyte concentration of the positive electrolyte, the chemical equilibrium constant of the positive electrolyte, the number of electrons in the electrolyte valence of the positive electrolyte, and the total electric quantity of the positive single cell.
And (3) calculating the charge state of the negative single cell by using the formula (3) according to the electrolyte concentration of the negative electrolyte, the chemical equilibrium constant of the negative electrolyte, the dielectric valence electron number of the negative electrolyte and the total electric quantity of the negative single electrode.
Further, the overall state of charge calculation unit 33 obtains the state of charge of the flow battery by using the following formula:
wherein the content of the first and second substances,
indicating the state of charge to the flow battery,
indicates the temperature correction coefficient of the positive electrode cell,
indicates the state of charge of the positive electrode unit cell,
indicates the temperature correction coefficient of the negative electrode single cell,
indicating the state of charge of the negative electrode cell.
In the present embodiment, the state of charge of the positive electrode single electrode is corrected by the temperature correction coefficient of the positive electrode single electrode, and the state of charge of the negative electrode single electrode is corrected by the temperature correction coefficient of the negative electrode single electrode, and then the smaller value of the two is taken as the state of charge of the flow battery.
As shown in fig. 3, the present invention further provides an online monitoring method for a state of charge of a flow battery, including:
and step S1, emitting laser signals with preset frequency into the positive and negative liquid storage tanks of the redox flow battery, wherein the laser signals are emitted from the positive and negative liquid storage tanks in the form of scattered light signals after being scattered by positive and negative electrolytes in the positive and negative liquid storage tanks.
Step S2, collecting the scattered light signal, splitting the scattered light signal into a first optical signal and a second optical signal, filtering the first optical signal to obtain a third optical signal that does not include the preset frequency, and performing photoelectric conversion on the third optical signal and the second optical signal to obtain a first electrical signal and a second electrical signal, respectively.
And step S3, acquiring the first electric signal and the second electric signal, processing the first electric signal to obtain the current temperature and the corresponding temperature correction coefficient, processing the second electric signal to obtain the charge states of the positive and negative single cells, and correcting the charge states of the positive and negative single cells according to the temperature correction coefficient to obtain the charge state of the flow battery.
And step S4, collecting the state of charge of the flow battery, and sending the state of charge to a controller of the flow battery.
In the embodiment, the concentration of the dielectric medium in the positive electrolyte and the concentration of the dielectric medium in the negative electrolyte are obtained through analysis and processing by collecting the transmission scattered light generated after incident laser passes through the positive electrolyte and the negative electrolyte, and the charge state of the flow battery is determined according to the number of the dielectric medium reaction valence electrons.
The method is convenient to operate, the structure of the conventional flow battery is not required to be changed, the conventional flow battery is not in direct contact with corrosive electrolyte, and long-term effective online monitoring is ensured.
The method has the advantages that external parameters such as current and voltage are not indirectly monitored, the state of charge is determined by directly analyzing reactants, the accuracy of monitoring the state of charge of the flow battery is improved, and the problem that the overall state of charge of the battery is not uniform with the states of charge of positive and negative single batteries is effectively solved.
Meanwhile, the temperature of the electrolyte can be additionally monitored, and the accuracy of online monitoring of the charge state of the flow battery is improved by introducing a temperature correction coefficient.
The charge state of the flow battery can be output to a battery controller of the flow battery in real time on line, and the battery controller is convenient to control the charge and discharge process of the flow battery.
The functions of the on-line monitoring system for the state of charge of the flow battery can correspond to the method.
The present application is not limited to the above embodiments, and it will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the principle of the present application, and such modifications and improvements are also considered to be within the scope of the present application.
Claims (10)
1. The flow battery state of charge on-line monitoring system is characterized by comprising:
the light source module is used for emitting laser signals with preset frequency into the positive and negative liquid storage tanks of the redox flow battery, and the laser signals are emitted from the positive and negative liquid storage tanks in the form of scattered light signals after being scattered by positive and negative electrolytes in the positive and negative liquid storage tanks;
the optical acquisition module is used for acquiring the scattered light signals, splitting the scattered light signals into beams to obtain first optical signals and second optical signals, and filtering the first optical signals to obtain third optical signals which do not contain the preset frequency, and then respectively performing photoelectric conversion on the third optical signals and the second optical signals to obtain first electric signals and second electric signals;
the optical analysis module is connected with the optical acquisition module, and is used for acquiring the first electric signal and the second electric signal, processing the first electric signal to obtain the current temperature and the corresponding temperature correction coefficient, processing the second electric signal to obtain the charge states of the positive and negative single cells, and correcting the charge states of the positive and negative single cells according to the temperature correction coefficient to obtain the charge state of the flow battery;
and the communication module is connected with the optical analysis module and used for collecting the charge state of the flow battery and sending the charge state to the controller of the flow battery.
2. The flow battery state of charge on-line monitoring system of claim 1, wherein the light collection module is integrated inside the light collection device, the light collection device is transparent towards the light receiving surface of the optical signal exit region, and the light receiving surface is matched with the shape of the optical signal exit region to wrap the optical signal exit region.
3. The flow battery state of charge on-line monitoring system of claim 1, wherein the light collection module comprises:
the lens unit is used for receiving the scattered light signals, converging the scattered light signals and outputting the converged scattered light signals;
the light splitting unit is connected with the lens unit and used for receiving the converged scattered light signals, splitting the scattered light signals into a first light signal and a second light signal and outputting the first light signal and the second light signal;
the filtering unit is connected with the optical splitting unit and used for receiving the first optical signal, filtering the first optical signal to filter light with a preset frequency to obtain a third optical signal, and then outputting the third optical signal;
and the photoelectric conversion unit is connected with the light splitting unit and the filtering unit, and is used for receiving the third optical signal and the second optical signal, performing photoelectric conversion on the third optical signal and the second optical signal respectively to obtain a first electric signal and a second electric signal, and outputting the first electric signal and the second electric signal.
4. The flow battery state of charge on-line monitoring system of claim 3, wherein the light collection module further comprises:
and the data temporary storage unit is connected with the photoelectric conversion unit, and is used for receiving and storing the first electric signal and the second electric signal, and sending the first electric signal and the second electric signal to the optical analysis module at a preset speed when receiving an acquisition request sent by the optical analysis module.
5. The flow battery state of charge on-line monitoring system of claim 1, wherein the optical analysis module comprises:
the temperature identification unit is used for acquiring the first electric signal, obtaining the power ratio of the Stokes light and the anti-Stokes light according to the first electric signal, obtaining the current temperature according to the power ratio and obtaining a temperature correction coefficient according to the current temperature;
the electrolyte concentration identification unit is used for acquiring the second electric signal, processing the second electric signal to obtain the electrolyte concentrations of the positive and negative electrode electrolytes, and processing the electrolyte concentrations to obtain the charge states of the positive and negative single cells;
and the overall charge state calculation unit is connected with the temperature identification unit and the electrolyte concentration identification unit and is used for correcting the charge state of the positive and negative single cells according to the temperature correction coefficient to obtain the charge state of the flow battery.
6. The flow battery state of charge on-line monitoring system of claim 5, wherein the temperature identification unit calculates a temperature correction coefficient by using the following formula:
wherein the content of the first and second substances,
eta represents the temperature correction coefficient of the positive and negative single cells;
t represents the current temperature of the positive and negative electrolytes.
7. The flow battery state of charge on-line monitoring system of claim 5, wherein the electrolyte concentration identification unit calculates the electrolyte concentration by using the following formula:
wherein the content of the first and second substances,
l represents the optical path of the laser signal in the positive and negative electrolyte;
8. The flow battery state of charge on-line monitoring system of claim 7, wherein the electrolyte concentration recognition unit calculates the state of charge of positive and negative single cells by using the following formula:
wherein the content of the first and second substances,
9. The system for on-line monitoring of the state of charge of the flow battery according to claim 5, wherein the overall state of charge calculation unit calculates the state of charge of the flow battery by using the following formula:
wherein the content of the first and second substances,
10. The method for monitoring the state of charge of the flow battery on line is characterized by comprising the following steps:
emitting laser signals with preset frequency into positive and negative liquid storage tanks of the redox flow battery, wherein the laser signals are emitted from the positive and negative liquid storage tanks in the form of scattered light signals after being scattered by positive and negative electrolytes in the positive and negative liquid storage tanks;
collecting the scattered light signals, splitting the scattered light signals to obtain first optical signals and second optical signals, filtering the first optical signals to obtain third optical signals which do not contain the preset frequency, and respectively carrying out photoelectric conversion on the third optical signals and the second optical signals to obtain first electric signals and second electric signals;
acquiring the first electric signal and the second electric signal, processing according to the first electric signal to obtain the current temperature and the corresponding temperature correction coefficient, processing according to the second electric signal to obtain the charge states of the positive and negative single cells, and correcting the charge states of the positive and negative single cells according to the temperature correction coefficient to obtain the charge state of the flow battery;
and collecting the charge state of the flow battery, and sending the charge state to a controller of the flow battery.
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