CN104155611A - Alternating-current impedance analytical method of electrochemical energy storage device and analytical method of working state of electrochemical energy storage device - Google Patents
Alternating-current impedance analytical method of electrochemical energy storage device and analytical method of working state of electrochemical energy storage device Download PDFInfo
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Abstract
The invention discloses an alternating-current impedance analytical method of an electrochemical energy storage device. The method comprises steps as follows: an integrated DC/DC converter is provided and comprises a first DC/DC converter, a disturbance source and a controller, and the first DC/DC converter is connected with the disturbance source in parallel; the controller switches on the disturbance source and controls the disturbance source to generate a current disturbance signal simultaneously; the output current of the electrochemical energy storage device is disturbed by the current disturbance signal; the disturbed output current and the output voltage of the electrochemical energy storage device are detected; the impedance corresponding to the frequency of the current disturbance signal is calculated according to the current disturbance signal as well as the disturbed output current and the output voltage, the frequency of the current disturbance signal is changed, and the output current of the electrochemical energy storage device is disturbed again to obtain the alternating-current impedance spectrum of the electrochemical energy storage device.
Description
Technical Field
The invention relates to an alternating current impedance analysis method of an electrochemical energy storage device and a monitoring method of the working state of the electrochemical energy storage device.
Background
A hydrogen-oxygen Proton Exchange Membrane Fuel Cell (PEMFC) is an electrochemical device, which directly converts chemical energy into electric energy, and the energy conversion of a traditional internal combustion engine is limited by carnot cycle, while the energy conversion of the hydrogen-oxygen Proton Exchange Membrane Fuel Cell is not limited by carnot cycle, and theoretically, the energy conversion efficiency is higher. Because the substances participating in the reaction are hydrogen and air, the reaction product is water, and no harmful emissions are generated, the method is favored by people and is gradually applied to the fields of standby power stations, transportation, mobile power supplies and the like.
The output characteristic of the proton exchange membrane fuel cell is direct current, the output voltage of a single piece of the proton exchange membrane fuel cell is less than 1V, typically 0.7V, and in order to provide higher voltage, a plurality of fuel cell single pieces are required to be connected in series to form a fuel cell stack, and the output power is correspondingly improved. The fuel cell single chip is composed of an anode Gas Diffusion Layer (GDL), a Membrane Electrode Assembly (MEA), and a cathode Gas Diffusion Layer.
The fuel cell stack is a core component of a fuel cell power generation system, and a plurality of accessory systems are arranged at the periphery of the stack to assist the fuel cell stack to work, wherein the accessory systems comprise an air system, a hydrogen system, a cooling system, a power regulation system, a humidification system, a control system and the like. The air system is responsible for providing a proper amount of oxidant namely air for the galvanic pile, and the temperature, the pressure and the flow of the air entering the galvanic pile need to be adjusted according to the working condition; the hydrogen system is responsible for supplying hydrogen to the galvanic pile, and the pressure and the flow of the hydrogen entering the galvanic pile need to be adjusted according to the working condition; the cooling system keeps the temperature of the galvanic pile at a proper level in a coolant circulation mode, so that the stable and reliable operation of the galvanic pile is ensured; the power regulating system enables the output characteristic of the fuel cell system to meet the load requirement in a mode of regulating the output voltage or the output current of the fuel cell stack; the humidifying system is responsible for adjusting the humidity of air entering the galvanic pile, and over-drying or over-wetting has adverse effects on a proton exchange membrane and the galvanic pile, so that the humidity of the air entering the galvanic pile needs to be controlled; the control system is the brain of the whole fuel cell power generation system, and particularly performs optimal control on each subsystem at the periphery of the galvanic pile, so that the galvanic pile is in an optimal working state, and the long-term stable and reliable operation of the galvanic pile is ensured.
Referring to fig. 1, a typical fuel cell system 100 includes a fuel cell stack 10, a hydrogen system 12, an air system 14, a cooling system 16, a recovery system 18, and a DC/DC controller 19. The air system 14 includes an air compressor 142, a radiator 144, a humidifier 146, and a first flow control valve 148. The recovery system 18 includes a condenser 182 and a second flow control valve 184. The ambient air is compressed by the air compressor 142 and then enters the radiator 144, and after being cooled by the radiator 144, the ambient air enters the humidifier 146 for humidification, and then enters the fuel cell stack 10, and the oxygen on the cathode side of the fuel cell stack 10 and the hydrogen ions from the anode side undergo a chemical reaction, and water (gas or liquid) is generated while outputting electric energy. The oxygen content in the cathode air after the reaction is reduced and the water content (humidity) is increased. After moisture is recovered from the air at the outlet of the fuel cell stack 10 by the condenser 182, the air is discharged to the air atmosphere through the second flow control valve 184. The air flow and the air pressure entering the fuel cell stack 10 can be controlled by the coordinated control of the air compressor 142, the first flow control valve 148 and the second flow control valve, the intake air temperature can be adjusted by the radiator 144, and the intake air humidity can be controlled by the humidifier 146.
According to the operating principle and performance characteristics of PEMFCs, since water (gaseous or liquid) generated by the reaction inside the fuel cell stack needs to be carried out through the cathode reaction channel, if the generated liquid water is not removed in time, the generated water will block the flow channel, i.e. the so-called flooding phenomenon, which results in the performance degradation of the stack and affects the use of the fuel cell. In order to improve the drainage capacity, it is necessary to increase the flow rate or flow velocity of air so as to smoothly blow off liquid water. When idling or small load, because the generated water quantity is small, if the air flow is always kept large, the water on the surfaces of the flow channel and the proton exchange membrane is easy to be dried, so that the membrane is over-dried and the performance is reduced; if the air flow rate is kept small all the time, liquid water in the flow passage is not easy to blow away, and flooding is caused.
In a fuel cell control system, based on the existing sensor configuration, including cathode and anode inlet temperature and pressure sensors, cathode and anode outlet temperature and pressure sensors, and cathode inlet and outlet humidity sensors, the operating state inside a fuel cell stack is usually observed by adopting a lumped parameter model, but because the fuel cell stack is formed by connecting a plurality of single sheets in series and is limited by the structure of a stack gas supply system, the inlet pressure, the temperature, the humidity and the inlet components of each fuel cell single sheet are different, the voltage of the single sheet is inconsistent due to the difference of the gas supply state and the temperature difference of the single sheets, and when the structure of a system is unreasonable and the number of the single sheets is increased, the voltage inconsistency of the single sheets is more obvious. Because the working state of the fuel cell single chip cannot be observed in real time, and particularly, whether the single chip is flooded or dry membrane cannot be effectively judged in time, the internal working state of the fuel cell can be adjusted by controlling the gas supply system and the humidification system of the fuel cell, so that the phenomenon of flooding or dry membrane of the local fuel cell single chip is difficult to avoid, and the improvement of the performance of the fuel cell system is very unfavorable.
How to accurately obtain the working state of the fuel cell single chip and judge whether the fuel cell single chip is in an abnormal working state such as dry membrane or flooding so as to adjust the control links of the fuel cell gas supply system and the humidification system in time to improve the performance of the fuel cell is a challenge of the control of the fuel cell system.
With the progress of science and technology, through continuous and intensive research, people find that the performance characteristics of the fuel cell can be researched in an equivalent circuit mode, and the working state of the fuel cell and the impedance element in the equivalent circuit have a certain corresponding relation. According to the relationship between the fuel cell equivalent circuit and the fuel cell performance and the corresponding relationship between the resistance element and the capacitance element of the fuel cell equivalent circuit and the states of different components of the fuel cell stack, the working state of a fuel cell single chip and the whole working state of the fuel cell stack, such as the working conditions (temperature, humidity and the like) of each element, can be accurately predicted by acquiring the impedance value changes of the resistance element and the capacitance element in the fuel cell equivalent circuit in real time. In order to obtain resistance and capacitance parameters in an equivalent circuit of a fuel cell, alternating current impedance research needs to be carried out, the prices of commercial alternating current impedance analysis equipment in the current market, such as products produced and developed by Kikusui chrysanthemum and water corporation of Japan and Solarton corporation of England, are more than one hundred thousand yuan, the working voltage range and the current range of the equipment cannot meet the requirements of the existing fuel cell bus system, and large-scale real-vehicle application is naturally difficult to realize.
Disclosure of Invention
In view of the above, it is necessary to provide a simple, effective and low-cost method for analyzing ac impedance of an electrochemical energy storage device and monitoring the operating state thereof.
An alternating current impedance analysis method of an electrochemical energy storage device, comprising the steps of:
providing an integrated DC/DC converter, wherein the integrated DC/DC converter comprises a first DC/DC converter, a disturbance source and a controller, the first DC/DC converter is connected with the disturbance source in parallel, the input end of the first DC/DC converter is connected with the output end of an electrochemical energy storage device, the disturbance source comprises a switching device, the output end of the first DC/DC converter is connected with a load and used for regulating and controlling the output of the electrochemical energy storage device to meet the output of the load, and the controller selectively turns on or off the disturbance source;
the controller starts the disturbance source and regulates and controls the disturbance source to generate a current disturbance signal;
disturbing the output current of the electrochemical energy storage device by using the current disturbance signal;
detecting the output current and the output voltage of the electrochemical energy storage device after disturbance;
calculating an impedance corresponding to the frequency of the current disturbance signal according to the current disturbance signal and the disturbed output current and output voltage, an
And changing the frequency of the current disturbance signal, and re-disturbing the output current of the electrochemical energy storage device to obtain the alternating current impedance frequency spectrum of the electrochemical energy storage device.
A method for analyzing the working state of an electrochemical energy storage device comprises the following steps:
providing a typical ac impedance spectrum comprising a plurality of typical frequency impedance correspondences reflecting the operating conditions of the various components of the ideal electrochemical energy storage device;
obtaining an actual AC impedance spectrum of the electrochemical energy storage device using the AC impedance spectrum analysis method described above, wherein the electrochemical energy storage device is of the same type as the ideal electrochemical energy storage device, an
Comparing the actual AC impedance spectrum to the representative AC impedance spectrum to analyze the operating conditions of various components in the electrochemical energy storage device.
According to the analysis method provided by the embodiment of the invention, current disturbance signals with different frequencies are applied to the output end of the electrochemical energy storage device through the disturbance source in the integrated DC/DC converter, the electrochemical alternating current impedance spectrum of the electrochemical energy storage device can be obtained by detecting the current and the voltage at the output end of the electrochemical energy storage device, and the working state of the electrochemical energy storage device can be analyzed according to the alternating current impedance spectrum, so that the working condition of the electrochemical energy storage device can be adjusted to keep the electrochemical energy storage device in a better working state.
Drawings
Fig. 1 is a schematic configuration diagram of a fuel cell system in the related art.
Fig. 2 is a functional block diagram of an electrochemical energy storage system according to an embodiment of the present invention.
Fig. 3 is an equivalent circuit diagram of an electrochemical energy storage cell according to an embodiment of the present invention.
FIG. 4 is an electrochemical AC impedance spectrum corresponding to the equivalent circuit of FIG. 3.
Fig. 5 is a schematic structural diagram of an integrated DC/DC converter according to an embodiment of the present invention.
Fig. 6 is a circuit configuration diagram of a second DC/DC converter according to an embodiment of the present invention.
Fig. 7 is a circuit diagram of a disturbance source according to an embodiment of the present invention.
Fig. 8 is a circuit diagram of a disturbance source according to another embodiment of the present invention.
Fig. 9 is a circuit diagram of a disturbance source according to another embodiment of the present invention.
Fig. 10 is a diagram illustrating an operation process of a first DC/DC converter in the integrated DC/DC converter according to the embodiment of the present invention.
Fig. 11 is a flowchart of a current perturbation signal generation method in the electrochemical ac impedance spectroscopy method according to an embodiment of the present invention.
Fig. 12 is a flowchart of a method for analyzing and calculating ac impedance in the electrochemical ac impedance spectroscopy method according to an embodiment of the present invention.
Fig. 13 is a flowchart of a method for analyzing an operating state of an electrochemical energy storage device according to an embodiment of the present invention.
Fig. 14 is a polarization graph of current disturbance at the output end of the fuel cell stack provided in embodiment 1 of the present invention.
Fig. 15 is a signal diagram of an output current and a response output voltage of a fuel cell stack output terminal current through a signal disturbance according to embodiment 1 of the present invention.
Fig. 16 is a graph of the electrochemical ac impedance spectrum of the fuel cell stack according to example 1 of the present invention. Description of the main elements
Electrochemical energy storage system 20
Electrochemical energy storage device 22
Control system 24
Integrated DC/DC converter 200
First DC/DC converter 202
Second DC/DC converter 204
First voltage sensor 206
Second voltage sensor 208
First current sensor 210
Second current sensor 212
Third current sensor 214
Fourth current sensor 216
Controller 218
Voltage inspection device 220
The following detailed description will further illustrate the invention in conjunction with the above-described figures.
Detailed Description
The electrochemical energy storage system, the integrated DC/DC converter, the method for ac impedance spectrum analysis, and the method for analyzing the operating state of the electrochemical energy storage device provided by the present invention will be further described in detail with reference to the accompanying drawings and specific embodiments.
Referring to fig. 2, an electrochemical energy storage system 20 according to an embodiment of the present invention includes an electrochemical energy storage device 22, a control system 24, and an integrated DC/DC converter 200. The control system 24 ensures stable output of the electric energy of the electrochemical energy storage device 22 through regulation, and the integrated DC/DC converter 200 is connected to the electrochemical energy storage device 22 and regulates the electric energy output by the electrochemical energy storage device 22 to meet the demand of the load.
The electrochemical energy storage device 22 may include one or more electrochemical energy storage cells that generate electrical energy through a chemical reaction. The electrochemical energy storage cell includes a positive electrode, a negative electrode, and a dielectric separator disposed between the positive and negative electrodes. Referring to fig. 3, the performance characteristics of the electrochemical energy storage cell can be equivalent by using an equivalent circuit, specifically, the equivalent circuit of the electrochemical energy storage cell includes an nernst voltage ENernstAnd an anode double electric layer capacitor Cdl,AAnd anode resistance RACathode double electric layer capacitor Cdl,CAAnd a cathode resistance RCAAnd a proton exchange membrane resistance RΩWherein the anode is an electric double layer capacitor Cdl,AAnd anode resistance RAAn anode RC circuit and a cathode double electric layer capacitor C are formed in paralleldl,CAAnd a cathode resistance RCAParallel to form a cathode RC circuit, a stedt voltage ENernstCathode RC circuit, proton exchange membrane resistance RΩAnd an anode RC circuit in series. Referring to fig. 4, the ac impedance spectrum corresponding to the electrochemical energy storage cell equivalent circuit and each parameter of the telephone energy storage cell equivalent circuit have the following correspondence:
Z(0)＝RΩ+RA+RCA＝Rinternal。
wherein Z (ω) is the impedance of the fuel cell equivalent circuit, which depends on the angular frequency ω, RinternalIs the total internal resistance exhibited by the electrochemical cell when the output signal is a dc signal.
By detecting the impedances in the equivalent circuit during the operation of the electrochemical energy storage device 22, the operating environment conditions (such as temperature, humidity, etc.) of the components in the electrochemical energy storage device 22 can be determined, so that the operating environment conditions can be dynamically adjusted to effectively improve the efficiency of the electrochemical energy storage device 22. Preferably, the electrochemical energy storage cell may be at least one of a fuel cell, a lithium ion battery and a supercapacitor. In the embodiment of the present invention, the electrochemical energy storage unit is a fuel cell, and correspondingly, the electrochemical energy storage device 22 is a fuel cell stack formed by connecting a plurality of fuel cells in series.
The control system 24 is determined based on the type of electrochemical energy storage device 22. For example, when the electrochemical energy storage device 22 is a lithium ion battery pack, the control system 24 may be a lithium ion battery management unit for detecting the temperature and electrical parameters of the lithium ion battery pack or each lithium ion battery to adjust the consistency of the lithium ion battery. In the embodiment of the present invention, the control system 24 corresponds to the fuel cell stack, and the control system 24 may include a hydrogen system, an air system, a cooling system, a recycling system, a temperature and humidity detecting system, and an operating condition adjusting system. The working condition adjusting system adjusts the working environment of the fuel cell stack by using the working condition parameters detected by other systems.
Referring to fig. 5, the integrated DC/DC converter 200 includes a first DC/DC converter 202, a second DC/DC converter 204, a first voltage sensor 206, a second voltage sensor 208, a first current sensor 210, a second current sensor 212, a third current sensor 214, a fourth current sensor 216, and a controller 218, the first DC/DC converter 202 is connected in parallel with the second DC/DC converter 204, an input of the first DC/DC converter 202 is connected to an output of the electrochemical energy storage device 22, an output of the first DC/DC converter 202 is connected to a load, the first voltage sensor 206 is connected in parallel to an input of the first DC/DC converter 202 for detecting an output voltage of the electrochemical energy storage device 22, the second voltage sensor 208 is connected in parallel to an output of the first DC/DC converter 202, for detecting the output voltage of the first DC/DC converter 202, the first current sensor 210 is connected in series to the output of the electrochemical energy storage device 22 for detecting the output current of the electrochemical energy storage device 22, the second current sensor 212 is connected in series to the input of the second DC/DC converter 204 for detecting the current at the input of the second DC/DC converter 204, the third current sensor 214 is connected in series to the output of the first DC/DC converter 202 for detecting the current at the output of the first DC/DC converter 202, the fourth current sensor 216 is connected in series to the output of the second DC/DC converter 204 for detecting the current at the output of the second DC/DC converter 204, and the controller 218 receives the first voltage sensor 206, the first current sensor 210, the second current sensor 216, the first current sensor 206, the second current sensor 204, the second current sensor 216, and the second current sensor 204, The signals collected by the second voltage sensor 208 and the third current sensor 214 regulate the output of the electrochemical energy storage device 22 through the first DC/DC converter 202, and the controller 218 controls the second DC/DC converter 204 to be turned on or off, and controls the second DC/DC converter 204 to regulate the current at the output of the electrochemical energy storage device 22 in a current disturbance manner when the second DC/DC converter is turned on, so as to obtain the electrochemical ac impedance spectrum of the electrochemical energy storage device 22.
The first DC/DC converter 202 and the second DC/DC converter 204 may be any type of DC/DC converter, such as at least one of a boost type DC/DC converter, a buck type DC/DC converter, and a boost type DC/DC converter. Preferably, the first DC/DC converter 202 is a DC/DC converter suitable for vehicle power requirements, and more preferably, the first DC/DC converter 202 is a high-power DC/DC converter suitable for vehicle power requirements. The power of the first DC/DC converter 202 is preferably equal to or greater than 20 kw. In the embodiment of the present invention, the power of the first DC/DC converter 202 is 20 kw to 80 kw. The first DC/DC converter 202 is used to regulate the output of the electrochemical energy storage device 22 to meet the load requirements.
The second DC/DC converter 204 is used as a signal disturbance source to adjust the output current of the electrochemical energy storage device 22 in a current disturbance mode to detect the electrochemical ac impedance spectrum of the electrochemical energy storage device 22. The second DC/DC converter 204 is preferably a high frequency DC/DC converter. The use of a high frequency DC/DC converter facilitates detection of the electrochemical ac impedance spectrum of the electrochemical energy storage device 22 and reduces the interference or effect of current disturbances of the second DC/DC converter 204 on the load output. The frequency of the high frequency DC/DC converter is preferably 0.1Hz to 1 kHz.
Referring to fig. 6, in the embodiment of the invention, the second DC/DC converter 204 is a Boost type Boost DC/DC converter, and the second DC/DC converter 204 includes an inductor L1, a diode D1, a switching device G1, and a capacitor C1. One end of the inductor L1 serves as a forward input end of the second DC/DC converter 204, the other end of the inductor L1 is connected to the anode of the diode D1, and the cathode of the diode D1 serves as a forward output end of the second DC/DC converter 204. The switching device G1 has a gate connected to the controller 218, a collector connected to the anode of the diode D1, and an emitter that serves as both the negative input and the negative output of the second DC/DC converter 204. One end of the capacitor C1 is connected to the cathode of the diode D1, and the other end is connected to the emitter of the switching device G1. The switching device G1 is preferably an IGBT.
The operation of the second DC/DC converter 204 is as follows: when the switching device G1 is turned on, the input voltage UinThe generated current flows through an inductor L1, the current flowing through the inductor L1 is increased linearly according to the physical characteristics of the inductor, in the electric energy storage and inductor L1, the inductor L1 and the switching device G1 form a conducting loop, at the moment, the anode of the diode D1 is connected with the cathode of the input power supply, the cathode of the diode D1 is connected with the anode of the output power supply, and the diode D1 is cut off reversely; when the switching device G1 is turned off from on, the current flowing through the inductor L1 cannot change abruptly according to the physical characteristics of the inductor, thereby generating an electromotive force, the direction of which is in accordance with the input voltage UinThe same direction, the electric energy stored in the inductor L1 is continuously discharged, the capacitor C1 is charged through the diode D1 and the load is supplied with energy, and at this time, the inductor L1, the diode D1, the capacitor C1 and the load form a loop. When the on and off of the switching device G1 are periodically controlled, the energy can be transferred from UinDelivery to the Uo. The controller 218 may control the on and off states of the switching device G1 at different times to generate the current perturbation signal.
The first voltage sensor 206 and the first current sensor 210 are components that enable measurement of an electrical parameter of the electrochemical energy storage device 22 as a whole.
The fourth current sensor 216 may cooperate with the second current sensor 212 to monitor the efficiency of the second DC/DC converter 204, and may monitor the current change at the output of the second DC/DC converter and transmit the current change to the controller 218 to determine whether the current change has a greater effect on the load.
The controller 218 receives the data from the sensors and regulates the first DC/DC converter 202 and the second DC/DC converter 204 according to the load demand and the demand of the ac impedance spectrum analysis.
In a normal operating state of the integrated DC/DC converter 200, the first DC/DC converter 202 is turned on, the second DC/DC converter 204 is turned off, and the controller 218 adjusts the output of the electrochemical energy storage device 22 through the first DC/DC converter 202 according to the data collected by the first voltage sensor 206, the second voltage sensor 208, the first current sensor 210, and the third current sensor 214 to meet the load requirement.
When the ac impedance spectrum of the electrochemical energy storage device 22 is to be analyzed, the first DC/DC converter 202 and the second DC/DC converter 204 are turned on simultaneously, and the controller 218 still adopts the above-mentioned normal operation process to adjust the output of the electrochemical energy storage device 22 through the first DC/DC converter 202 to meet the load requirement. Meanwhile, the controller 218 receives data collected by the second current sensor 212 and the third current sensor 214 (and may also receive data collected by the fourth current sensor 216), and controls the second DC/DC converter 204 to regulate and control the output current of the electrochemical energy storage device 22 in a current disturbance manner according to the data to obtain the electrochemical ac impedance spectrum of the electrochemical energy storage device 22.
Further, when the electrochemical energy storage device includes a plurality of electrochemical energy storage cells, the integrated DC/DC converter 200 may further include a voltage polling device 220, and the voltage polling device 220 may collect the voltage of each electrochemical energy storage cell and transmit the voltage to the controller 218. The voltage patrol device 220 may be utilized to obtain an electrochemical ac impedance spectrum for each electrochemical energy storage cell in the electrochemical energy storage device 22.
In addition, the disturbance source may not be limited to the second DC/DC converter 204, and any circuit that can generate a disturbance current signal may be used as the disturbance source. This type of disturbance source available is connected in parallel with the first DC/DC converter 202. This type of disturbance source comprises a switching device that is turned on or off to generate the required current disturbance signal. Referring to fig. 7, an embodiment of the invention provides a disturbance source 204a, where the disturbance source 204a includes an inductor L1a, a capacitor C1a, a switching device G1a, and a diode D1a, where one end of the inductor L1a is connected to a positive input terminal, the other end is connected to an emitter of the switching device G1a, the capacitor C1a is connected to the input terminal in parallel, a cathode of the diode D1a is connected to the emitter of the switching device G1a, an anode of the diode D1a is connected to a negative input terminal, a base of the switching device G1a is connected to the controller 218, and a collector of the diode is connected to an output terminal. The switching device G1a is preferably an IGBT.
Referring to fig. 8, another embodiment of the invention provides a disturbance source 204b, where the disturbance source 204b includes resistors R1b and R2b, a transformer T1b, and switching devices G1b, G2b, G3b, and G4 b. The transformer T1b comprises a primary coil and a secondary coil, wherein one end of the primary coil is connected with a positive input end, the other end of the primary coil is connected with a negative input end after being connected with a resistor R1b in series, one end of the secondary coil is connected with a resistor R2b in series and then is connected with an emitter of a switching device G1b, and the other end of the secondary coil is connected with an emitter of a switching device G2 b. The switching devices G1b, G2b, G3b and G4b constitute a bridge circuit, and specifically, bases of the switching devices G1b, G2b, G3b and G4b are all connected to the controller 218, an emitter of the switching device G1b is connected to a collector of the switching device G3b, a collector of the switching device G1b is connected to a collector of the switching device G2b and serves as a positive output terminal, an emitter of the switching device G2b is connected to a collector of the switching device G4b, and an emitter of the switching device G3b is connected to an emitter of the switching device G4b and serves as a negative output terminal. The switching devices G1b, G2b, G3b and G4b are preferably IGBTs.
The disturbance sources 204a, 204b, and 204 each generate a current disturbance signal of a desired frequency and amplitude by the controller 218 regulating the on and off of the switching devices.
Referring to fig. 9, the embodiment of the present invention further provides a method for analyzing an electrochemical ac impedance spectrum of the electrochemical energy storage device 22 based on the integrated DC/DC converter 200, which includes the following steps:
s1, turning on the second DC/DC converter 204, and the controller 218 controlling the second DC/DC converter 204 to generate a current disturbance signal;
s2, perturbing the output current of the electrochemical energy storage device 22 by using the current perturbation signal;
s3, detecting the output current and the output voltage of the electrochemical energy storage device 22 after disturbance;
s4, calculating the impedance corresponding to the frequency of the current disturbance signal according to the current disturbance signal, the output current and the output voltage, an
And S5, changing the frequency of the current disturbance signal, and re-disturbing the output current of the electrochemical energy storage device to obtain the electrochemical alternating-current impedance frequency spectrum of the electrochemical energy storage device 22.
Before and during the electrochemical ac impedance spectroscopy, the first DC/DC converter 202 always works normally and outputs to the load, specifically, referring to fig. 10, the working process of the first DC/DC converter 202 includes the following steps:
s1a, selecting the control mode of the first DC/DC converter 202 and the target output signal value according to the load demand
S1b, detecting an output current and an output voltage of the electrochemical energy storage device 22, and an output current and an output voltage of the first DC/DC converter 202;
s1c, comparing the output current and the output voltage of the first DC/DC converter 202 detected in step S1b with the target output signal value and determining whether the target output signal value is reached:
if yes, continuously outputting to meet the load requirement;
if not, the controller 218 regulates the on and off times of the switching devices in the first DC/DC converter 202 to bring the output of the first DC/DC converter 202 to the target output signal value.
In the above step S1a, the control mode is selected according to the demand of the load, and the control mode includes current output and voltage output.
In step S1c, when the target output signal value is not reached, the controller 218 may regulate the on and off time of the switching device in the first DC/DC converter 202 to make the electrochemical energy storage device 22 output the corresponding current and voltage to meet the load requirement.
Referring to fig. 11, the step S1 specifically includes the following steps:
s11, judging whether to carry out alternating current impedance analysis, if so, turning on the second DC/DC converter 204, and simultaneously executing the step S12, if not, turning off the second DC/DC converter 204;
s12, selecting the frequency to be analyzed;
s13, selecting the amplitude of the current disturbance signal corresponding to the frequency;
s14, determining the current disturbance signal according to the frequency and the amplitude;
s15, detecting the output current of the electrochemical energy storage device 22 and the current at the input end of the second DC/DC converter 204, an
S16, determining whether the current at the input end of the second DC/DC converter 204 reaches the current disturbance signal, if not, the controller 218 regulates and controls the on and off time of the switching device in the second DC/DC converter 204 to reach the predetermined current disturbance signal.
In the step S12, the method may further include determining whether the frequency to be analyzed for the ac impedance is a single frequency, and if the frequency is a single frequency, performing the steps S13-16, and if there are multiple frequencies, performing the following steps:
s12a, determining the amplitude of the current disturbance signal corresponding to each frequency;
s12b, forming a plurality of current disturbance signals;
s12c, superposing and synthesizing the current disturbance signals into a mixed disturbance current signal, an
S12d, executing the steps S15-S16.
In the above step S15, the purpose of detecting the output current of the electrochemical energy storage device 22 is to further determine whether the amplitude of the disturbed output current of the electrochemical energy storage device 22 is consistent with the amplitude of the current disturbance signal, and if not, the current disturbance signal may be readjusted to make the amplitude of the disturbed output current of the electrochemical energy storage device 22 consistent with the amplitude of the current disturbance signal.
In the above step S16, the perturbed output current of the electrochemical energy storage device 22 may be further referred to ensure that the superposition of the current perturbation signal does not affect the load requirement as a whole.
In the above step S1, the current disturbance signal is preferably a small-amplitude sinusoidal current disturbance signal, and the disturbance of the output current of the electrochemical energy storage device 22 by using the small-amplitude current disturbance signal can avoid a large influence on the load demand, and on the other hand, the disturbance signal and the response of the entire system of the integrated DC/DC converter 200 can be approximately in a linear relationship, so that the mathematical processing of the subsequent measurement result is simplified.
The magnitude of the amplitude may be 1% to 10% of the output current of the electrochemical energy storage device 22. Preferably, the amplitude is 5% of the output current of the electrochemical energy storage device 22.
In step S2, when the current disturbance signal is applied to the output current of the electrochemical energy storage device 22, the electrochemical energy storage device 22 generates a response signal with the same frequency as the current disturbance signal. The electrochemical alternating current impedance corresponding to the selected frequency can be calculated by using the response signal and the current disturbance signal.
In order to further accurately obtain the electrochemical ac impedance corresponding to the frequency, referring to fig. 12, the step S3 further includes:
s31, continuously recording the output current of the electrochemical energy storage device 22 and the input current of the second DC/DC converter 204 for a period of time;
s32, judging whether the current disturbance signal can be sampled and analyzed to calculate the alternating current impedance according to the current collected in the time period, if not, executing the step S31, and if so, executing the step S33;
s33, continuously collecting the output current and the output voltage of the electrochemical energy storage device 22 for a period of time, and
and S34, calculating the amplitude and the phase of the alternating current impedance at the frequency according to the output current and the output voltage.
In step S31, since there is a certain response time for generating the response signal when the current disturbance signal is applied to the output current of the electrochemical energy storage device 22, it is necessary to record the response output current of the electrochemical energy storage device 22 and the input current of the second DC/DC converter 204 for a period of time in advance. The time period in step S31 is related to the frequency, and at high frequency, the time period may be selected with more cycles (e.g., 10 cycles), and at low frequency, the time period may be selected with less cycles (less than 2 cycles). Preferably, the time period in the step S31 is 1 cycle to 10 cycles.
Further, in the step S31, the output current of the first DC/DC converter 202 may be collected at the same time to ensure that the demand of the load is satisfied.
In step S32, it is determined whether a corresponding response signal is obtained, and if so, electrochemical ac impedance analysis can be started.
In the above step S33, the purpose of continuing to collect the output voltage and the output current for a period of time, preferably less than 0.2 seconds, is also to satisfy the response while reducing the power consumption.
After the step S33, the output current and the output voltage collected in the step S33 may be further filtered and processed by fourier transform (FFT).
The output current after applying the current perturbation signal to the output of the electrochemical energy storage device 22 is:
i＝I1+ΔI×sin(2πf×t+φ1)；
wherein, I1Is the reference current value at the output of the electrochemical energy storage device 22, the amplitude of the Delta I current perturbation signal, f is the selected frequency of the perturbation signal, t is the time, phi1The initial phase of the current perturbation signal.
The output voltage of the response after the current disturbance is:
u＝U1+ΔU×sin(2πf×t+φ1+φ)；
wherein, U1Is the reference voltage value at the output end of the electrochemical energy storage device 22, Δ U is the amplitude of the disturbance response signal, f is the frequency of the response signal is the same as the frequency of the disturbance signal, and Φ is the lag phase of the response signal relative to the current disturbance signal.
The ac impedance of the electrochemical energy storage device 22 at the selected frequency f is:
wherein,j is the ac impedance amplitude at the frequency f, and is an imaginary unit.
By varying the frequency, the electrochemical ac impedance value of the electrochemical energy storage device 22 at different frequencies can be obtained, thereby obtaining the electrochemical ac impedance spectrum of the electrochemical energy storage device 22. When the electrochemical energy storage device 22 includes a plurality of electrochemical energy storage cells, the electrochemical ac impedance spectrum of each electrochemical energy storage cell can be obtained by measuring the output voltage and the output current of each electrochemical energy storage cell and using the above method.
Referring to fig. 13, the embodiment of the invention further provides a method for analyzing the working state of the electrochemical energy storage device 22, which includes the following steps:
t1 providing a representative ac impedance spectrum comprising a plurality of representative frequency impedance correspondences reflecting the operating conditions of the various components of the ideal electrochemical energy storage device;
t2, obtaining an actual AC impedance spectrum of the electrochemical energy storage device 22 using the aforementioned AC impedance spectroscopy method, wherein the electrochemical energy storage device 22 is of the same type as the ideal electrochemical energy storage device, and
and T3, comparing the actual AC impedance spectrum with the typical AC impedance spectrum to analyze the working state of each component in the electrochemical energy storage device.
In step T1, the typical ac impedance spectrum may be obtained by measuring the electrochemical ac impedance of an ideal electrochemical energy storage device of the same type as the electrochemical energy storage device 22, performing better and under a more ideal operating environment. The typical ac impedance spectrum obtaining method can also be obtained by the analysis method provided by the embodiment of the present invention. In the typical ac impedance spectrum, the plurality of typical frequency impedance correspondences may reflect preferred operating conditions of various components in the electrochemical energy storage device of the type.
In the step T3, the operation state of each component in the electrochemical energy storage device 22 can be determined by comparing the typical ac impedance spectrum with the actual ac impedance spectrum, so that the operation state can be adjusted in time to keep the electrochemical energy storage device 22 in a better operation state.
In addition, in this analysis method, only the ac impedance of a specific frequency which is dependent on the operating state of the individual components of the electrochemical energy storage device can be detected.
The integrated DC/DC converter provided by the embodiment of the invention not only can flexibly adjust the output characteristics of the electrochemical energy storage device, but also can monitor the working state of the electrochemical energy storage device in real time, specifically, current disturbance signals with different frequencies are applied to the output end of the electrochemical energy storage device through the second DC/DC converter, the electrochemical alternating current impedance frequency spectrum of the electrochemical energy storage device can be obtained by detecting the current and the voltage of the output end of the electrochemical energy storage device, and the working state of the electrochemical energy storage device can be analyzed according to the alternating current impedance frequency spectrum, so that the working condition of the electrochemical energy storage device can be adjusted to keep the electrochemical energy storage device in a better working state. In addition, the integrated DC/DC converter is low in cost and beneficial to vehicle-mounted, and the mounting space can be greatly saved during vehicle-mounted.
Example 1
The electrochemical energy storage device 22 in the present embodiment is a fuel cell stack. Referring to fig. 14-15, the output current of the fuel cell stack is disturbed by using a small-amplitude disturbing current, and the fuel cell stack can be ensured to show a linear characteristic near the operating point a because the amplitude of the current disturbing signal is small. The electrochemical ac impedance spectrum of the fuel cell stack can be obtained by calculation according to the above formula, as shown in fig. 16, wherein the specific frequency can reflect the operating states of the different components of the fuel cell stack.
In particular, the frequency f0The low frequency ac impedance of the fuel cell stack, typically 0.1Hz, is representative of the internal mass transfer impedance of the fuel cell stack, i.e., how fast the fuel cell system is delivering reactants to the catalyst layer. The low frequency ac impedance increases when the gas diffusion layers on the bipolar plates of the fuel cell stack become clogged with liquid water or the partial pressure of the reactant gas decreases or the excess air ratio decreases.
Frequency f1Represents the medium frequency ac impedance of the fuel cell stack, with a typical frequency of 4Hz, which is characteristic of the dynamics of the catalyst inside the fuel cell. When the catalyst is lost or the catalyst is out of service (such as catalyst poisoning by CO), the medium frequency ac impedance and the low frequency ac impedance may increase.
Frequency f2The high frequency ac impedance of the fuel cell stack is represented, with a typical frequency of 1kHz, and is indicative of the capacitive impedance of the fuel cell stack. High frequency ac impedance increases when the fuel cell stack is not properly compacted or the collector plates are constantly eroded over time. Meanwhile, the high-frequency high-sulfur impedance is the representation of the water content of the proton exchange membrane, specifically, the representation shows that the proton exchange membrane is in a saturated state or a dried state, and the two states can cause the increase of the proton transfer impedance.
In addition, other modifications within the spirit of the invention will occur to those skilled in the art, and it is understood that such modifications are included within the scope of the invention as claimed.
Claims (9)
1. An alternating current impedance analysis method of an electrochemical energy storage device, comprising the steps of:
providing an integrated DC/DC converter, wherein the integrated DC/DC converter comprises a first DC/DC converter, a disturbance source and a controller, the first DC/DC converter is connected with the disturbance source in parallel, the input end of the first DC/DC converter is connected with the output end of an electrochemical energy storage device, the disturbance source comprises a switching device, the output end of the first DC/DC converter is connected with a load and used for regulating and controlling the output of the electrochemical energy storage device to meet the output of the load, and the controller selectively turns on or off the disturbance source;
the controller starts the disturbance source and regulates and controls the disturbance source to generate a current disturbance signal;
disturbing the output current of the electrochemical energy storage device by using the current disturbance signal;
detecting the output current and the output voltage of the electrochemical energy storage device after disturbance;
calculating an impedance corresponding to the frequency of the current disturbance signal according to the current disturbance signal and the disturbed output current and output voltage, an
And changing the frequency of the current disturbance signal, and re-disturbing the output current of the electrochemical energy storage device to obtain the alternating current impedance frequency spectrum of the electrochemical energy storage device.
2. The method of ac impedance analysis of an electrochemical energy storage device of claim 1, wherein said current perturbation signal generation process comprises the steps of:
s11, judging whether to carry out AC impedance analysis, if yes, executing step S12, if no, not conducting the disturbance source;
s12, selecting the frequency to be analyzed;
s13, selecting the amplitude of the current disturbance signal corresponding to the frequency;
s14, determining the current disturbance signal according to the frequency and the amplitude;
s15, detecting the output current of the electrochemical energy storage device and the input end current of the disturbance source, and
and S16, judging whether the current of the input end of the disturbance source reaches the current disturbance signal, if not, regulating the on-off time of a switch device in the disturbance source by the controller to reach the preset current disturbance signal.
3. The ac impedance analysis method of an electrochemical energy storage device according to claim 2, wherein in step S12, it is further determined whether the frequency to be subjected to the ac impedance analysis is a single frequency, if so, the steps S13-S16 are performed, and if there are a plurality of frequencies, the following steps are performed:
s12a, determining the amplitude of the current disturbance signal corresponding to each frequency;
s12b, forming a plurality of current disturbance signals;
s12c, superposing and synthesizing the current disturbance signals into a mixed disturbance current signal, an
S12d, executing the steps S15-S16.
4. The method of ac impedance analysis of an electrochemical energy storage device of claim 1, wherein said current perturbation signal is a sinusoidal current perturbation signal having a small amplitude ranging from 1% to 10% of the output current of said electrochemical energy storage device.
5. The method for ac impedance analysis of an electrochemical energy storage device of claim 1, wherein the step of acquiring the perturbed output voltage and output current of the electrochemical energy storage device comprises the steps of:
s31, continuously recording the output current of the electrochemical energy storage device and the input end current of the disturbance source for a period of time;
s32, judging whether the current disturbance signal can be sampled and analyzed to calculate the alternating current impedance according to the current collected in the time period, if not, executing the step S31, and if so, executing the step S33;
s33, continuously collecting the output current and the output voltage of the electrochemical energy storage device for a period of time, and
s34, calculating the amplitude and phase of the AC impedance at the frequency according to the output current and the output voltage collected in the step S33;
wherein, the collecting time period in the steps S31 and S33 may satisfy the response time.
6. The method for ac impedance analysis of an electrochemical energy storage device of claim 5, wherein after said step S33, the ac impedance magnitude and phase at said frequency are further calculated after filtering and fourier transforming said output current and output voltage collected in said step S33.
7. The method of ac impedance analysis of an electrochemical energy storage device of claim 1, wherein the impedance corresponding to the frequency of said current perturbation signal is calculated by:
the output current after the current disturbance signal is applied to the output end of the electrochemical energy storage device is as follows: i ═ I1+ΔI×sin(2πf×t+φ1) (ii) a Wherein, I1Is the reference current value of the output end of the electrochemical energy storage device, delta I is the amplitude of the current disturbance signal, f is the selected frequency of the current disturbance signal, t is the time, phi1Is the initial phase of the current perturbation signal;
the output voltage of the electrochemical energy storage device response after the current perturbation is: u is equal to U1+ΔU×sin(2πf×t+φ1+ phi); wherein, U1Is the reference voltage value of the output end of the electrochemical energy storage device, delta U is the amplitude of a disturbance response signal, f is the frequency of the response signal, the frequency of the response signal is the same as that of the disturbance signal, and phi is the lag phase of the response signal relative to the current disturbance signal;
the ac impedance of the electrochemical energy storage device at the selected frequency f is:wherein,j is the ac impedance amplitude at the frequency f, and is an imaginary unit.
8. The method of ac impedance analysis of an electrochemical energy storage device according to claim 1, wherein when said electrochemical energy storage device comprises a plurality of electrochemical energy storage cells, an electrochemical ac impedance spectrum of each electrochemical energy storage cell is obtained by measuring an output voltage and an output current of each electrochemical energy storage cell.
9. A method for analyzing the working state of an electrochemical energy storage device comprises the following steps:
providing a typical ac impedance spectrum comprising a plurality of typical frequency impedance correspondences reflecting the operating conditions of the various components of the ideal electrochemical energy storage device;
obtaining an actual AC impedance spectrum of the electrochemical energy storage device using the method of AC impedance spectroscopy of any one of claims 1 to 8, wherein the electrochemical energy storage device is of the same type as the ideal electrochemical energy storage device, and
comparing the actual AC impedance spectrum to the representative AC impedance spectrum to analyze the operating conditions of various components in the electrochemical energy storage device.
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