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
A kind of ac resistance analysis method that the present invention relates to electrochemical energy storage device with and the monitoring method of duty.
Background technology
Hydrogen-oxygen proton exchange membrane fuel cell (Proton Exchange Membrane Fuel Cell, be called for short PEMFC) be a kind of electrochemical appliance, directly chemical energy is converted to electric energy, traditional combustion engine energy conversion is subject to Carnot cycle restriction, and hydrogen-oxygen proton exchange membrane fuel cell energy conversion is not limited by Carnot cycle, its energy conversion efficiency is higher in theory.Owing to participating in the material of reaction, be hydrogen and air, reaction product is water, does not produce noxious emission, is therefore subject to people's favor, is applied to gradually the fields such as stand-by station, communications and transportation and portable power source.
Proton Exchange Membrane Fuel Cells output characteristics is direct current, and its monolithic output voltage is less than 1V, is typically 0.7V, for higher voltage can be provided, a lot of fuel cell monolithics need to be cascaded, and forms fuel cell pile, the corresponding raising of its output power.Fuel cell monolithic is comprised of anode gas diffusion layer (Gas Diffusion Layer is called for short GDL), membrane electrode assembly (Membrane Electrode Assemblies is called for short MEA) and cathode gas diffusion layer.
Fuel cell pile is the core component of fuel cell generation, at pile, be with many accessory system auxiliary fuel cell piles outward and carry out work, comprise air system, hydrogen gas system, cooling system, power regulating system, humidification system and control system etc.Air system is responsible for pile, and appropriate oxygenant is provided is air, need to enter according to regulating working conditions temperature, pressure and the flow of the air of pile; Hydrogen gas system is responsible for pile supply of hydrogen, need to enter according to regulating working conditions Hydrogen Vapor Pressure and the flow of pile; Cooling system makes stack temperature keep proper level by the mode of circulate coolant, guarantees the reliable and stable operation of pile; Power regulating system makes fuel cell system output characteristics can meet loading demand by the mode of fuel metering battery pile output voltage or output current; Humidification system is responsible for regulating the humidity of the air that enters pile, and overdrying or mistake are wet has adverse influence to PEM and pile, therefore need to carry out humidity control to entering the air of pile; Control system is whole fuel cell generation " brain ", especially the subsystems of pile periphery is optimized to control, makes pile in optimum Working, guarantees the operation of pile long time stability.
Refer to Fig. 1, a kind of typical fuel cell system 100 comprises fuel cell pile 10, hydrogen gas system 12, air system 14, cooling system 16, recovery system 18 and DC/DC controller 19.Wherein, air system 14 comprises air compressor machine 142, heating radiator 144, humidifier 146 and first flow operation valve 148.Described recovery system 18 comprises condenser 182 and second control valve 184.Surrounding air enters heating radiator 144 after compressing via air compressor machine 142, after cooling by heating radiator 144, enter humidifier 146 and carry out humidification, after humidification, enter fuel cell pile 10, the oxygen of fuel cell pile 10 cathode sides and from the hydrogen ion generation chemical reaction of anode-side produces water (gaseous state or liquid state) in output electric energy.Therefore in participating in reacted cathode air, oxygen content declines, and liquid water content (humidity) increases.Air in fuel cell pile 10 outlets reclaims after moisture through condenser 182, by second control valve 184, enters in air ambient.Wherein, can control air mass flow and the air pressure that enters fuel cell pile 10 by the coordination of air compressor machine 142, first flow operation valve 148 and second control valve, can adjust intake air temperature by heating radiator 144, by humidifier 146, control ambient humidity.
Known according to the principle of work of PEMFC and performance characteristics, because the water (gaseous state or liquid state) that fuel cell pile internal-response generates need to be taken out of through cathode reaction passage, if the aqueous water generating is got rid of not in time, the water generating can hinder runner, it is so-called water logging phenomenon, cause Performance data to decline, affect the use of fuel cell.In order to improve drainability, need to improve the flow of air or flow velocity to blow down smoothly aqueous water.When idling or little load, because the water yield generating is less than normal, if keep larger air mass flow always, easily runner and Surface modification of proton exchange membrane water are all dried up, cause film overdrying and hydraulic performance decline; If keep less air mass flow always, be not easy to blow away the aqueous water in runner and cause water logging.
In Fuel Cell Control System, based on existing sensor configuration, comprise anode and cathode inlet temperature and pressure transducer, anode and cathode outlet temperature and pressure transducer, negative electrode is imported and exported humidity sensor, conventionally adopt lumped parameter model to observe fuel cell pile internal work state, but because fuel cell pile is in series by many monolithics, be subject to the restriction of pile air supply system structure, each fuel cell monolithic admission pressure, temperature, humidity and air-intake component be difference to some extent all, monolithic air feed state difference and temperature contrast cause monolithic voltage to occur inconsistency, when and monolithic quantity unreasonable for system architecture increase, monolithic voltage inconsistency is more obvious.Due to duty that can not real-time monitored fuel cell monolithic, especially can not timely and effectively judge whether monolithic occurs water logging or the dry phenomenon of film, therefore by the control of fuel cell air supply system and humidification system being realized to fuel metering inside battery duty, be difficult to avoid occurring that water logging or the dry phenomenon of film appear in local burnup's battery monomer, to fuel cell system, performance boost is very disadvantageous for this.
How accurately to learn fuel cell monolithic duty, judge whether or the water logging as dry in film in abnormal operating state of fuel cell monolithic, adjusting in time fuel cell air supply system and humidification system controlling unit, to improve fuel battery performance, is the challenge that fuel cell system is controlled.
Along with scientific and technical progress, by constantly furtheing investigate, it is found that the Performance Characteristics of fuel cell can be studied by the mode of equivalent electrical circuit, between the duty of fuel cell and equivalent electrical circuit middle impedance unit, there is certain corresponding relation.Relation between fuel cell equivalent electrical circuit and fuel battery performance, and the corresponding relation that fuel cell equivalent electrical circuit resistance is first, electric capacity is first between assembly status different from fuel cell pile, by the change in impedance value of resistance unit and electric capacity unit in Real-time Obtaining fuel cell equivalent electrical circuit, just can Accurate Prediction fuel cell monolithic duty and fuel cell pile overall work state, as the condition of work of each element (temperature, humidity etc.).For obtaining resistance and capacitance parameter in fuel cell equivalent electrical circuit, need to carry out Study on AC impedance, commercialization ac resistance analysis equipment in the market, as the product of Japanese KIKUSUI chrysanthemum waters corporation and Britain Solarton company production development, its price is all more than 100,000 yuans, its operating voltage range and range of current all cannot meet the requirement of existing fuel cell motor bus system, are naturally difficult to realize large-scale real vehicle application.
Summary of the invention
In view of this, the necessary a kind of ac resistance analysis method that simple effective and lower-cost electrochemical energy storage device is provided with and the monitoring method of duty.
An ac resistance analysis method for electrochemical energy storage device, comprises the following steps:
One integrated DC/DC transducer is provided, this integrated DC/DC transducer comprises a DC/DC transducer, disturbing source and controller, a described DC/DC transducer is in parallel with this disturbing source, a described input end for DC/DC transducer and the output terminal of electrochemical energy storage device are connected, described disturbing source comprises switching device, the output terminal of the one DC/DC transducer is connected with load, in order to regulate and control the output of described electrochemical energy storage device, to meet load, export, described disturbing source is optionally opened or turn-offed to described controller;
Described controller is opened described disturbing source, regulates and controls described disturbing source simultaneously and produces a current disturbing signal;
Utilize this current disturbing signal to carry out disturbance to the output current of described electrochemical energy storage device;
Detect output current and output voltage after this electrochemical energy storage device disturbance;
According to the output current after this current disturbing signal and described disturbance and output voltage, calculate the impedance corresponding with the frequency of this current disturbing signal, and
Change the frequency of described current disturbing signal, again the output current of described electrochemical energy storage device is carried out to disturbance, to obtain the AC impedance frequency spectrum of this electrochemical energy storage device.
An analytical approach for electrochemical energy storage device duty, comprises the following steps:
One typical AC impedance frequency spectrum is provided, and this typical case's AC impedance frequency spectrum comprises the typical frequencies impedance respective value of all parts duty in the desirable electrochemical energy storage device of a plurality of reflections;
Adopt the method for above-mentioned AC impedance spectrum analysis to obtain the actual AC impedance frequency spectrum of this electrochemical energy storage device, wherein, described electrochemical energy storage device is identical with the type of described desirable electrochemical energy storage device, and
Described actual AC impedance frequency spectrum and described typical AC impedance frequency spectrum are compared to analyze to the duty of all parts in described electrochemical energy storage device.
In the analytical approach that the embodiment of the present invention provides, by the disturbing source in described integrated DC/DC transducer, at the output terminal of described electrochemical energy storage device, apply the current disturbing signal of different frequency, and by detecting the electric current of described electrochemical energy storage device output terminal and the electrochemical impedance spectroscopy that voltage can obtain this electrochemical energy storage device, according to this AC impedance frequency spectrum, can analyze the duty of this electrochemical energy storage device, thereby can regulate so that this electrochemical energy storage device can remain on good duty the condition of work of this electrochemical energy storage device.
Accompanying drawing explanation
Fig. 1 is the structural representation of fuel cell system of the prior art.
The structure function block diagram of the electrochemical energy storage system that Fig. 2 provides for the embodiment of the present invention.
The equivalent circuit diagram of the electrochemical energy storage monomer that Fig. 3 provides for the embodiment of the present invention.
Fig. 4 is the electrochemical AC impedance spectrogram that embodiment of the present invention Fig. 3 equivalent electrical circuit is corresponding.
The structural representation of the integrated DC/DC transducer that Fig. 5 provides for the embodiment of the present invention.
The circuit structure diagram of the 2nd DC/DC transducer that Fig. 6 provides for the embodiment of the present invention.
The circuit structure diagram of the disturbing source that Fig. 7 provides for a certain embodiment of the present invention.
The circuit structure diagram of the disturbing source that Fig. 8 provides for another embodiment of the present invention.
The circuit structure diagram of the disturbing source that Fig. 9 provides for further embodiment of this invention.
The process chart of a DC/DC transducer in the integrated DC/DC transducer that Figure 10 provides for the embodiment of the present invention.
The process flow diagram of current disturbing signal generating method in the electrochemical impedance spectroscopy analytical approach that Figure 11 provides for the embodiment of the present invention.
The process flow diagram of analytical calculation AC impedance method in the electrochemical impedance spectroscopy analytical approach that Figure 12 provides for the embodiment of the present invention.
The process flow diagram of the electrochemical energy storage device Working state analysis method that Figure 13 provides for the embodiment of the present invention.
The fuel cell pile output end current that Figure 14 provides for the embodiment of the present invention 1 is through the polarization curve of disturbance.
The fuel cell pile output end current that Figure 15 provides for the embodiment of the present invention 1 is through the output current of signal disturbance and the signal graph of response output voltage.
The electrochemical impedance spectroscopy figure of the fuel cell pile that Figure 16 provides for the embodiment of the present invention 1.Main element symbol description
Electrochemical energy storage system 20
Electrochemical energy storage device 22
Control system 24
Integrated DC/DC transducer 200
The one DC/DC transducer 202
The 2nd DC/DC transducer 204
The first voltage sensor 206
Second voltage sensor 208
The first current sensor 210
The second current sensor 212
The 3rd current sensor 214
The 4th current sensor 216
Controller 218
Voltage polling device 220
Following embodiment further illustrates the present invention in connection with above-mentioned accompanying drawing.
Embodiment
Below in conjunction with the accompanying drawings and the specific embodiments electrochemical energy storage system provided by the invention, integrated DC/DC transducer, the method for AC impedance spectrum analysis and the analytical approach of electrochemical energy storage device duty are described in further detail.
Refer to Fig. 2, first the embodiment of the present invention provides a kind of electrochemical energy storage system 20, and this electrochemical energy storage system 20 comprises electrochemical energy storage device 22, control system 24 and integrated DC/DC transducer 200.Described control system 24 guarantees the stable output of described electrochemical energy storage device 22 electric energy by regulation and control, described integrated DC/DC transducer 200 is connected with described electrochemical energy storage device 22, and the electric energy of described electrochemical energy storage device 22 outputs is regulated and controled to meet the demand of load.
Described electrochemical energy storage device 22 can comprise one or more electrochemical energy storage monomers, and this electrochemical energy storage monomer produces electric energy by chemical reaction.This electrochemical energy storage monomer comprise positive pole, negative pole and be arranged on positive pole and negative pole between dielectric spacer.Refer to Fig. 3, the Performance Characteristics of this electrochemical energy storage monomer can be come with equivalent electrical circuit equivalent, and particularly, the equivalent electrical circuit of this electrochemical energy storage monomer comprises can nernst voltage E
nernst, anode electric double layer capacitance C
dl, Awith anode resistance R
a, negative electrode electric double layer capacitance C
dl, CAwith cathode resistor R
cAand PEM resistance R
Ω, wherein, anode electric double layer capacitance C
dl, Awith anode resistance R
acompose in parallel anode RC circuit, negative electrode electric double layer capacitance C
dl, CAwith cathode resistor R
cAcompose in parallel negative electrode RC circuit, nernst voltage E
nernst, negative electrode RC circuit, PEM resistance R
Ωand anode RC circuit series connection.Refer to Fig. 4, the parameters of the ac impedance spectroscopy that this electrochemical energy storage monomer equivalent electrical circuit is corresponding and this telephoning telephony energy storage monomer equivalent electrical circuit has following corresponding relation:
Z(0)＝R
Ω+R
A+R
CA＝R
internal。
Wherein, Z (ω) is the impedance of fuel cell equivalent electrical circuit, and this impedance depends on angular frequency, R
internalit is total internal resistance that this electrochemical cell output signal shows while being direct current signal.
By in described electrochemical energy storage device 22 courses of work, detect each impedance in above-mentioned equivalent electrical circuit can judge electrochemical energy storage device 22 in the working environment state (as temperature, humidity etc.) of each element, thereby dynamically regulate described working environment state effectively to improve the effect of this electrochemical energy storage device 22.Preferably, this electrochemical energy storage monomer can be at least one in fuel cell, lithium ion battery and ultracapacitor.The monomer of electrochemical energy storage described in the embodiment of the present invention is fuel cell, accordingly, and the fuel cell pile that described electrochemical energy storage device 22 is a plurality of fuel cell series.
Described control system 24 is determined according to the type of described electrochemical energy storage device 22.As when as described in electrochemical energy storage device 22 while being lithium ion battery group, this control system 24 can lithium ion battery administrative unit, for detection of temperature, the electric parameter of lithium ion battery group or each lithium ion battery, the consistance of this lithium ion battery is regulated.In the embodiment of the present invention, the corresponding described fuel cell pile of this control system 24, this control system 24 can comprise hydrogen gas system, air system, cooling system, recovery system, temperature humidity detection system and condition of work regulating system.Described condition of work regulating system utilizes the condition of work parameter that other system detects to regulate the working environment of described fuel cell pile.
Refer to Fig. 5, described integrated DC/DC transducer 200 comprises a DC/DC transducer 202, the 2nd DC/DC transducer 204, the first voltage sensor 206, second voltage sensor 208, the first current sensor 210, the second current sensor 212, the 3rd current sensor 214, the 4th current sensor 216 and controller 218, a described DC/DC transducer 202 is in parallel with described the 2nd DC/DC transducer 204, the output terminal of electrochemical energy storage device 22 described in the input termination of a described DC/DC transducer 202, the output termination load of a described DC/DC transducer 202, described the first voltage sensor 206 is connected in parallel on the input end of a described DC/DC transducer 202, output voltage for detection of described electrochemical energy storage device 22, described second voltage sensor 208 is connected in parallel on the output terminal of a described DC/DC transducer 202, output voltage for detection of a DC/DC transducer 202, described the first current sensor 210 is connected on the output terminal of described electrochemical energy storage device 22, output current for detection of described electrochemical energy storage device 22, described the second current sensor 212 is connected on the input end of described the 2nd DC/DC transducer 204, electric current for detection of the 2nd DC/DC transducer 204 input ends, described the 3rd current sensor 214 is connected on the output terminal of a described DC/DC transducer 202, electric current for detection of DC/DC transducer 202 output terminals, described the 4th current sensor 216 is connected on the output terminal of described the 2nd DC/DC transducer 204, electric current for detection of the 2nd DC/DC transducer 204 output terminals, described controller 218 receives described the first voltage sensor 206, the first current sensor 210, the signal that second voltage sensor 208 and the 3rd current sensor 214 collect, and by the output of the described electrochemical energy storage device 22 of described DC/DC transducer 202 regulation and control, in addition, this controller 218 is controlled unlatching or the shutoff of described the 2nd DC/DC transducer 204, and under the state of opening at described the 2nd DC/DC transducer, control the electrochemical impedance spectroscopy that electric current that described the 2nd DC/DC transducer 204 regulates and controls described electrochemical energy storage device 22 output terminals in the mode of current disturbing obtains this electrochemical energy storage device 22.
A described DC/DC transducer 202 and the 2nd DC/DC transducer 204 can be the DC/DC transducer of any type, as being at least one in step-up DC/DC transducer, voltage-dropping type DC/DC transducer and buck-boost type DC/DC transducer.Preferably, a described DC/DC transducer 202 is for being applicable to the DC/DC transducer of vehicle-mounted power demand, and more preferably, a described DC/DC transducer 202 is for being applicable to the high power D C/DC transducer of vehicle-mounted power demand.The power of the one DC/DC transducer 202 is preferably greater than and equals 20 kilowatts.In the embodiment of the present invention, the power of a described DC/DC transducer 202 is 20 kilowatts to 80 kilowatts.The one DC/DC transducer 202 for the output that regulates and controls described electrochemical energy storage device 22 to meet the demand of load.
Described the 2nd DC/DC transducer 204, as a signal disturbance source, detects the electrochemical impedance spectroscopy of this electrochemical energy storage device 22 with the output current of electrochemical energy storage device 22 described in current disturbing mode tuning.The 2nd DC/DC transducer 204 is preferably high frequency DC/DC transducer.The interfere with or compromise that the current disturbing that adopts high frequency DC/DC transducer to be more conducive to detect the electrochemical impedance spectroscopy of this electrochemical energy storage device 22 and can reduce the 2nd DC/DC transducer 204 is exported described load.The calibration of this high frequency DC/DC transducer is 0.1Hz to 1kHz.
Refer to Fig. 6, in the embodiment of the present invention, the 2nd DC/DC transducer 204 is selected the Boost type DC/DC transducer that boosts, and the 2nd DC/DC transducer 204 comprises inductance L 1, diode D1, switching device G1 and capacitor C 1.Wherein, one end of described inductance L 1 is as the positive input of described the 2nd DC/DC transducer 204, the anode of diode D1 described in another termination, and the negative electrode of described diode D1 is as the 2nd DC/DC transducer 204 forward output terminals.Described switching device G1 has gate pole, collector and emitter, gate pole is connected with described controller 218, the anodic bonding of described collector and described diode D1, described emitter is simultaneously as described the 2nd DC/DC transducer 204 negative inputs and negative sense output terminal.The negative electrode of diode D1 described in one termination of described capacitor C 1, the emitter of switching device G1 described in another termination.This switching device G1 is preferably IGBT.
The course of work of the 2nd DC/DC transducer 204 is as follows: when described switching device G1 conducting, and input voltage U
inthe electric current the producing inductance L 1 of flowing through, according to the physical characteristics of inductance, linear the increasing of electric current of the inductance L of flowing through 1, in power storage and inductance L 1, inductance L 1 and switching device G1 form conducting loop, now, the anode of diode D1 is connected on the positive pole that the negative pole of input power, negative electrode are connected on out-put supply, and diode D1 oppositely ends; When described switching device G1 is become while turn-offing from conducting, according to the physical characteristics of inductance, the electric current of the inductance L of flowing through 1 can not produce sudden change, thereby produces electromotive force, the direction of electromotive force and input voltage U
indirection identical, the electric energy being stored in inductance L 1 constantly discharges, by diode D1, to capacitor C 1 charging with provide energy to load, now, inductance L 1, diode D1, capacitor C 1 and load form loop.When the conducting of periodicity gauge tap device G1 is when turn-offing, can realize energy by U
intransmission to Uo.Described controller 218 can, by controlling this switching device G1 at conducting and off state in the same time not, be realized the generation of current disturbing signal.
Described the first voltage sensor 206 and the first current sensor 210 are parts of realizing the electric parameter of measuring described electrochemical energy storage device 22 integral body.
Described the 4th current sensor 216 can coordinate to monitor with described the second current sensor 212 efficiency of described the 2nd DC/DC transducer 204, simultaneously can monitor described the 2nd DC/DC converter output terminal curent change, and be transferred to described controller 218 and judge whether this curent change can produce considerable influence to load.
Described controller 218 receives the data that above-mentioned each sensor transmits, and regulates and controls a described DC/DC transducer 202 and the 2nd DC/DC transducer 204 according to the demand of loading demand and AC impedance spectrum analysis.
This integrated DC/DC transducer 200 in normal operation, described DC/DC transducer 202 conductings, the 2nd DC/DC transducer 204 disconnects, the data that described controller 218 collects according to described the first voltage sensor 206, second voltage sensor 208, the first current sensor 210, the 3rd current sensor 214, realize the adjusting of described electrochemical energy storage device 22 outputs to meet the demand of load by a described DC/DC transducer 202.
In the time will analyzing the AC impedance frequency spectrum of described electrochemical energy storage device 22, a described DC/DC transducer 202 and the 2nd DC/DC transducer 204 conductings simultaneously, described controller 218 still adopts the process of above-mentioned normal operating conditions, and the output by 202 pairs of described electrochemical energy storage devices 22 of a described DC/DC transducer regulates to meet loading demand.Simultaneously described controller 218 receives the data that described the second current sensors 212 and the 3rd current sensor 214 (also can simultaneously receive described the 4th current sensor 216) collect, and in the mode of current disturbing, the output current of described electrochemical energy storage device 22 is regulated and controled to obtain the electrochemical impedance spectroscopy of this electrochemical energy storage device 22 according to the 2nd DC/DC transducer 204 described in this Data Control.
Further, when described electrochemical energy storage device comprises a plurality of described electrochemical energy storage monomer, this integrated DC/DC transducer 200 can further comprise a voltage polling device 220, this voltage polling device 220 can gather the voltage of each electrochemical energy storage monomer, and is transferred in described controller 218.Adopt this voltage polling device 220 can obtain the electrochemical impedance spectroscopy of each electrochemical energy storage monomer in this electrochemical energy storage device 22.
In addition, described disturbing source also can be not limited to described the 2nd DC/DC transducer 204, as long as can produce the circuit of current perturbation signal, all can be used as described disturbing source.Such available disturbing source is in parallel with a described DC/DC transducer 202.Such disturbing source comprises switching device, by conducting or turn-off described switching device and produce required current disturbing signal.Please further consult Fig. 7, the a certain embodiment of the present invention provides a kind of disturbing source 204a, this disturbing source 204a comprises inductance L 1a, capacitor C 1a, switching device G1a and diode D1a, wherein, a termination positive input terminal of described inductance L 1a, the emitter of another termination switching device G1a, capacitor C 1a is connected in parallel on input end, emitter, anode that the negative electrode of diode D1a meets described switching device G1a connect negative input, the base stage of described switching device G1a connects described controller 218, and collector connects output terminal.Described switching device G1a is preferably IGBT.
Refer to Fig. 8, another embodiment of the present invention provides a kind of disturbing source 204b, and this disturbing source 204b comprises resistance R 1b, R2b, transformer T1b and switching device G1b, G2b, G3b, G4b.Described transformer T1b comprises primary coil and secondary coil, one termination positive input of described primary coil, the other end connects negative input after connecting with resistance R 1b, one end of described secondary coil connects the emitter of switching device G1b after connecting with resistance R 2b, the emitter of another termination switching device G2b.Described switching device G1b, G2b, G3b and G4b form bridge circuit, particularly, the base stage of described switching device G1b, G2b, G3b and G4b is all connected with described controller 218, the emitter of switching device G1b is connected with the collector of switching device G3b, the collector of switching device G1b is connected with the collector of switching device G2b and as forward output terminal, the emitter of switching device G2b is connected with the collector of switching device G4b, and the emitter of switching device G3b is connected with the emitter of switching device G4b and as negative sense output terminal.Described switching device G1b, G2b, G3b and G4b are preferably IGBT.
Described disturbing source 204a, 204b and 204 are are all regulated and controled the conducting of described switching device and are turn-offed the current disturbing signal that produces required frequency and amplitude by described controller 218.
Refer to Fig. 9, the embodiment of the present invention, based on above-mentioned integrated DC/DC transducer 200, further provides a kind of analytical approach of electrochemical impedance spectroscopy of described electrochemical energy storage device 22, comprises the following steps:
S1, the 2nd DC/DC transducer 204 described in conducting, described the 2nd DC/DC transducer 204 of simultaneously described controller 218 regulation and control produces current disturbing signals;
S2, utilizes this current disturbing signal to carry out disturbance to the output current of described electrochemical energy storage device 22;
S3, detects output current and output voltage after described electrochemical energy storage device 22 disturbances;
S4, according to described current disturbing signal and described output current and the output voltage calculating impedance corresponding with the frequency of this current disturbing signal, and
S5, changes the frequency of described current disturbing signal, again the output current of described electrochemical energy storage device is carried out to disturbance, to obtain the electrochemical impedance spectroscopy of this electrochemical energy storage device 22.
Before above-mentioned electrochemical impedance spectroscopy is analyzed and in analytic process, a described DC/DC transducer 202 all the time normal work outputs to load, particularly, refers to Figure 10, and described DC/DC transducer 202 courses of work comprise the following steps:
S1a, selects control model and the target output signal value of a described DC/DC transducer 202 according to loading demand
S1b, detects output current and the output voltage of described electrochemical energy storage device 22 and the output current of a described DC/DC transducer 202 and output voltage;
S1c, the output current of the described DC/DC transducer 202 that step S1b is detected and output voltage and described target output signal value compare and judge whether to reach this target output signal value:
If so, continue output to meet loading demand;
If not, in described controller 218 regulation and control the one DC/DC transducers 202 conducting of switching device and turn-off time so that the output of a described DC/DC transducer 202 reaches described target output signal value.
In above-mentioned steps S1a, described control model is selected according to the demand of load, and this control model comprises electric current output and Voltage-output.
In above-mentioned steps S1c, when not reaching described target output signal value, the conducting that described controller 218 can be by the switching device in a described DC/DC the transducer 202 and turn-off time regulates and controls so that the described electrochemical energy storage device 22 corresponding electric currents of output and voltage meet the demand of load.
Refer to Figure 11, above-mentioned steps S1 specifically comprises the following steps:
S11, judges whether to carry out ac resistance analysis, and if so, the 2nd DC/DC transducer 204 described in conducting performs step S12 simultaneously, if not, and the 2nd DC/DC transducer 204 described in not conducting;
S12, the selected frequency that will carry out ac resistance analysis;
S13, selects the amplitude to current disturbing signal that should frequency;
S14, determines described current disturbing signal according to described frequency and amplitude;
S15, detects the output current of described electrochemical energy storage device 22 and the electric current of described the 2nd DC/DC transducer 204 input ends, and
S16, whether the electric current that judges described the 2nd DC/DC transducer 204 input ends reaches described current disturbing signal, if not, in described the 2nd DC/DC transducer 204 of described controller 218 regulation and control, the conducting of switching device and turn-off time reach predetermined described current disturbing signal.
In above-mentioned steps S12, can further comprise that judgement will carry out whether the frequency of ac resistance analysis is single-frequency, if single-frequency is carried out described step S13-16, if while having a plurality of frequency, carry out the following step:
S12a, determines the amplitude of the current disturbing signal that each frequency is corresponding;
S12b, forms a plurality of current disturbing signals;
S12c, synthesizes a hybrid perturbation current signal by the plurality of current disturbing signal stack, and
S12d, carries out described step S15-S16.
In above-mentioned steps S15, the object that detects the output current of described electrochemical energy storage device 22 is, whether the amplitude of further determining the output current of this electrochemical energy storage device 22 after disturbance is consistent with the amplitude of described current disturbing signal, readjusts described current disturbing signal so that the amplitude of the output current of described electrochemical energy storage device 22 after disturbance and the amplitude of described current disturbing signal are consistent if inconsistent.
In above-mentioned steps S16, can to guarantee the stack integral body of described current disturbing signal, not affect the demand of load with further reference to the output current of the described electrochemical energy storage device 22 after disturbance.
In above-mentioned steps S1, described current disturbing signal is preferably the sinusoidal current disturbing signal of a small magnitude, the current disturbing signal of employing small magnitude carries out disturbance to the output current of described electrochemical energy storage device 22 and can avoid loading demand to produce large impact on the one hand, on the other hand also can be so that approximate linear between the response of the whole system of this disturbing signal and this integrated DC/DC transducer 200, thus make the mathematics manipulation of subsequent measurement become simple.
The size of described amplitude can be 1% to 10% of described electrochemical energy storage device 22 output currents.Preferably, described amplitude is 5% of described electrochemical energy storage device 22 output currents.
In above-mentioned steps S2, when applying described current disturbing signal to the output current of described electrochemical energy storage device 22, the response signal of the corresponding meeting generation one of this electrochemical energy storage device 22 and this current disturbing signal same frequency.Utilize this response signal and current disturbing signal can calculate the electrochemical AC impedance of the selected frequency of described correspondence.
In order further to obtain accurately electrochemical AC impedance corresponding to described frequency, refer to Figure 12, described step S3 further comprises:
S31, the input end electric current of the output current of the described electrochemical energy storage device 22 of continuous recording a period of time and described the 2nd DC/DC transducer 204;
S32, judges whether that according to the electric current gathering in the above-mentioned time period can carry out sampling analysis to described current disturbing signal calculates AC impedance, if not, carries out described step S31, if so, performs step S33;
S33, continuation gathers output current and the output voltage of the described electrochemical energy storage device 22 of a period of time, and
S34, calculates AC impedance amplitude and the phase place at described frequency place according to this output current and output voltage.
In above-mentioned steps S31, while being applied to the output current of described electrochemical energy storage device 22 due to current disturbing signal, produce response signal and have certain response time, therefore the response output current of described electrochemical energy storage device 22 and the input end electric current of described the 2nd DC/DC transducer 204 that, need pre-recorded a period of time.Time period in this step S31 is relevant with described frequency, and during high frequency, the described time period can be chosen the more cycle (as 10 cycles), can choose the less cycle (being less than 2 cycles) during low frequency.Preferably, the time period in described step S31 is 1 cycle in cycle to 10.
The output current that further, can simultaneously gather a described DC/DC transducer 202 in above-mentioned steps S31 is to guarantee to meet the demand of load.
In above-mentioned steps S32, judge whether to obtain corresponding response signal, if can start to carry out electrochemical AC impedance analysis.
In above-mentioned steps S33, continue the collection output voltage of a period of time and the object of output current is to reduce power consumption in order to meet response equally simultaneously, and preferably, this time period is less than 0.2 second.
After above-mentioned steps S33, the output current that can further collect described step S33 and output voltage carry out filtering and Fourier transform (FFT) is processed.
The output current applying after described current disturbing signal at the output terminal of described electrochemical energy storage device 22 is:
i＝I
1+ΔI×sin(2πf×t+φ
1)；
Wherein, I
1electrochemical energy storage device 22 output terminal reference current values, Δ I current disturbing signal amplitude, f is the frequency of selected described disturbing signal, t is the time, φ
1initial phase for this current disturbing signal.
The output voltage responding after current disturbing is:
u＝U
1+ΔU×sin(2πf×t+φ
1+φ)；
Wherein, U
1be electrochemical energy storage device 22 output terminal reference voltage values, Δ U is disturbance response signal amplitude, and f is that response signal frequency is identical with disturbing signal frequency, and φ is that response signal is with respect to the lagging phase of described current disturbing signal.
The AC impedance of the electrochemical energy storage device 22 under selected described frequency f is:
Wherein,
for the AC impedance amplitude under described frequency f, j is imaginary unit.
By changing described frequency, can obtain the electrochemical AC impedance value of the electrochemical energy storage device 22 under different frequency, thereby obtain the electrochemical impedance spectroscopy of this electrochemical energy storage device 22.When described electrochemical energy storage device 22 comprises a plurality of electrochemical energy storage monomer, by measuring output voltage and the output current of each electrochemical energy storage monomer, and utilize said method can obtain the electrochemical impedance spectroscopy of each electrochemical energy storage monomer.
Refer to Figure 13, the embodiment of the present invention further provides a kind of analytical approach of electrochemical energy storage device 22 duties, comprises the following steps:
T1, provides a typical AC impedance frequency spectrum, and this typical case's AC impedance frequency spectrum comprises the typical frequencies impedance respective value of all parts duty in the desirable electrochemical energy storage device of a plurality of reflections;
T2, adopts the method for aforementioned AC impedance spectrum analysis to obtain the actual AC impedance frequency spectrum of this electrochemical energy storage device 22, and wherein, described electrochemical energy storage device 22 is identical with the type of described desirable electrochemical energy storage device, and
T3, compares described actual AC impedance frequency spectrum and described typical AC impedance frequency spectrum to analyze the duty of all parts in described electrochemical energy storage device.
In above-mentioned steps T1, described typical AC impedance frequency spectrum can obtain by repeatedly measuring with the electrochemical AC impedance of described electrochemical energy storage device 22 same types, better performances and the desirable electrochemical energy storage device under a comparatively ideal working environment.The described analytical approach that the preparation method of this typical case's AC impedance frequency spectrum also can provide by the embodiment of the present invention obtains.In this typical case's AC impedance frequency spectrum, described a plurality of typical frequencies impedance respective value can reflect the better duty of all parts in the electrochemical energy storage device of this type.
In above-mentioned steps T3, by described typical AC impedance frequency spectrum and described actual AC impedance frequency spectrum are compared, can judge the duty of all parts in described electrochemical energy storage device 22, thereby can adjust in time, make this electrochemical energy storage device 22 remain on a preferably duty.
In addition,, in this analytical approach, also can only detect the AC impedance of all parts duty correlated frequency of specific and described electrochemical energy storage device.
The integrated DC/DC transducer that the embodiment of the present invention provides not only can flexible electrochemical energy storage device output characteristics, the duty of all right Real-Time Monitoring electrochemical energy storage device, particularly, by described the 2nd DC/DC transducer, at the output terminal of described electrochemical energy storage device, apply the current disturbing signal of different frequency, and by detecting the electric current of described electrochemical energy storage device output terminal and the electrochemical impedance spectroscopy that voltage can obtain this electrochemical energy storage device, according to this AC impedance frequency spectrum, can analyze the duty of this electrochemical energy storage device, thereby can regulate so that this electrochemical energy storage device can remain on good duty the condition of work of this electrochemical energy storage device.In addition, this integrated DC/DC transducer cost is low and be beneficial to vehicle-mountedly, and can save greatly installing space when vehicle-mounted.
Embodiment 1
Electrochemical energy storage device described in the embodiment of the present invention 22 is fuel cell pile.Please refer to Figure 14-15, adopt the current perturbation of small magnitude to carry out disturbance to the output current of fuel cell pile, because this current disturbing signal amplitude is less, can guarantee that this fuel cell shows linear characteristic near piling up working point A.According to above-mentioned formula, calculate the electrochemical impedance spectroscopy that can obtain this fuel cell pile, as shown in figure 16, wherein, characteristic frequency can reflect the duty of the different parts of fuel cell pile.
Particularly, frequency f
0represented the low-frequency ac impedance of this fuel cell pile, typical frequencies is 0.1Hz, is the sign of fuel cell pile internal soundness transfer impedance, and fuel cell system is transferred to reactant the speed degree of catalyst layer.In fuel cell pile bipolar plates be left to or when gas diffusion layers is blocked by aqueous water or reacting gas dividing potential drop reduces or excess air coefficient reduces, low-frequency ac impedance all can increase to some extent.
Frequency f
1represented the midfrequent AC impedance of fuel cell pile, typical frequencies is 4Hz, is the dynamic (dynamical) sign of fuel battery inside catalyzer.When catalyst loss or catalyst failure (such as the catalyst poisoning being caused by CO), midfrequent AC impedance and low-frequency ac impedance meeting increase to some extent.
Frequency f
2represented the high-frequency ac impedance of fuel cell pile, typical frequencies is 1kHz, is the sign of fuel cell pile capacitive reactances.When fuel cell pile does not carry out, appropriateness compresses or collector plate constantly corrosion in time, and high-frequency ac impedance meeting increases to some extent.Meanwhile, this high frequency high-sulfur impedance is the sign of proton exchange water content of membrane, is exactly specifically, has characterized PEM in state of saturation or mummification state, and this two states all can cause proton transfer impedance to increase.
In addition, those skilled in the art also can do other and change in spirit of the present invention, and certainly, the variation that these are done according to spirit of the present invention, within all should being included in the present invention's scope required for protection.
Claims (9)
1. an ac resistance analysis method for electrochemical energy storage device, comprises the following steps:
One integrated DC/DC transducer is provided, this integrated DC/DC transducer comprises a DC/DC transducer, disturbing source and controller, a described DC/DC transducer is in parallel with this disturbing source, a described input end for DC/DC transducer and the output terminal of electrochemical energy storage device are connected, described disturbing source comprises switching device, the output terminal of the one DC/DC transducer is connected with load, in order to regulate and control the output of described electrochemical energy storage device, to meet load, export, described disturbing source is optionally opened or turn-offed to described controller;
Described controller is opened described disturbing source, regulates and controls described disturbing source simultaneously and produces a current disturbing signal;
Utilize this current disturbing signal to carry out disturbance to the output current of described electrochemical energy storage device;
Detect output current and output voltage after this electrochemical energy storage device disturbance;
According to the output current after this current disturbing signal and described disturbance and output voltage, calculate the impedance corresponding with the frequency of this current disturbing signal, and
Change the frequency of described current disturbing signal, again the output current of described electrochemical energy storage device is carried out to disturbance, to obtain the AC impedance frequency spectrum of this electrochemical energy storage device.
2. the ac resistance analysis method of electrochemical energy storage device as claimed in claim 1, is characterized in that, the process that described current disturbing signal produces comprises the following steps:
S11, judges whether to carry out ac resistance analysis, if so, and execution step S12, if not, disturbing source described in not conducting;
S12, the selected frequency that will carry out ac resistance analysis;
S13, selects the amplitude to current disturbing signal that should frequency;
S14, determines described current disturbing signal according to described frequency and amplitude;
S15, detects the output current of described electrochemical energy storage device and the input end electric current of described disturbing source, and
S16, judges whether the input end electric current of described disturbing source reaches described current disturbing signal, and if not, described controller regulates and controls the conducting of switching device in described disturbing source and turn-off time and reaches predetermined described current disturbing signal.
3. the ac resistance analysis method of electrochemical energy storage device as claimed in claim 2, it is characterized in that, in described step S12, further judgement will carry out whether the frequency of described ac resistance analysis is single-frequency, if it is carry out described step S13-S16, if while having a plurality of frequency, carry out the following step:
S12a, determines the amplitude of the current disturbing signal that each frequency is corresponding;
S12b, forms a plurality of current disturbing signals;
S12c, synthesizes a hybrid perturbation current signal by the plurality of current disturbing signal stack, and
S12d, carries out described step S15-S16.
4. the ac resistance analysis method of electrochemical energy storage device as claimed in claim 1, it is characterized in that, the sinusoidal current disturbing signal that described current disturbing signal is a small magnitude, the size of this amplitude is 1% to 10% of described electrochemical energy storage device output current.
5. the ac resistance analysis method of electrochemical energy storage device as claimed in claim 1, is characterized in that, the output voltage of the described electrochemical energy storage device after disturbance and the collection of output current comprise the following steps:
S31, the input end electric current of the output current of the described electrochemical energy storage device of continuous recording a period of time and described disturbing source;
S32, judges whether that according to the electric current gathering in the above-mentioned time period can carry out sampling analysis to described current disturbing signal calculates AC impedance, if not, carries out described step S31, if so, performs step S33;
S33, continuation gathers output current and the output voltage of the described electrochemical energy storage device of a period of time, and
S34, AC impedance amplitude and phase place that the output current gathering according to this step S33 and output voltage calculate described frequency place;
Wherein, the acquisition time section in described step S31 and S33 meets the response time.
6. the ac resistance analysis method of electrochemical energy storage device as claimed in claim 5, it is characterized in that, after described step S33, the output current further described step S33 being collected and output voltage carry out calculating after filtering and Fourier transform processing AC impedance amplitude and the phase place at described frequency place again.
7. the ac resistance analysis method of electrochemical energy storage device as claimed in claim 1, is characterized in that, following process computation is passed through in the impedance corresponding with the frequency of described current disturbing signal:
The output current applying after described current disturbing signal at the output terminal of described electrochemical energy storage device is: i=I
1+ Δ I * sin (2 π f * t+ φ
1); Wherein, I
1described electrochemical energy storage device output terminal reference current value, the amplitude of current disturbing signal described in Δ I, f is the frequency of selected described current disturbing signal, t is the time, φ
1initial phase for this current disturbing signal;
After current disturbing, the output voltage of the response of described electrochemical energy storage device is: u=U
1+ Δ U * sin (2 π f * t+ φ
1+ φ); Wherein, U
1be the output terminal reference voltage value of described electrochemical energy storage device, Δ U is disturbance response signal amplitude, and f is response signal frequency, identical with described disturbing signal frequency, and φ is that response signal is with respect to the lagging phase of described current disturbing signal;
The AC impedance of the electrochemical energy storage device under selected described frequency f is:
wherein,
for the AC impedance amplitude under described frequency f, j is imaginary unit.
8. the ac resistance analysis method of electrochemical energy storage device as claimed in claim 1, it is characterized in that, when described electrochemical energy storage device comprises a plurality of electrochemical energy storage monomer, by measuring output voltage and the output current of each electrochemical energy storage monomer, and utilize said method to obtain the electrochemical impedance spectroscopy of each electrochemical energy storage monomer.
9. an analytical approach for electrochemical energy storage device duty, comprises the following steps:
One typical AC impedance frequency spectrum is provided, and this typical case's AC impedance frequency spectrum comprises the typical frequencies impedance respective value of all parts duty in the desirable electrochemical energy storage device of a plurality of reflections;
Adopt the method for AC impedance spectrum analysis as claimed in any of claims 1 to 8 in one of claims to obtain the actual AC impedance frequency spectrum of this electrochemical energy storage device, wherein, described electrochemical energy storage device is identical with the type of described desirable electrochemical energy storage device, and
Described actual AC impedance frequency spectrum and described typical AC impedance frequency spectrum are compared to analyze to the duty of all parts in described electrochemical energy storage device.
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| PCT/CN2015/078178 WO2016019744A1 (en) | 2014-08-08 | 2015-05-04 | Integrated dc/dc converter and electrochemical energy storage system as well as alternating-current impedance analytical method for electrochemical energy storage device and analytical method for working state of electrochemical energy storage device |
| US14/973,905 US9897663B2 (en) | 2014-08-08 | 2015-12-18 | Integrated DC/DC converter, electrochemical energy storage system, and methods for analyzing electrochemical impedance spectroscopy and working state of electrochemical energy storage apparatus |
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