CN108663631B - Electrochemical impedance spectrum on-line measuring device for lithium ion battery pack - Google Patents

Electrochemical impedance spectrum on-line measuring device for lithium ion battery pack Download PDF

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CN108663631B
CN108663631B CN201810469418.5A CN201810469418A CN108663631B CN 108663631 B CN108663631 B CN 108663631B CN 201810469418 A CN201810469418 A CN 201810469418A CN 108663631 B CN108663631 B CN 108663631B
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resistor
lithium ion
ion battery
operational amplifier
voltage
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CN108663631A (en
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吕超
张滔
刘海洋
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Harbin Institute of Technology
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Harbin Institute of Technology
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Abstract

An electrochemical impedance spectrum on-line measuring device of a lithium ion battery pack relates to the field of electrochemical impedance spectrum on-line measurement of the lithium ion battery pack. The invention aims to solve the problems that the electrochemical impedance spectrum of the lithium ion battery is measured by adopting an alternating current impedance method in the prior art, the measuring method needs special testing equipment, the testing period is long, and the integration and online measurement in a system are difficult to realize. The processor is used for grouping the sine waves of all frequencies and loading the grouped sine waves of all frequencies into different sections of the sine signal of the lowest frequency respectively; obtaining a voltage excitation signal through a signal generator; the switch switching circuit enables the lithium ion battery monomer to receive current excitation signals of different sections; the V-I conversion circuit converts the voltage excitation signal into a current excitation signal; the sampling circuit obtains response voltage signals of different sections; the processor is also used for carrying out fast Fourier transform on the response voltage signal to obtain an impedance spectrum. For measuring impedance spectra of lithium ion batteries.

Description

Electrochemical impedance spectrum on-line measuring device for lithium ion battery pack
Technical Field
The invention relates to an online measuring device for an electrochemical impedance spectrum of a lithium ion battery pack, and belongs to the field of online measurement of the electrochemical impedance spectrum of the lithium ion battery pack.
Background
The lithium ion battery as a novel high-energy chemical power supply has a series of characteristics of high specific energy, long wet storage life, flat discharge voltage, high charge-discharge efficiency, environmental friendliness and the like, so that the lithium ion battery has wide attention in different application occasions.
However, in some applications requiring high safety and reliability of the system, such as electric vehicles, in-orbit satellites, emergency equipment, etc., the core energy components need to be monitored to ensure the system operates properly. Monitoring the health status of a lithium ion battery is difficult to achieve for this purpose, because lithium ion batteries are a chemical power source, and their health status is mainly determined by internal electrochemical parameters and is difficult to obtain directly from external parameters. In order to solve the problem, a great deal of research is carried out by many scholars at home and abroad, and research finds that the electrochemical impedance spectrum of the battery is closely related to the service life and the charge state of the battery, so that the measurement of the electrochemical impedance spectrum becomes the key for monitoring the health state of the lithium ion battery.
Currently, the measurement of electrochemical impedance spectroscopy mainly uses an alternating current impedance method (frequency domain impedance spectroscopy measurement method), that is, a voltage or current excitation with a certain frequency is applied to a lithium ion battery under the condition that the battery is at a balanced potential, and the impedance at the frequency point is calculated after response data of several periods are obtained. The method needs special test equipment, has long test period and is difficult to realize integration and online measurement in the system.
Disclosure of Invention
The invention aims to solve the problems that the electrochemical impedance spectrum of the lithium ion battery is measured by adopting an alternating current impedance method in the prior art, the measuring method needs special testing equipment, the testing period is long, and the integration and online measurement in a system are difficult to realize. An online electrochemical impedance spectroscopy measuring device for a lithium ion battery pack is provided.
An electrochemical impedance spectrum on-line measuring device of a lithium ion battery pack comprises a processor 1, a signal generator 2, a V-I conversion circuit 3, a switch switching circuit 4 and a sampling circuit 5,
the processor 1 is used for grouping the sine waves of all frequencies and loading the grouped sine waves of all frequencies into different sections of the sine signal of the lowest frequency respectively;
the signal generator 2 is used for obtaining the loaded voltage excitation signals of different sections;
the processor 1 is also used for controlling the switching of the switch switching circuit 4;
the switch switching circuit 4 is used for switching different lithium ion battery monomers so that the lithium ion battery monomers selected by switching receive current excitation signals of different sections;
the V-I conversion circuit 3 is used for respectively converting the voltage excitation signals of the different sections into current excitation signals;
the sampling circuit 5 is used for obtaining response voltage signals of different sections from the lithium ion battery monomer selected by switching;
the processor 1 is further configured to perform fast fourier transform on the obtained response voltage signals of different sections to obtain voltage vectors of different sections of the lithium ion battery cell, obtain impedances at various frequencies through the voltage vectors and the current excitation signals obtained by the V-I conversion circuit 3, and fit the impedances at various frequencies to obtain impedance spectra of the lithium ion battery cell under various excitation signals.
The invention has the beneficial effects that:
according to the method and the device, the circuit design is adopted in hardware, and the time domain measurement mode is adopted in software, so that the frequency of signals does not need to be accurately controlled, complicated circuits such as phase-locked loops are omitted, and hardware circuits are simplified. And the additional error caused by external environmental factors is reduced by means of component integration.
In the electrochemical impedance spectrum testing process, in order to ensure that the electrochemical balance state in the lithium ion battery is not broken, the method adopts a current excitation and voltage response mode to carry out measurement. In order to realize the measurement of the electrochemical impedance spectrum in the time domain, FFT or Laplace transformation needs to be carried out on the excitation and response signals. In order to ensure the measurement accuracy, each frequency point should have a considerable signal intensity, so the method adopts a mode of synthesizing sine waves with the same amplitude at all frequency points to be measured to generate current excitation signals. In order to ensure the safety of the battery, the method adopts a dislocation synthesis mode to process the excitation signal, and avoids the over-strong current excitation. The scheme solves the possible problems in a series of test processes, simplifies the test flow and improves the test efficiency.
In the aspect of data processing, the method can reduce the data volume to be processed to a greater extent and improve the calculation efficiency by carrying out segmented processing on the sampling signals. In addition, the memory occupation of the processor can be reduced after the signal is processed in a segmented mode, and the implementation of the method in an embedded system is facilitated.
Drawings
FIG. 1 is a schematic diagram of an online electrochemical impedance spectroscopy measurement apparatus for a lithium ion battery pack according to a first embodiment;
FIG. 2 is a circuit schematic of a V-I converter circuit;
FIG. 3 is a schematic circuit diagram of a switching circuit, wherein each Cell1-Celln represents a lithium ion battery Cell;
FIG. 4 is a simulated resultant current excitation signal;
FIG. 5 is a graph of the collected response voltage signal;
fig. 6 is a graph comparing the measurement results obtained using the apparatus of the present application with the measurement results obtained using a dedicated device.
Detailed Description
The first embodiment is as follows: referring to fig. 1 to explain the embodiment specifically, the device for measuring electrochemical impedance spectroscopy of the lithium ion battery pack in the embodiment comprises a processor 1, a signal generator 2, a V-I conversion circuit 3, a switch switching circuit 4 and a sampling circuit 5,
the processor 1 is used for grouping the sine waves of all frequencies and loading the grouped sine waves of all frequencies into different sections of the sine signal of the lowest frequency respectively;
the signal generator 2 is used for obtaining the loaded voltage excitation signals of different sections;
the processor 1 is also used for controlling the switching of the switch switching circuit 4;
the switch switching circuit 4 is used for switching different lithium ion battery monomers so that the lithium ion battery monomers selected by switching receive current excitation signals of different sections;
the V-I conversion circuit 3 is used for respectively converting the voltage excitation signals of the different sections into current excitation signals;
the sampling circuit 5 is used for obtaining response voltage signals of different sections from the lithium ion battery monomer selected by switching;
the processor 1 is further configured to perform fast fourier transform on the obtained response voltage signals of different sections to obtain voltage vectors of different sections of the lithium ion battery cell, obtain impedances at various frequencies through the voltage vectors and the current excitation signals obtained by the V-I conversion circuit 3, and fit the impedances at various frequencies to obtain impedance spectra of the lithium ion battery cell under various excitation signals.
In the present embodiment, in the test of measuring the electrochemical impedance spectrum in the time domain, the excitation signal used determines which frequency points of impedance characteristics are included in the test result, and previous studies have shown that, for a lithium ion battery, the impedance characteristics are mainly distributed in the range of 0.01Hz to 1000 Hz. Therefore, the method selects a plurality of characteristic impedance frequency points which can represent the health and the service life state of the battery most in the frequency band to synthesize the excitation signal. In the process of synthesizing the sine signals, the sine waves of each frequency need to have corresponding amplitude under the influence of the precision of the tested equipment, and when a plurality of sine waves are synthesized into the excitation signals, the problem that the amplitude of the synthesized excitation signals is too large and exceeds the output capacity of the equipment or the chemical balance state of the lithium ion battery is influenced, so that the measurement precision is reduced can occur. For this reason, the present application employs a means of segmented dislocation synthesis to avoid this problem. Firstly, the sine wave of each frequency is subjected to phase control to control the amplitude of the synthesized signal, and secondly, the sine wave of each frequency is subjected to grouping processing and is loaded in different sections of the sine signal of the lowest frequency respectively, so that the sine signals of different frequencies loaded by the signal at the same moment are reduced to control the amplitude of the synthesized integral signal.
After the battery cell to be measured is selected by switching and a predetermined excitation is output, the response signal needs to be measured. In order to ensure the measurement accuracy, the high-resolution sampling circuit 5 is adopted to simultaneously acquire the voltage at the two ends of the R12 and the voltage at the two ends of the battery in the figure 2, and because the resistance value of the R12 is known, the excitation signal and the response signal which are actually applied to the single battery can be directly obtained. Under the condition that the segmented synthesis mode of the excitation signal is known, FFT analysis can be carried out on the acquired signal, and therefore the characteristic impedance of the single lithium ion battery at each frequency point is obtained. For example: to determine the impedance spectrum of a cell, ω is required0、ω1……ωn(frequency increases in order) the cell impedance at these n +1 frequencies, in terms of frequencyIs omega0Based on the sine fundamental wave of (a), from ω1To omeganDivided into m groups, each superposed at a frequency of ω0T of the sine fundamental wave of1s~t1e,t2s~t2e……tms~tmeAnd obtaining the superposed test voltage excitation signal. The excitation signal is converted into I through a V-I conversion circuitω0、Iω1……IωnThe n +1 current excitation signals with the sine waves of the frequency are added to the battery monomer to be tested. Measuring the voltage signal in response to t of the response signal1s~t1e,t2s~t2e……tns~tneThe segments are respectively subjected to fast Fourier transform to obtain corresponding Uω0、Uω1……UωnFrom Z ═ U/I, ω can be determined0、ω1……ωnImpedance Z at these n +1 frequenciesω0、Zω1……Zωn. And obtaining the impedance spectrum curve of the battery monomer by using methods such as universal curve fitting and the like.
In a system, a battery pack is often formed by connecting a plurality of battery cells in series and in parallel, and if each test needs to sequentially measure all the battery cells, a lot of time is consumed. Therefore, there is a need for a screening means to make a preliminary estimate of the state of health of all cells to determine the cells that are specifically needed for electrochemical impedance spectroscopy. According to the method, the method for extracting the external parameters of the batteries as the estimation indexes of the health states of the batteries is adopted to carry out primary screening on all the battery monomers, and the battery monomers with potential health hazards are further tested, so that the time for testing and analyzing the health state of a certain battery pack can be greatly shortened.
The second embodiment is as follows: referring to fig. 2 to explain this embodiment in detail, this embodiment is to further explain an online electrochemical impedance spectroscopy measurement apparatus of a lithium ion battery pack according to the first embodiment, in this embodiment, the V-I conversion circuit 3 includes resistors R1-R12, resistor Rs, diodes D1-D2, transistors Q1-Q2, and operational amplifiers U1-U3,
the voltage excitation signal output end of the signal generator 2 is simultaneously connected with one end of a resistor R5 and one end of a resistor R6, the other end of the resistor R5 is connected with a power ground, the other end of the resistor R6 is simultaneously connected with the inverting input end of an operational amplifier U1, one end of a resistor R9 and one end of a resistor R8, the non-inverting input end of the operational amplifier U1 is connected with one end of a resistor R7, the other end of the resistor R7 is connected with the power ground,
the positive power supply end of an operational amplifier U1 is simultaneously connected with a +15V power supply, one end of a resistor R1 and one end of a resistor R3, the other end of the resistor R1 is simultaneously connected with the anode of a diode D1 and the base of a triode Q1, the cathode of a diode D1 is simultaneously connected with the output end of the operational amplifier U1 and the anode of a diode D2, the cathode of a diode D2 is simultaneously connected with one end of a resistor R2 and the base of a triode Q2, the other end of the resistor R2 is simultaneously connected with the negative power supply end of the operational amplifier U1, the 15V power supply and one end of a resistor R4, the other end of the resistor R4 is connected with the collector of a triode Q2, the emitter of a triode Q2 is simultaneously connected with the emitter of the triode Q1, the other end of the resistor R8 and one end of a resistor Rs,
the other end of the resistor Rs is simultaneously connected with one end of a resistor R12 and the non-inverting input end of an operational amplifier U3, the inverting input end of the operational amplifier U3 is simultaneously connected with the output end of the operational amplifier U3 and one end of a resistor R11, the other end of the resistor R11 is simultaneously connected with one end of a resistor R10 and the inverting input end of the operational amplifier U2, the non-inverting output end of the operational amplifier U2 is connected with the power ground, the other end of the resistor R10 is simultaneously connected with the output end of the operational amplifier U2 and the other end of the resistor R9,
the other end of the resistor R12 and the grounding wire are both connected with the lithium ion battery pack 6.
The third concrete implementation mode: referring to fig. 3, this embodiment is further described with respect to an on-line measuring apparatus for electrochemical impedance spectroscopy of a lithium ion battery pack according to the first embodiment, in this embodiment, the switch switching circuit 4 includes n pairs of opposite MOS transistors,
the positive output end of a current excitation signal of the V-I conversion circuit (3) is simultaneously connected with one end of n opposite-top MOS tubes, the negative output end of the current excitation signal of the V-I conversion circuit (3) is simultaneously connected with one end of the other n opposite-top MOS tubes, a lithium ion battery monomer is connected between the other end of each pair of opposite-top MOS tubes in series, and the n lithium ion battery monomers are connected in series.
In this embodiment, in order to realize online measurement of the electrochemical impedance spectrum of the lithium ion battery pack, a problem to be solved is how to effectively switch and select the single lithium ion battery to be measured. The switching selection of different lithium ion battery monomers is realized by adopting the following switching topological structure. The switching topology is shown in fig. 3. The left input end of the battery is connected to the output end of the V-I conversion circuit 3, VF 1-VF 2n are opposite-top Mos tubes, and two opposite-top MOS tubes are arranged on two sides of each battery monomer. When a certain lithium ion battery cell is selected, the controller controls the switch switching circuit 4 to open the MOS tubes on the positive side and the negative side of the corresponding lithium ion battery cell. For example, if the lithium ion battery Cell2 needs to be selected, the VF2 and VF8 may be opened.
The fourth concrete implementation mode: in this embodiment, the on-line measuring device for electrochemical impedance spectroscopy of a lithium ion battery pack according to the third embodiment is further described, in this embodiment, the sampling circuit 5 collects the response voltage of each lithium ion battery cell from both ends of the lithium ion battery cell.
The fifth concrete implementation mode: in this embodiment, the on-line measuring device for electrochemical impedance spectroscopy of a lithium ion battery pack according to the second embodiment is further described, in this embodiment, the excitation current I output by the V-I conversion circuit 3outComprises the following steps:
in the formula, VinExcitation voltage, R, input to the V-I converter circuitSIs the resistance value of the resistor Rs.
In the present embodiment, the processor is adopted to control the high-resolution signal generator 2 as a signal generating source, and this part of the circuit is a relatively common circuit. For the voltage excitation signal generated by the signal generator 2, the voltage signal is converted into current excitation by the V-I conversion circuit 3. The structure of this part of the circuit is shown in fig. 2, and the output current of the right port is:
and (3) experimental verification:
in the experiment, the feasibility and the accuracy of the electrochemical impedance spectroscopy method based on time domain measurement are verified by measuring 14500P ternary lithium ion batteries produced by Nissan Sanyo corporation.
The resulting current excitation signal according to the method of the present application is shown in fig. 4. The voltage response signal collected is shown in fig. 5.
The electrochemical impedance spectrum obtained by FFT analysis of the above excitation and response signals and the results of measurement using a dedicated test apparatus are shown in FIG. 6, in which the frequency range is 0.1Hz to 10 kHz. The results of the two methods are relatively similar, and the method is relatively accurate.
The method adopts a time domain impedance spectrum measurement technology and combines a switch topological structure to realize the online measurement of the electrochemical impedance spectrum of the lithium ion battery pack, and solves the problems that the traditional frequency domain impedance spectrum measurement equipment is too large in size, low in integration level, too slow in test speed and incapable of realizing online measurement. Meanwhile, through technical improvement of some details, the testing efficiency is improved, the hardware cost is reduced, and the method has a considerable practical value.

Claims (5)

1. The on-line measuring device for the electrochemical impedance spectrum of the lithium ion battery pack is characterized by comprising a processor (1), a signal generator (2), a V-I conversion circuit (3), a switch switching circuit (4) and a sampling circuit (5),
the processor (1) is used for grouping the sine waves of all frequencies and loading the grouped sine waves of all frequencies into different sections of the sine signal of the lowest frequency;
at a frequency of ω0Based on the sine fundamental wave of (a), from ω1To omeganIs divided into m groups ofSuperposed at frequency omega0T of the sine fundamental wave of1s~t1e,t2s~t2e……tms~tmeA segment; the omega0Representing the frequency, ω, of the 1 st sine wave1Representing the frequency, ω, of the 2 nd sine wavenRepresents the frequency of the n +1 th sine wave;
the signal generator (2) is used for obtaining the loaded voltage excitation signals of different sections;
the processor (1) is also used for controlling the switching of the switch switching circuit (4);
the switch switching circuit (4) is used for switching different lithium ion battery monomers so that the lithium ion battery monomers selected by switching receive current excitation signals of different sections;
the V-I conversion circuit (3) is used for converting the voltage excitation signals of different sections into current excitation signals respectively;
the sampling circuit (5) is used for obtaining response voltage signals of different sections from the lithium ion battery cells selected by switching;
the processor (1) is further configured to perform fast fourier transform on the obtained response voltage signals of different sections to obtain voltage vectors of different sections of the lithium ion battery cell, obtain impedances at various frequencies through the voltage vectors and current excitation signals obtained by the V-I conversion circuit (3), and fit the impedances at various frequencies to obtain impedance spectra of the lithium ion battery cell under various excitation signals.
2. The lithium ion battery pack electrochemical impedance spectroscopy on-line measuring device as claimed in claim 1, wherein the V-I conversion circuit (3) comprises resistors R1-R12, resistor Rs, diodes D1-D2, transistors Q1-Q2 and operational amplifiers U1-U3,
the voltage excitation signal output end of the signal generator (2) is simultaneously connected with one end of a resistor R5 and one end of a resistor R6, the other end of a resistor R5 is connected with a power ground, the other end of a resistor R6 is simultaneously connected with the inverting input end of an operational amplifier U1, one end of a resistor R9 and one end of a resistor R8, the non-inverting input end of the operational amplifier U1 is connected with one end of a resistor R7, the other end of a resistor R7 is connected with the power ground,
the positive power supply end of an operational amplifier U1 is simultaneously connected with a +15V power supply, one end of a resistor R1 and one end of a resistor R3, the other end of the resistor R1 is simultaneously connected with the anode of a diode D1 and the base of a triode Q1, the cathode of a diode D1 is simultaneously connected with the output end of the operational amplifier U1 and the anode of a diode D2, the cathode of a diode D2 is simultaneously connected with one end of a resistor R2 and the base of a triode Q2, the other end of the resistor R2 is simultaneously connected with the negative power supply end of the operational amplifier U1, the 15V power supply and one end of a resistor R4, the other end of the resistor R4 is connected with the collector of a triode Q2, the emitter of a triode Q2 is simultaneously connected with the emitter of the triode Q1, the other end of the resistor R8 and one end of a resistor Rs,
the other end of the resistor Rs is simultaneously connected with one end of a resistor R12 and the non-inverting input end of an operational amplifier U3, the inverting input end of the operational amplifier U3 is simultaneously connected with the output end of the operational amplifier U3 and one end of a resistor R11, the other end of the resistor R11 is simultaneously connected with one end of a resistor R10 and the inverting input end of the operational amplifier U2, the non-inverting output end of the operational amplifier U2 is connected with the power ground, the other end of the resistor R10 is simultaneously connected with the output end of the operational amplifier U2 and the other end of the resistor R9,
the other end of the resistor R12 and the grounding wire are both connected with the lithium ion battery pack (6).
3. The lithium ion battery pack electrochemical impedance spectroscopy on-line measuring device of claim 1, wherein the switch switching circuit (4) comprises n pairs of opposite top MOS tubes,
the positive output end of a current excitation signal of the V-I conversion circuit (3) is simultaneously connected with one end of n opposite-top MOS tubes, the negative output end of the current excitation signal of the V-I conversion circuit (3) is simultaneously connected with one end of the other n opposite-top MOS tubes, a lithium ion battery monomer is connected between the other end of each pair of opposite-top MOS tubes in series, and the n lithium ion battery monomers are connected in series.
4. The lithium ion battery pack electrochemical impedance spectroscopy on-line measuring device of claim 3, wherein the sampling circuit (5) collects the response voltage of each lithium ion battery cell from the two ends of the lithium ion battery cell.
5. The lithium ion battery pack electrochemical impedance spectroscopy on-line measuring device as claimed in claim 2, wherein the excitation current I output by the V-I conversion circuit (3)outComprises the following steps:
in the formula, VinExcitation voltage, R, input to the V-I converter circuitSIs the resistance value of the resistor Rs.
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