CN113533992B - Lithium ion battery thermal runaway early warning method based on ultrasonic guided wave sensor - Google Patents
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Abstract
The invention discloses a lithium ion battery thermal runaway early warning method based on an ultrasonic guided wave sensor, wherein the ultrasonic guided wave sensor is fixed on the surface of the lithium ion battery on the same side, and the sensor is connected with a microcontroller chip; carrying out a plurality of complete charge-discharge cycles, wherein the ultrasonic guided wave sensor regularly excites and receives ultrasonic signals passing through the lithium ion battery, and the ultrasonic guided wave signals are collected on line through a microcontroller chip; calculating the difference quotient of TOF and SA measured in two adjacent times, and selecting the difference quotient with the largest absolute value as a threshold value of the thermal runaway early warning of the lithium ion battery; in the actual working process of the lithium ion battery, ultrasonic signals passing through the lithium ion battery are excited and received at regular time through the ultrasonic guided wave sensor, the difference quotient of TOF and SA measured in two adjacent times is calculated by the microcontroller chip, and if the value repeatedly exceeds a threshold value, a thermal runaway early warning signal is sent out. The invention has sufficient basis for judging thermal runaway and good timeliness and reliability.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a lithium ion battery thermal runaway early warning method based on an ultrasonic guided wave sensor.
Background
The lithium ion battery is widely applied to an electric automobile power system by virtue of the advantages of high energy density, high power density, long service life, no memory effect and the like. However, battery safety accidents represented by thermal runaway often occur, which causes casualties and property loss, and affects the vigorous development of the whole electric automobile market.
During the actual use of lithium ion batteries, the occurrence of thermal runaway is very rapid and unpredictable. Abuse conditions are a major source of occurrence of thermal runaway of batteries, which can be classified into mechanical abuse (crushing, dropping, soaking, etc.), electrical abuse (forced overcharge, overdischarge, short circuit, etc.), and thermal abuse (fire, thermal shock, overheat, etc.). When these abuses exceed the allowable range of the battery, side reactions occur inside the battery with a concomitant increase in temperature. Subsequently, a series of reactions such as SEI film decomposition, anode-electrolyte reaction, electrolyte decomposition and diaphragm melting occur in the battery, and finally thermal runaway of the battery is caused.
The thermal runaway of the battery has more causes and complicated mechanism, but the most intuitive expression is the temperature rise. The temperature sensor can detect the change of the surface temperature of the battery, and then early warning is carried out on the thermal runaway of the battery. In practical application, however, one temperature sensor is usually shared by a plurality of battery cells; meanwhile, under the condition of high-rate discharge, the temperature difference between the interior and the surface of the battery can reach 20 ℃. Therefore, the occurrence of thermal runaway cannot be diagnosed in time using a temperature sensor. The detection dimensionality of the lithium ion battery is required to be expanded, and a new perception and thermal runaway early warning method is developed.
Disclosure of Invention
The invention aims to overcome the defects of the existing thermal runaway diagnosis technology and provides a lithium ion battery thermal runaway early warning method based on an ultrasonic guided wave sensor. Carrying out ultrasonic measurement on a working battery at certain time intervals, and calculating TOF and SA of each measurement; and if the difference quotient of TOF and SA of two adjacent measurements exceeds the threshold value at the same time, diagnosing that the battery is in thermal runaway. The early warning method provided by the invention can simultaneously detect various thermal runaway physical phenomena, including gas generation, electrode layering and temperature rise; compared with the method for detecting the temperature rise of the surface of the battery to judge thermal runaway, the detection method based on the ultrasonic guided wave has better timeliness and reliability. Meanwhile, the ultrasonic guided wave sensor has the advantages of small volume, light weight and wide detection range, and is convenient to integrate in a battery management system.
The purpose of the invention is realized by the following technical scheme: a lithium ion battery thermal runaway early warning method based on an ultrasonic guided wave sensor comprises the following steps:
s1, selecting a lithium ion battery, fixing an ultrasonic guided wave sensor on the surface on the same side of the lithium ion battery, and connecting the sensor with a microcontroller chip;
s2, selecting a plurality of lithium ion batteries integrating the ultrasonic guided wave sensors as in S1, carrying out a plurality of complete charge and discharge cycles, wherein the ultrasonic guided wave sensors are excited at regular time and receive ultrasonic signals passing through the lithium ion batteries, and acquiring the ultrasonic guided wave signals on line through a microcontroller chip;
s3, calculating the TOF and the amplitude SA of each measurement by the microcontroller chip, calculating the difference quotient of the TOF and the SA of two adjacent measurements, and selecting the difference quotient with the largest absolute value as the threshold value of the thermal runaway early warning of the lithium ion battery;
s4, in the actual working process of the lithium ion battery, timely exciting and receiving ultrasonic signals passing through the lithium ion battery through the ultrasonic guided wave sensor, calculating the TOF and SA difference quotient of two adjacent measurements by the microcontroller chip, and if the value repeatedly exceeds the threshold determined in S3, sending out a thermal runaway early warning signal.
Wherein, supersound guided wave sensor include: a pair of ultrasonic pulse transmitting sheets and ultrasonic pulse receiving sheets; the ultrasonic pulse transmitting sheet and the ultrasonic pulse receiving sheet are respectively fixed at two ends of the same surface of the lithium ion battery; the ultrasonic pulse transmitting chip and the ultrasonic pulse receiving chip are also in communication connection with the microcontroller chip respectively;
the micro-controller chip sends out instructions at regular time to control the ultrasonic guided wave sensor to send out pulse excitation and receive response signals; and the signals sensed by the ultrasonic guided wave sensor are sent to a microcontroller chip to perform real-time processing on the ultrasonic signals.
The excitation pulse of the micro-controller chip to the ultrasonic pulse transmitting sheet is square wave or cosine wave; the frequency range of the ultrasonic guided wave is between 100 and 300KHz, and the range of the pulse width is 1-5 microseconds.
And one microcontroller chip is connected with a pair of ultrasonic pulse transmitting chips and ultrasonic pulse receiving chips of a single lithium ion battery, or is connected with a plurality of pairs of ultrasonic pulse transmitting chips and ultrasonic pulse receiving chips of a plurality of lithium ion batteries.
Further, the step S2 includes the following sub-steps:
s201, charging the lithium ion batteries to a state of charge SOC of 100% by adopting a constant current first and then constant voltage CCCV method for the plurality of lithium ion batteries, and after standing, completely discharging the lithium ion batteries by adopting a constant current CC discharging method; the microcontroller chip sends instructions at regular time, controls the ultrasonic guided wave sensor to transmit and receive ultrasonic signals passing through the lithium ion battery at certain time intervals, and communicates the received ultrasonic signals to the microcontroller chip;
s202, repeating the charging and discharging circulation in the step S201 until the capacity of the lithium ion battery is attenuated to 80% of the initial capacity.
The step S3 includes the following sub-steps:
s301, calculating TOF and SA of each ultrasonic measurement by a microcontroller chip;
s302, calculating the difference quotient of TOF and SA obtained by two adjacent ultrasonic measurements, wherein the calculation formula is as follows:
wherein the subscriptkAndk-1 each representskSub-sumk-The number of measurements was 1, and,trepresents time;
s303, selecting TOF and SA difference quotient results with the maximum absolute values, and recording the results as
、
；
S304, the threshold values a and b for diagnosing the occurrence of the thermal runaway are respectively defined as:
wherein the content of the first and second substances,nfor safety factor, it is 3-10.
The TOF calculation method in sub-step S301 includes using cross-correlation analysis, and SA is calculated from the maximum amplitude or the cumulative amplitude of the acquired signal.
The step S4 specifically includes:
in the actual use process of the lithium ion battery, ultrasonic measurement is carried out at fixed time intervals, and the time intervals are 5-10 seconds; calculating TOF and SA corresponding to each ultrasonic guided wave measurement, and carrying out difference quotient operation on the TOF and the SA of two adjacent ultrasonic measurements; if this happens continuously:
the microcontroller chip sends a thermal runaway warning signal.
The invention has the beneficial effects that: the invention provides a lithium ion battery thermal runaway early warning method based on an ultrasonic guided wave sensor, which is used for carrying out ultrasonic measurement on a lithium ion battery in actual use, calculating TOF and SA, and diagnosing the thermal runaway of the lithium ion battery according to the fact that the difference quotient of the TOF and the SA repeatedly exceeds a threshold value. The method of the invention has three advantages: firstly, thermal runaway of lithium ion batteries directly leads to internal temperature rise and electrode delamination, both of which contribute to a rapid increase in the ultrasonic characteristic TOF; meanwhile, the thermal runaway period is also accompanied by the generation of internal gas, which weakens the amplitude of the received ultrasonic signal; therefore, the method has sufficient basis for judging thermal runaway and has good timeliness and reliability; secondly, the used ultrasonic guided wave sensor has the frequency of 100KHz order of magnitude, has the advantages of small volume, light weight and wide detection range, and is convenient to integrate in a lithium ion battery management system; thirdly, the invention can realize the early warning of the thermal runaway of the lithium ion battery only by simple differential quotient operation without complex algorithm.
Drawings
FIG. 1 is a flow chart of a method of the present invention;
FIG. 2a is a schematic diagram of a schematic view of an arrangement of an ultrasonic guided wave sensor and a microcontroller chip according to the present invention;
FIG. 2b is a schematic top view of an arrangement of an ultrasonic guided wave sensor and a microcontroller chip according to the present invention;
FIG. 3a is a graph of reference signal versus offset signal amplitude for a cross-correlation analysis;
fig. 3b shows the relationship between the amplitude correlation of the offset signal and the reference signal in the cross-correlation analysis.
The same reference numbers will be used throughout the drawings to refer to the same or like elements or structures, wherein:
1-lithium ion battery 2-ultrasonic pulse transmitting sheet 3-ultrasonic pulse receiving sheet 4-microcontroller chip.
Detailed Description
The technical solutions of the present invention are described in further detail below with reference to the accompanying drawings, but the scope of the present invention is not limited to the following.
As shown in fig. 1, a lithium ion battery thermal runaway early warning method based on an ultrasonic guided wave sensor includes the following steps:
s1, selecting a plurality of lithium ion batteries, fixing an ultrasonic guided wave sensor on the surface on the same side of each lithium ion battery, and connecting a microcontroller chip;
as shown in fig. 2a and 2b, an ultrasonic guided wave sensor includes: a pair of ultrasonic pulse transmitting sheets 2 and ultrasonic pulse receiving sheets 3;
respectively fixing an ultrasonic pulse transmitting sheet 2 and an ultrasonic pulse receiving sheet 3 at two ends of the same surface of the lithium ion battery 1, and carrying out curing treatment; epoxy resin can be used for fixation, the curing time is generally not less than 5 hours, and the lithium ion battery 1 is a soft package battery or a square-shell battery;
the ultrasonic pulse transmitting sheet 2 and the ultrasonic pulse receiving sheet 3 are respectively in communication connection with a microcontroller chip 4;
repeating the installation method, and installing ultrasonic guided wave sensors for the plurality of lithium ion batteries;
the working mode is as follows: the micro-controller chip sends out instructions at regular time to control the ultrasonic guided wave sensor to send out pulse excitation and receive response signals; and the signals sensed by the ultrasonic guided wave sensor are sent to a microcontroller chip to perform real-time processing on the ultrasonic signals.
Specifically, the excitation pulse of the microcontroller chip to the ultrasonic pulse emitting chip can be a square wave or a cosine wave, but is not limited to the above form; the frequency range of the ultrasonic guided wave can be selected between 100 and 300KHz, and the range of the pulse width can be 1-5 microseconds.
Specifically, the microcontroller chip may be connected to a pair of ultrasonic pulse transmitting chips and ultrasonic pulse receiving chips of a single lithium ion battery, or to a plurality of pairs of ultrasonic pulse transmitting chips and ultrasonic pulse receiving chips of a plurality of lithium ion batteries; the plurality of lithium ion batteries realize ultrasonic guided wave measurement, and the purpose is to collect ultrasonic data of the plurality of lithium ion batteries and avoid the accidental ultrasonic measurement of a single lithium ion battery.
S2, selecting a plurality of lithium ion batteries integrating the ultrasonic guided wave sensors as in S1, carrying out a plurality of complete charge and discharge cycles, wherein the ultrasonic guided wave sensors are excited at regular time and receive ultrasonic signals passing through the lithium ion batteries, and acquiring the ultrasonic guided wave signals on line through a microcontroller chip;
s201, charging the lithium ion batteries to a state of charge SOC of 100% by adopting a constant current first and then constant voltage CCCV method for the plurality of lithium ion batteries, and completely discharging the lithium ion batteries by adopting a constant current CC discharging method after standing. And in the period, the microcontroller chip sends a command at regular time, controls the ultrasonic guided wave sensor to transmit and receive ultrasonic signals passing through the lithium ion battery at a certain time interval, and communicates the received ultrasonic signals to the microcontroller chip.
S202, repeating the charging and discharging circulation in the step S201 until the capacity of the lithium ion battery is attenuated to 80% of the initial capacity.
S3, calculating the TOF and the amplitude SA of each measurement by the microcontroller chip, calculating the difference quotient of the TOF and the SA of two adjacent measurements, and selecting the difference quotient with the largest absolute value as the threshold value of the thermal runaway early warning of the lithium ion battery;
s301, calculating TOF and SA of each ultrasonic measurement by a microcontroller chip;
s302, calculating the difference quotient of TOF and SA obtained by two adjacent ultrasonic measurements, wherein the calculation formula is as follows:
wherein the subscriptkAndk-1 each representskSub-sumk-The number of measurements was 1, and,trepresents time;
s303, selecting TOF and SA difference quotient results with the maximum absolute values, and recording the results as
、
；
S304, the threshold values a and b for diagnosing the occurrence of the thermal runaway are respectively defined as:
wherein the content of the first and second substances,nfor safety factor, 3-10 can be selected.
Specifically, the TOF calculation method in the sub-step S301 includes, but is not limited to, a cross-correlation analysis method. Cross-correlation analysis accurately determines the amount of TOF offset between different ultrasound measurements. As shown in fig. 3a and 3b, TOF measured in the early cycle of the lithium ion battery is selected as a reference signal; subsequently, an offset is applied to a given ultrasonic signal relative to a reference signal, and the amplitude correlation of the reference signal and the offset signal is calculated. The offset corresponding to the maximum amplitude correlation degree is the TOF offset, and the cross-correlation analysis method can be expressed by a formula as follows:
wherein the content of the first and second substances,fis a reference signal that is a reference signal,gis the given ultrasonic signal or signals that are,
is the amount of time offset of the ultrasonic wave,tis the time;
the SA is calculated from the maximum or cumulative amplitude of the acquired signal. Particular embodiments employ a cumulative amplitude that can be expressed as:
wherein the content of the first and second substances,t 1 andt 2 respectively, the start time and the end time of the ultrasonic signal.
S4, in the actual working process of the lithium ion battery, timely exciting and receiving ultrasonic signals passing through the lithium ion battery through an ultrasonic guided wave sensor, calculating the difference quotient of TOF and SA of two adjacent measurements by a microcontroller chip, and if the difference quotient repeatedly exceeds the threshold determined in S3, sending out a thermal runaway early warning signal;
in the actual use process of the lithium ion battery, ultrasonic measurement is carried out at fixed time intervals, and the time intervals can be selected to be 5-10 seconds; and calculating TOF and SA corresponding to each ultrasonic guided wave measurement, and carrying out difference quotient operation on the TOF and the SA of two adjacent ultrasonic measurements. If this happens continuously:
the microcontroller chip sends a thermal runaway warning signal.
It should be noted that: in the actual use process of the lithium ion battery, the TOF and SA of the ultrasonic characteristics show regular changes; as the charging process progresses, TOF shows a decreasing trend and SA as a whole shows an increasing trend; for the discharge process, the opposite is true; however, within an ultrasonic measurement time interval of several seconds, the ultrasonic signal change caused by normal use of the lithium ion battery is small and can be approximately ignored compared with the change caused by thermal runaway. Therefore, the difference quotient of the TOF and the SA can be used as a basis for judging the thermal runaway of the lithium ion battery. In addition, this patent detects thermal runaway's accuracy can not receive the ageing influence of lithium ion battery.
According to the steps, early warning can be timely given when the lithium ion battery is out of control due to heat, and further casualties and property loss are avoided.
In the embodiment of the patent, the NMC soft package battery is taken as an experimental object, and the experiment is carried out in the environment of 30 ℃. According to the method, the ultrasonic guided wave sensor is fixed on the surface of the lithium ion battery by using the Hysol E20HP structural epoxy adhesive, and the curing time is 24 hours; the ultrasonic guided wave sensor used is a piezoelectric ceramic wafer with the diameter of 6.35mm and the thickness of 0.254mm, and the frequency is 125 KHz. Then, in order to determine a thermal runaway threshold, carrying out CCCV charging and CC discharging processes on 5 soft package batteries; the constant current charging current in the CCCV stage is 1C, the upper limit cutoff voltage is 4.2V, and the lower limit cutoff current is C/20; standing for 15 minutes; the current during the CC discharge was still 1C, with the lower limit cut-off voltage of 3.0V. Completing ultrasonic measurement every 10 seconds in the charging and discharging process, calculating TOF by adopting a cross-correlation analysis method, and selecting accumulated amplitude to represent SA; the safety factor in the thermal runaway threshold is taken to be 5. In the actual work of the lithium ion battery, ultrasonic measurement is completed every 10 seconds; in the embodiment, if the difference quotient result of TOF and SA exceeds the threshold value for three times, the micro-controller chip sends out a thermal runaway early warning signal. Therefore, the method is expected to give early warning about 1 minute after thermal runaway occurs.
In summary, the invention provides a lithium ion battery thermal runaway early warning method based on an ultrasonic guided wave sensor, which uses the ultrasonic guided wave sensor with small volume to carry out measurement, calculates TOF, SA and difference quotient results thereof according to collected signals, and compares the results with a threshold value to further early warn the thermal runaway of the lithium ion battery. The process for monitoring the thermal runaway of the lithium ion battery is essentially to monitor various thermal runaway phenomena, namely the rise of the internal temperature of the lithium ion battery, gas generation and electrode layering; the method overcomes the defects of the traditional method that the single phenomenon of thermal runaway is monitored and the traditional method is difficult to integrate in a lithium ion battery management system, and has very obvious practical value.
The above description is only for the preferred embodiment of the present invention and is not intended to limit the present invention, and any deduction, modification or replacement made within the spirit of the present invention is also included in the protection scope of the present invention.
Claims (8)
1. A lithium ion battery thermal runaway early warning method based on an ultrasonic guided wave sensor is characterized by comprising the following steps:
s1, selecting a lithium ion battery, fixing an ultrasonic guided wave sensor on the surface on the same side of the lithium ion battery, and connecting the sensor with a microcontroller chip;
s2, selecting a plurality of lithium ion batteries integrating the ultrasonic guided wave sensors as in S1, carrying out a plurality of complete charge and discharge cycles, periodically exciting and receiving ultrasonic signals passing through the lithium ion batteries by the ultrasonic guided wave sensors, and collecting the ultrasonic guided wave signals on line through a microcontroller chip;
s3, calculating the TOF and the amplitude SA of each measurement by the microcontroller chip, calculating the difference quotient of the TOF and the SA of two adjacent measurements, and selecting the difference quotient with the largest absolute value as the threshold value of the thermal runaway early warning of the lithium ion battery;
s4, in the actual working process of the lithium ion battery, the ultrasonic guided wave sensor is used for exciting and receiving ultrasonic signals passing through the lithium ion battery at regular time, the microcontroller chip calculates the difference quotient of TOF and SA of two adjacent measurements, and if the value repeatedly exceeds the threshold determined in S3, a thermal runaway early warning signal is sent out.
2. The lithium ion battery thermal runaway early warning method based on the ultrasonic guided wave sensor as claimed in claim 1, wherein the ultrasonic guided wave sensor comprises: a pair of ultrasonic pulse transmitting sheets and ultrasonic pulse receiving sheets; the ultrasonic pulse transmitting sheet and the ultrasonic pulse receiving sheet are respectively fixed at two ends of the same surface of the lithium ion battery; the ultrasonic pulse transmitting chip and the ultrasonic pulse receiving chip are also in communication connection with the microcontroller chip respectively;
the micro-controller chip sends out instructions at regular time to control the ultrasonic guided wave sensor to send out pulse excitation and receive response signals; and the signals sensed by the ultrasonic guided wave sensor are sent to a microcontroller chip to perform real-time processing on the ultrasonic signals.
3. The lithium ion battery thermal runaway early warning method based on the ultrasonic guided wave sensor as claimed in claim 2, wherein the excitation pulse of the micro controller chip to the ultrasonic pulse emission chip is a square wave or a cosine wave; the frequency range of the ultrasonic guided wave is between 100 and 300KHz, and the range of the pulse width is 1-5 microseconds.
4. The lithium ion battery thermal runaway early warning method based on the ultrasonic guided wave sensor as claimed in claim 2, wherein one microcontroller chip is connected with a pair of ultrasonic pulse transmitting chips and ultrasonic pulse receiving chips of a single lithium ion battery, or is connected with a plurality of pairs of ultrasonic pulse transmitting chips and ultrasonic pulse receiving chips of a plurality of lithium ion batteries.
5. The lithium ion battery thermal runaway early warning method based on the ultrasonic guided wave sensor as claimed in claim 1, wherein the step S2 includes the following substeps:
s201, charging the lithium ion batteries to a state of charge SOC of 100% by adopting a constant current first and then constant voltage CCCV method for the plurality of lithium ion batteries, and after standing, completely discharging the lithium ion batteries by adopting a constant current CC discharging method; the microcontroller chip sends instructions at regular time, controls the ultrasonic guided wave sensor to transmit and receive ultrasonic signals passing through the lithium ion battery at certain time intervals, and communicates the received ultrasonic signals to the microcontroller chip;
s202, repeating the charging and discharging circulation in the step S201 until the capacity of the lithium ion battery is attenuated to 80% of the initial capacity.
6. The lithium ion battery thermal runaway early warning method based on the ultrasonic guided wave sensor as claimed in claim 1, wherein the step S3 includes the following substeps:
s301, calculating TOF and SA of each ultrasonic measurement by a microcontroller chip;
s302, calculating the difference quotient of TOF and SA obtained by two adjacent ultrasonic measurements, wherein the calculation formula is as follows:
wherein the subscriptkAndk-1 each representskSub-sumk-The number of measurements was 1, and,trepresents time;
s303, selecting TOF and SA difference quotient results with the maximum absolute values, and recording the results as
、
；
S304, the threshold values a and b for diagnosing the occurrence of the thermal runaway are respectively defined as:
wherein the content of the first and second substances,nfor safety factor, it is 3-10.
7. The method as claimed in claim 6, wherein the TOF calculation method in the substep S301 includes a cross-correlation analysis method, and SA is calculated from the maximum amplitude or the cumulative amplitude of the collected signal.
8. The lithium ion battery thermal runaway early warning method based on the ultrasonic guided wave sensor as claimed in claim 6, wherein the step S4 specifically includes:
in the actual use process of the lithium ion battery, ultrasonic measurement is carried out at fixed time intervals, and the time intervals are 5-10 seconds; calculating TOF and SA corresponding to each ultrasonic guided wave measurement, and carrying out difference quotient operation on the TOF and the SA of two adjacent ultrasonic measurements; if this happens continuously:
the microcontroller chip sends a thermal runaway warning signal.
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