CN112881929B - Lithium ion battery EIS low-frequency band online measurement method based on step wave - Google Patents
Lithium ion battery EIS low-frequency band online measurement method based on step wave Download PDFInfo
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Abstract
The invention belongs to the technical field of rapid measurement of battery impedance, and relates to a lithium ion battery EIS low-frequency band online measurement method based on step waves, which comprises the steps of determining proper step numbers and current amplitudes of the step waves based on electrochemical reaction characteristics and actual needs of the lithium ion battery; step wave current in a proper frequency range is applied to the lithium ion battery, sine fitting is carried out on the step wave current obtained by sampling and response voltage, impedance values of a required low frequency band are obtained, and then a low frequency band electrochemical impedance spectrum, namely a low frequency band EIS, of the lithium ion battery is formed. The low-frequency EIS online measurement method can accurately reflect the low-frequency impedance information of the lithium ion battery; the method has the effects of high precision of the low-frequency EIS test result of the lithium ion battery, easy realization of engineering and the like, and provides effective technical support for quick evaluation of the health state of the battery and safety early warning.
Description
Technical Field
The invention belongs to the technical field of rapid measurement of battery Impedance, and relates to a lithium ion battery EIS (Electrochemical Impedance Spectroscopy) low-frequency band online measurement method based on a step wave, in particular to a lithium ion battery EIS low-frequency band online high-precision measurement method based on the step wave.
Background
The performance detection, state evaluation and safety early warning of the lithium ion battery are always the problems that need to be mainly solved in the use process of the lithium ion battery, but in the actual use process, due to the complex operation condition and limited test data of the lithium ion battery, the state of the lithium ion battery is difficult to accurately judge and evaluate the performance of the lithium ion battery. In laboratory research, it is found that more important battery performance and state information can be obtained by analyzing low-frequency-band data of electrochemical impedance spectrum. Particularly, the low-frequency data of the electrochemical impedance spectrum is more important when the quick evaluation of the health state of the lithium ion battery, the capacity diving early warning and the thermal runaway early warning are realized.
However, the conventional EIS measurement method is difficult to implement in practical applications because it requires a special device to output a sine wave excitation; the existing square wave EIS measuring method in the prior engineering obtains a corresponding sine wave by decomposing a square wave. Because the harmonic amplitude and the fundamental amplitude obtained after decomposition have differences, and the error in the EIS low frequency band is relatively large, further improvement of the measurement accuracy becomes necessary. The step wave is closer to the sine wave excitation, the amplitude of each frequency is consistent, and the mechanism is superior to that of a square wave; and the required working condition can be output by charger equipment, the sampling frequency requirement is not high, and the engineering realization is easy.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a lithium ion battery EIS low-frequency band online high-precision measurement method based on step waves, which can solve the problems that the prior art cannot realize online high-precision measurement of lithium ion battery EIS low-frequency bands and sine current test EIS in engineering and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a lithium ion battery EIS low-frequency band online measurement method based on step waves comprises the following steps:
s1, according to the formula (1), the sine wave current required by the electrochemical impedance spectrum test is equivalent to the step wave current, the step number N of the step wave current corresponding to the sine wave current in one period is determined,
yn＝Asin((n-1)H+H/2) (1)
wherein, ynThe current amplitude of the nth step is shown, A is the current amplitude of the electrochemical impedance spectrum test, N is 1,2,3, …, N, the number of the steps in the step wave current is shown, N is the step number, H is calculated by formula (2),
H＝2π/N (2)；
s2, determining the current amplitude of each step in the step wave current, namely y, according to the sine wave current amplitude of the electrochemical impedance spectrum test needing to be equivalent1,y2,…,yn；
S3, applying step wave current to the lithium ion battery, determining the frequency range of the applied step wave current according to actual needs, calculating the total time T of the applied step wave current under each frequency, further determining the current duration T of each step in the step wave current under different frequencies, and combining the step wave current under each frequency to obtain a variable-frequency step wave current spectrum;
s4, applying a frequency conversion step wave current spectrum to the lithium ion battery, selecting a proper sampling frequency according to a sampling theorem, sampling the step wave current and the step wave response voltage, wherein the frequency range of the step wave current can be expanded upwards along with the increase of the sampling frequency of sampling equipment;
s5, respectively carrying out sine fitting on the step wave current and the step wave response voltage under different frequencies obtained by sampling to obtain the fitted sine current and the fitted sine response voltage under different frequencies;
and S6, dividing the fitted lithium ion battery sinusoidal response voltage under the corresponding frequency by the sinusoidal current to obtain complex impedance under the frequency, and combining the impedance values under different frequencies to obtain the electrochemical impedance spectrum of the low frequency band.
Based on the above technical solution, in step S1, N generally has to be 10, that is, 10 same intervals. The larger the value of N is, the better the effect that the step wave current is equivalent to the sine wave current is, but the larger the step number N is, the smaller the current duration t corresponding to each step is, which is not beneficial to practical application; if the value of N is too small, the sine wave current cannot be equivalent.
In addition to the above technical solution, in step S3, if the frequency of the step wave current is f, the total time T of the step wave current is calculated by equation (3),
T＝1/f (3)
the current duration t for each step at that frequency is calculated by equation (4),
t＝T/N (4)。
on the basis of the technical scheme, the step wave response voltage is the change value delta U of the voltage of the lithium ion battery after the lithium ion battery is excited by the step wave current, the expression formula is shown in formula (5),
ΔU＝UO-UOCV (5)
wherein, UOIs the terminal voltage U of the lithium ion battery after being excited by the step wave currentOCVIs the open circuit voltage of the lithium ion battery.
On the basis of the above technical solution, the formula for obtaining the complex impedance at the frequency in step S6 is shown in formulas (6), (7) and (8),
Re＝Z·cosθ (7)
Im＝Z·sinθ (8)
wherein, the delta U is the amplitude of the sinusoidal response voltage, namely the variation value delta U of the voltage of the lithium ion battery,
The phase angle of the sinusoidal response voltage, I is the amplitude of the sinusoidal current, alpha is the phase angle of the sinusoidal current, Z is impedance, theta is the impedance angle, Re is the real part of the impedance, and Im is the imaginary part of the impedance.
Based on the technical scheme, the delta U,
I and α are both positive by the fitting of step S5Chord current and sinusoidal response voltage data.
On the basis of the technical scheme, the lithium ion battery is a lithium manganate power battery, a lithium iron phosphate power battery or a ternary material power battery.
The lithium ion battery EIS low-frequency band online high-precision measurement method based on the step wave has the following beneficial technical effects:
1. the EIS low-frequency-band test is carried out through the step wave current, so that the EIS test can be equivalent to the sine wave EIS test in a mechanism better, the sine wave obtained by the EIS test is more accurate compared with the sine wave obtained by the square wave EIS test, meanwhile, the Fourier decomposition processing process is not needed, the calculation error is reduced, and the precision is higher;
2. the method for testing the EIS low frequency band of the lithium ion battery on line in engineering is provided, the Weber impedance information of the lithium ion battery is mastered on line in real time, and an effective method and data support are provided for quick evaluation and safety early warning of the health state of the lithium ion battery;
4. the lithium ion battery EIS measuring method based on the step wave is carried out at a low frequency band, the sampling frequency requirement is not high, the data volume is not large, the method is very suitable for online real-time measurement, and is particularly suitable for lithium ion battery electrochemical performance detection, health state quick evaluation, safety early warning and the like of practical vehicles.
Drawings
The invention has the following drawings:
FIG. 1 is a schematic flow diagram of the process of the present invention;
FIG. 2 is a schematic diagram of a response voltage curve of a lithium ion battery excited by a step wave current with a frequency of 0.5Hz and an equivalent sinusoidal current wave amplitude of 8A;
FIG. 3 is a schematic diagram of a sine-fitting curve of a stepped-wave current with a frequency of 0.5Hz and an equivalent sinusoidal current wave amplitude of 8A and a lithium ion battery response voltage under excitation thereof;
FIG. 4 is a Nyquist plot of staircase wave excitation versus sinusoidal excitation;
FIG. 5 is a graph of real part impedance Bode under stepped wave excitation and sinusoidal excitation;
FIG. 6 is a graph of imaginary impedance Bode under stepped wave excitation and sinusoidal excitation;
fig. 7 is a comparison graph of Nyqusit at a low frequency band under staircase wave excitation, square wave excitation, and sine wave excitation.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
As shown in fig. 1, the lithium ion battery EIS low-frequency band online measurement method based on the step wave includes the following steps:
s1, according to the formula (1), the sine wave current required by the electrochemical impedance spectrum test is equivalent to the step wave current, the step number N of the step wave current corresponding to the sine wave current in one period is determined,
yn＝Asin((n-1)H+H/2) (1)
wherein, ynThe current amplitude of the nth step is shown, A is the current amplitude of the electrochemical impedance spectrum test, N is 1,2,3, …, N, the number of the steps in the step wave current is shown, N is the step number, H is calculated by formula (2),
H＝2π/N (2)
s2, determining the current amplitude of each step in the step wave current, namely y, according to the sine wave current amplitude of the electrochemical impedance spectrum test needing to be equivalent1,y2,…,yn；
S3, applying step wave current to the lithium ion battery, and determining the frequency range of the applied step wave current according to actual needs, namely determining the EIS test frequency range shown in figure 1; calculating the total time T of applying step wave current under each frequency, further determining the current duration T of each step in the step wave current under different frequencies, and combining the step wave current under each frequency to obtain a variable-frequency step wave current spectrum;
s4, applying a frequency conversion step wave current spectrum to the lithium ion battery, selecting a proper sampling frequency according to a sampling theorem, sampling step wave current and step wave response voltage (as shown in figure 1, referred to as response voltage for short), wherein the frequency range of the step wave current can be expanded upwards along with the increase of the sampling frequency of sampling equipment;
s5, respectively carrying out sine fitting on the step wave current and the step wave response voltage under different frequencies obtained by sampling to obtain the fitted sine current and the fitted sine response voltage under different frequencies;
s6, dividing the fitted sinusoidal response voltage with the corresponding frequency by the sinusoidal current to obtain the impedance at the frequency, and combining the impedance values with different frequencies to obtain the electrochemical impedance spectrum of the low frequency band, i.e., the stepped wave EIS shown in fig. 1.
Based on the above technical solution, in step S1, N generally has to be 10, that is, 10 same intervals. The larger the value of N is, the better the effect that the step wave current is equivalent to the sine wave current is, but the larger the step number N is, the smaller the current duration t corresponding to each step is, which is not beneficial to practical application; if the value of N is too small, the sine wave current cannot be equivalent.
In addition to the above technical solution, in step S3, if the frequency of the step wave current is f, the total time T of the step wave current at the frequency is calculated by equation (3),
T＝1/f (3)
the current duration t for each step at that frequency is calculated by equation (4),
t＝T/N (4)
on the basis of the technical scheme, the lithium ion battery is a lithium manganate power battery, a lithium iron phosphate power battery or a ternary material power battery.
The following embodiments are described with reference to a certain brand of ternary power battery as an example.
When the state of charge (SOC) of the lithium ion battery is 96%, the lithium ion battery is excited by selecting the step wave current with the frequency points shown in the table 1 according to the range of the electrochemical impedance spectrum to be measured.
TABLE 1 step wave Current selection frequency Point List
A sine wave of one period is equivalent to a step wave with the step number N of 10, that is, one period is divided into 10 equally spaced segments.
The amplitude of the sinusoidal current excitation (namely the current amplitude of the electrochemical impedance spectroscopy test) is selected to be 8A, and the current amplitude of each step of 10 steps of the step wave current is calculated according to the formula (1). And determining the current duration of each step wave at each frequency point according to the frequency shown in the table 1. And applying set step wave current to the lithium ion battery, and sampling to obtain a response voltage signal under corresponding frequency. Fig. 2 is a schematic diagram of a response voltage curve of a lithium ion battery excited by a step wave current with an applied frequency of 0.5Hz and an equivalent sinusoidal current wave amplitude of 8A.
And respectively carrying out sine fitting on the step wave current excitation and the voltage response obtained by sampling to obtain equivalent sine wave current excitation and sine wave voltage response. Fig. 3 is a schematic diagram of a sine-fitting curve of an applied step wave current with a frequency of 0.5Hz and an equivalent sine wave current amplitude of 8A and a response voltage of a lithium ion battery under excitation of the step wave current.
The step wave response voltage used here is the change value delta U of the lithium ion battery voltage after the lithium ion battery is excited by the step wave current, the expression of which is shown in formula (5),
ΔU＝UO-UOCV (5)
wherein, UOIs the terminal voltage U of the lithium ion battery after being excited by the step wave currentOCVIs the open circuit voltage of the lithium ion battery.
Then, dividing the sinusoidal response voltage of the lithium ion battery obtained by sinusoidal fitting at each frequency by the excitation current (i.e., sinusoidal current), so as to obtain a complex impedance, as shown in equations (6), (7) and (8):
Re＝Z·cosθ (7)
Im＝Z·sinθ (8)
wherein, the delta U is the amplitude of the sinusoidal response voltage, namely the variation value delta U of the voltage of the lithium ion battery,
the phase angle of the sinusoidal response voltage, I the amplitude of the excitation current, and α the phase angle of the excitation current can be obtained from the sinusoidal wave data after the step wave fitting (i.e., the fitted sinusoidal current and sinusoidal response voltage data described in step S5), Z is impedance, θ is the impedance angle, Re is the real impedance part, and Im is the imaginary impedance part.
In this example, the resulting impedance is shown in fig. 4. It can be found that the low-frequency-band curves of the step wave EIS and the sine wave EIS are basically superposed, and the goodness of fit is extremely high.
When the real part of the impedance is analyzed, as shown in fig. 5, the real part of the impedance obtained by the step wave and the real part of the impedance obtained by the sine wave are substantially the same, and the error is extremely small.
Analyzing the imaginary part of the impedance, as shown in fig. 6, the imaginary part of the impedance obtained by the step wave is substantially the same as the imaginary part of the impedance obtained by the sine wave, and the error is also very small.
In a whole view, the EIS low-frequency band measured by the step wave can be well equivalent to the sine wave low-frequency band, and the error is very small, so that the method is higher in engineering feasibility.
Compared with the square wave EIS test method which is proposed at present, although the whole section of curve of the EIS can be measured, the calculation error in the decomposition process increases the result error of the square wave EIS test because the Fourier decomposition is involved. Particularly in the low frequency band, as shown in fig. 7, the square wave EIS measurement method has a large error, and the non-fundamental wave value obtained after each fourier decomposition of the band will be far away from the actual value of the sine wave EIS, which increases the difficulty in selecting and processing data points in practical application. However, the step wave can be well equivalent to a sine wave, a Fourier decomposition process is not needed, and the calculation error is reduced and is accurate enough.
The main reason that the traditional sine EIS is difficult to apply in practical engineering is that sine wave excitation is difficult to generate in practical application, but step wave excitation is easy to realize in practical application, so that the method for measuring the EIS low frequency band on line through the step wave has important significance to the practical engineering. On the other hand, although the existing square wave measurement EIS method is applied to practical engineering, the method involves square wave decomposition, and the error of the sine value obtained after decomposition is larger than that obtained after step wave fitting, so that the information of the EIS low frequency band cannot be accurately obtained. Therefore, the information of the EIS low frequency band is accurately measured on line through the step wave, and the method is very necessary for the existing practical application.
The method for measuring the EIS low frequency band on line by the step wave can be applied to the aspects of lithium ion battery electrochemical performance detection, health state quick evaluation, safety early warning and the like of an actual vehicle.
It should be understood that the illustrated embodiments are merely examples for clearly illustrating the invention and are not to be construed as limitations of the embodiments of the invention, and that various other changes and modifications may be made by those skilled in the art based on the above description.
The above embodiments are merely illustrative, and not restrictive, and those skilled in the relevant art can make various changes and modifications without departing from the spirit and scope of the invention, and therefore all equivalent technical solutions also belong to the scope of the invention.
Those not described in detail in this specification are within the knowledge of those skilled in the art.
Claims (7)
1. A lithium ion battery EIS low-frequency band online measurement method based on step waves is characterized by comprising the following steps:
s1, according to the formula (1), the sine wave current of the electrochemical impedance spectrum test is equivalent to the step wave current, the step number N of the step wave current corresponding to the sine wave current in one period is determined,
yn＝Asin((n-1)H+H/2) (1)
wherein, ynThe current amplitude of the nth step is shown, A is the current amplitude of the electrochemical impedance spectrum test, N is 1,2,3, …, N, the number of the steps in the step wave current is shown, N is the step number, H is calculated by formula (2),
H＝2π/N (2)；
s2, determining the current amplitude of each step in the step wave current according to the sine wave current amplitude tested by the electrochemical impedance spectroscopy;
s3, applying step wave current to the lithium ion battery, determining the frequency range of the applied step wave current according to actual needs, calculating the total time T of the applied step wave current under each frequency, further determining the current duration T of each step in the step wave current under different frequencies, and combining the step wave current under each frequency to obtain a variable-frequency step wave current spectrum;
s4, applying a frequency conversion step wave current spectrum to the lithium ion battery, selecting a proper sampling frequency according to a sampling theorem, and sampling the step wave current and the step wave response voltage;
s5, respectively carrying out sine fitting on the step wave current and the step wave response voltage under different frequencies obtained by sampling to obtain the fitted sine current and the fitted sine response voltage under different frequencies;
s6, dividing the fitted lithium ion battery sinusoidal response voltage under the corresponding frequency by the sinusoidal current to obtain a complex impedance under the frequency, and combining impedance values under different frequencies to obtain an electrochemical impedance spectrum of a low frequency band;
in step S1, N is 10.
2. The lithium ion battery EIS low-frequency band online measuring method based on the step wave as claimed in claim 1, is characterized in that: in step S3, if the frequency of the step wave current is f, the total time T of the step wave current is calculated by equation (3),
T＝1/f (3)
the current duration t for each step at that frequency is calculated by equation (4),
t＝T/N (4)。
3. the lithium ion battery EIS low-frequency band online measuring method based on the step wave as claimed in claim 1, is characterized in that: the step wave response voltage is a change value delta U of the voltage of the lithium ion battery after the lithium ion battery is excited by the step wave current, and the expression is shown as formula (5), wherein the delta U is UO-UOCV (5)
Wherein, UOIs the terminal voltage U of the lithium ion battery after being excited by the step wave currentOCVIs the open circuit voltage of the lithium ion battery.
4. The step wave-based EIS low-frequency band online measuring method for the lithium ion battery as claimed in claim 1 or 3, wherein the step wave-based EIS low-frequency band online measuring method comprises the following steps: the formula for obtaining the complex impedance at the frequency in step S6 is shown in formulas (6), (7) and (8),
Re＝Z·cosθ (7)
Im＝Z·sinθ (8)
wherein, Delta U is the amplitude of the sinusoidal response voltage,
The phase angle of the sinusoidal response voltage, I is the amplitude of the sinusoidal current, alpha is the phase angle of the sinusoidal current, Z is impedance, theta is the impedance angle, Re is the real part of the impedance, and Im is the imaginary part of the impedance.
5. The step wave-based EIS low-frequency band online measuring method for the lithium ion battery as claimed in claim 4, wherein the step wave-based EIS low-frequency band online measuring method comprises the following steps: the delta U,
Both I and α are fitted by step S5Sinusoidal current and sinusoidal response voltage data.
6. The lithium ion battery EIS low-frequency band online measuring method based on the step wave as claimed in claim 1, is characterized in that: the lithium ion battery is a lithium manganate power battery, a lithium iron phosphate power battery or a ternary material power battery.
7. The application of the lithium ion battery EIS low-frequency band online measuring method based on the step wave as claimed in any one of claims 1 to 6 in the fast evaluation of the health state of the lithium ion battery, the capacity diving early warning and the thermal runaway early warning.
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