CN109765496A - A kind of cell health state estimation method based on online electrochemical impedance spectrometry - Google Patents
A kind of cell health state estimation method based on online electrochemical impedance spectrometry Download PDFInfo
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Abstract
The invention discloses a kind of cell health state estimation methods based on online electrochemical impedance spectrometry, this method actually uses the voltage and current data progress signal processing under operating condition to collected battery using Morlet small echo and obtains the EIS of battery then with the SOH of its characterization battery, compared with the method based on data-driven, without carrying out many experiments and versatile;With it is existing based on the method for electrochemical model or equivalent circuit model parameter compared with, calculate simple and have higher accuracy.It is described using Morlet small echo to collected battery actually use the voltage and current data under operating condition converted to obtain the method for the EIS of battery compared with apply the method for motivating measurement EIS have the advantages that it is simple, at low cost, high-efficient and can on-line analysis.
Description
Technical field
The invention belongs to cell health state estimation technique field, in particular to a kind of electricity based on online impedance spectrometry
Pond health status estimation method.
Background technique
With the continuous aggravation of bad border problem and energy crisis, electric car is energy saving with its, zero waste discharge, makes an uproar
The advantages such as sound is low receive the favor of each enterprise of every country.Battery management system as one of electric car core technology
System is the important tie for connecting vehicle mounted dynamic battery and electric car.It must be able to real-time monitoring battery operation situation and estimates
The state-of-charge (state of charge, SOC) and health status (state of health, SOH) of battery, to be vehicle-mounted
Control system and driver or passenger provide relevant information necessary to decision.Outstanding battery management system can not only fill
Electric car superiority is waved in distribution, while can also give battery optimal protection, to extend the service life of electric car.
Key parameter one of of the battery SOH as battery is that the core of cell management system of electric automobile is asked all the time
Topic and technological difficulties urgently to be solved.Accurate SOH estimation is improving SOC estimated accuracy, is preventing from having in over-charging of battery over-discharge
The effect that can not ignore.
Currently, mainly being predicted both at home and abroad by two methods battery SOH: the first is the method based on data,
A large amount of data training genetic algorithm, neural network etc. are obtained with the algorithm compared with strong nonlinearity by experiment, make it
The SOH of battery can be predicted by data such as measurable voltage, electric currents, such methods needs, which take considerable time, is tested, and
The accuracy of SOH estimation relies heavily on the acquired data of experiment, and versatility is poor;Second is the method based on parameter,
It is primarily based on the battery model that related basic theories establishes electrochemistry, an equivalent circuit etc., then in Selection Model
It is certain to change with cell degradation and be convenient for measuring the parameter of estimation to characterize the SOH of battery, this method compared to
The former does not need largely to be tested, and versatility is stronger.
There are mainly two types of the existing methods based on parameter, and one is dense using the recyclable lithium ion in electrochemical model
Degree characterization battery SOH, one is battery SOH is indicated using the internal resistance in equivalent-circuit model.Electrochemical model is based on electricity
The model that the physical-chemical reaction really occurred inside pond is set up according to corresponding basic theory, thus the former has very
Real and intuitive physical significance and accuracy of estimation is higher, however, since the state equation of electrochemical model is one group by complexity
Partial differential equation of second order group it is discrete and come linear algebraic equation systems, the calculation amount of this method is larger not to be suitable for vehicle-mounted reality
When control system.Equivalent-circuit model used in the latter is to regard battery as to be made of basic circuit components such as capacitance resistances
Network, state equation is only simple ODE, thus calculation amount is small, speed is fast, however, due to solid-liquid in battery
Represented by the out-phase charge transfer process occurred on interface can not be by simple basic circuit component, this method it is accurate
Spend lower and no actual physical significance.
Electrochemical impedance spectroscopy (EIS) indicates electrification by introducing Faradaic impedance element varying with frequency in circuit
It learns the out-phase charge transfer process in pond and establishes a kind of model between electrochemical model and equivalent-circuit model and carry out table
Levy electrochemical cell.It can more completely characterize the performance state of electrochemical cell than equivalent-circuit model and calculate compared with electrochemical model
Simply.In field of batteries, this method is widely used to the performance in the design processing of battery to optimize battery.However,
Existing EIS measurement method is carried out by the way of applying excitation measurement respective response, this needs special electrochemistry
Work station or impedance analysis equipment, therefore it may not apply to cell management system of electric automobile and carries out on-line measurement.
Summary of the invention
In order to overcome the disadvantages of the above prior art, the purpose of the present invention is to provide one kind to be based on online electrochemical impedance
The cell health state estimation method of spectrometry, this method actually use under operating condition collected battery using Morlet small echo
Voltage and current data carry out time frequency analysis and obtain the SOH that the EIS of battery then characterizes battery with it, it is a large amount of real without carrying out
It tests, accuracy is high, calculates fastly, can preferably be applied in actual use.
The present invention adopts the following technical scheme that realize:
A kind of cell health state estimation method based on online electrochemical impedance spectrometry, comprising the following steps:
The first step, using the electrochemical workstation battery different to same batch degree of aging in identical environment temperature and phase
With being tested under SOC, its EIS is obtained;
Second step analyzes the battery EIS of acquisition, it is known that projection of the battery EIS low frequency inflection point on real axis and its
Degree of aging is positively correlated, to diagnose the SOH of battery by the real part of battery EIS low frequency inflection point;
Third step imitates the single order RC model that Gary road state of cyclic operation current data is applied to mesuring battary
Very, the voltage data under mesuring battary UDDS operating condition is obtained, to mesuring battary both end voltage electric current under UDDS operating condition obtained
Data carry out time frequency analysis respectively and obtain corresponding frequency spectrum, to point known to the spectrum analysis of acquisition it includes each Frequency point
Amount, therefore use the measurement of mesuring battary both end voltage current data progress mesuring battary impedance spectrum under actual condition;
4th step distinguishes mesuring battary both end voltage current data under UDDS operating condition obtained using Morlet small echo
It carries out Morlet wavelet transformation and extracts the impedance information under its different frequency, be than upper current data with transformed voltage data
It can get mesuring battary EIS;
The real part of the EIS low frequency inflection point of mesuring battary is normalized according to second step data acquired for 5th step
The mesuring battary SOH value to be estimated can be obtained.
A further improvement of the present invention lies in that battery is lead-acid battery.
A further improvement of the present invention lies in that battery is nickel-metal hydride battery.
A further improvement of the present invention lies in that battery is nickel-cadmium cell.
A further improvement of the present invention lies in that battery is lithium ion battery.
It can a further improvement of the present invention lies in that emulating resulting battery both end voltage current data according to UDDS operating condition
It replaces with and acquires resulting voltage and current data under true Electric Vehicles Driving Cycle.
A further improvement of the present invention lies in that Morlet small echo can replace with Fourier transformation.
A further improvement of the present invention lies in that Morlet small echo can replace with Hilbert-Huang transformation.
The present invention has following beneficial technical effect:
Cell health state estimation method based on online electrochemical impedance spectrometry proposed by the invention, this method are logical
It crosses and electricity is obtained to the voltage and current data progress time frequency analysis under collected battery actual use operating condition using Morlet small echo
The EIS in pond then characterizes the SOH of battery with it, compared with the method based on data-driven, without carrying out many experiments and general
Property is strong;With it is existing based on the method for electrochemical model or equivalent circuit model parameter compared with, calculate it is simple and have it is higher accurate
Degree.
Further, it is described using Morlet small echo to collected battery actually use operating condition under voltage and current data into
Row signal processing obtain the method for the EIS of battery compared with apply the method for motivating measurement EIS have it is simple, at low cost, high-efficient and
Can on-line analysis the advantages of.
Detailed description of the invention
Fig. 1 is overall framework figure of the invention.
Fig. 2 is the EIS of the NCR18650 battery used in the embodiment of the present invention.
Fig. 3 is the EIS of different degree of aging batteries in the embodiment of the present invention.
Fig. 4 is the flow chart for carrying out battery EIS analysis in the embodiment of the present invention using Morlet small echo.
Fig. 5 is the single order RC equivalent-circuit model of NCR18650 battery employed in the embodiment of the present invention.
Fig. 6 is Morlet small echo employed in the embodiment of the present invention, and wherein Fig. 6 (a) is that Morlet wavelet function is bent
Line,
Fig. 6 (b) is the several curves of Gaussian function, and Fig. 6 (c) is sinusoidal function item curve.
Fig. 7 is battery both end voltage current data and its frequency spectrum under UDDS operating condition in the embodiment of the present invention, wherein Fig. 7 (a)
For current signal, Fig. 7 (b) is voltage signal, and Fig. 7 (c) is current signal spectrogram, and Fig. 7 (d) is voltage signal spectrogram.
Fig. 8 is EIS pairs of the battery EIS analyzed in the embodiment of the present invention using Morlet Complex wavelet and theory
Than wherein Fig. 8 (a) is impedance spectrum, and Fig. 8 (b) is impedance magnitude, and Fig. 8 (c) is impedance angle.
Specific embodiment
The present invention is described in detail with reference to the accompanying drawings and examples.
Referring to Fig.1, a kind of cell health state estimation side based on online electrochemical impedance spectrometry provided by the invention
Method, comprising the following steps:
The first step, using electrochemical workstation to the battery different with a collection of batch degree of aging in identical environment temperature and
It is tested under identical SOC, obtains its EIS;
Second step analyzes the battery EIS of acquisition, it is known that projection of the battery EIS low frequency inflection point on real axis and its
Degree of aging is positively correlated, to diagnose the SOH of battery by the real part of battery EIS low frequency inflection point;
Gary road state of cyclic operation (UDDS) current data is applied to the single order RC model of mesuring battary by third step
It is emulated, obtains the voltage data under mesuring battary UDDS operating condition.To mesuring battary both ends electricity under UDDS operating condition obtained
Piezoelectricity flow data carries out time frequency analysis respectively, to it includes the components of each Frequency point known to the spectrum analysis of acquisition, therefore can be in fact
Mesuring battary both end voltage current data carries out the measurement of mesuring battary impedance spectrum under the operating condition of border;
4th step distinguishes mesuring battary both end voltage current data under UDDS operating condition obtained using Morlet small echo
It carries out Morlet wavelet transformation and extracts the impedance information under its different frequency, be than upper current data with transformed voltage data
It can get mesuring battary EIS;
The real part of the EIS low frequency inflection point of mesuring battary is normalized according to second step data acquired for 5th step
The mesuring battary SOH value to be estimated can be obtained.
The battery is lead-acid battery, nickel-metal hydride battery, nickel-cadmium cell or lithium ion battery.
The process for carrying out EIS analysis to battery using Morlet small echo are as follows: by Gary road state of cyclic operation
(UDDS) the single order RC model that current data is applied to battery is emulated, and obtains the voltage data under battery UDDS operating condition;It adopts
Morlet wavelet transformation is carried out respectively to battery both end voltage current data under UDDS operating condition obtained with Morlet small echo to mention
The impedance information under its different frequency is taken, can be obtained battery EIS than upper current data with transformed voltage data.
It is described that true electric car row can be replaced according to the resulting battery both end voltage current data of UDDS operating condition emulation
It sails and acquires resulting voltage and current data under operating condition.
The Morlet small echo can replace with Fourier transformation or Hilbert-Huang transformation.
Embodiment:
Battery used by the present embodiment is NCR18650 ternary lithium battery, and measuring battery, SOC is 80% at room temperature
The nyquist diagram of electrochemical impedance spectroscopy, referring to Fig. 2, wherein horizontal axis is impedance real part, and the longitudinal axis is the amplitude of imaginary impedance, from a left side
It is divided into high frequency (5Hz-5kHz), intermediate frequency (0.1Hz-3.5Hz), low frequency part (0.1Hz or less) to the right side, wherein low frequency inflection point
Position reaction inside battery solid electrolyte (SEI) film generate the degree that side reaction carries out.With circulating battery number
Increase, the SEI film of inside battery side reaction accumulation gradually thickeies, and leads to the continuous reduction of recyclable lithium concentration, while electricity
Pond internal resistance is also continuously increased, so as to cause the aggravation of degree of aging.On the EIS of battery, low frequency inflection point real part is shown as
Increase, therefore battery SOH can be estimated by the size of the EIS low frequency inflection point real part of analysis battery.
For the size of the EIS low frequency inflection point real part of verifying battery and the relationship of battery SOH, 5 pieces of degree of aging differences are chosen
Battery carry out static capacity experiment at room temperature, experimental result is shown in Table 1.
The actual measurement capacity of 1 five pieces of aging difference batteries of table
The maximum battery SOH of capacity is set as 100%, the smallest battery SOH of capacity is set as 0%, carries out to other batteries
The practical SOH value that normalized obtains 5 pieces of batteries is shown in Table 2.
The practical SOH of 2 five pieces of aging difference batteries of table
Offline EIS is carried out at room temperature using the electrochemical workstation battery different to selected 5 pieces of degree of agings to measure
To EIS such as Fig. 3 of its 1000Hz~0.01Hz, extreme value is taken to obtain its corresponding low frequency inflection point real part experiment gained EIS data
Amplitude is shown in Table 3.
The EIS low frequency inflection point real part amplitude of 3 five pieces of aging difference batteries of table
The battery SOH of real part amplitude maximum is set as 100%, the smallest battery SOH of real part amplitude is set as 0%, to other
Battery, which is normalized to obtain 5 pieces of batteries, is shown in Table 4 according to the SOH value that EIS low frequency inflection point real part amplitude is predicted.
The SOH of the EIS low frequency inflection point real part amplitude prediction of 4 five pieces of aging difference batteries of table
Using according to the resulting battery SOH value of capacity as criterion calculation 5 pieces of battery EIS low frequency inflection point real part amplitudes prediction
SOH value error is shown in Table 5.As shown in Table 5 according to the SOH value of battery EIS low frequency inflection point real part amplitude prediction compared with the practical SOH value of battery
Error is within 5%.
SOH estimation method error of the table 5 based on impedance spectrum
Battery EIS low frequency inflection point real part amplitude On-line Estimation SOH value is used to realize, need to realize online battery EIS measurement.
The present invention uses Morlet Complex wavelet to carry out time frequency analysis to battery actual condition voltage and current data to extract battery difference
Impedance information under frequency.Referring to Fig. 4, basic procedure are as follows: firstly, obtaining battery reality by electric current and voltage sensor measurement
Voltage and current data under the operating condition of border;Secondly, carrying out Morlet wavelet transformation respectively to obtained voltage and current data, to extract its right
The frequency domain information answered;Finally, by the voltage data V (s) after Morlet wavelet transformation divided by corresponding current data I (s)
Obtain the impedance information Z (s) under battery respective frequencies.
Online EIS measurement, the present embodiment effectively are carried out to battery for the small wave energy of Morlet designed by the verifying present invention
The emulation of online battery EIS measurement is carried out using single order RC model and UDDS data.Referring to Fig. 5, used in the present embodiment emulation
NCR18650 battery single order RC model by ideal constant pressure source E0, ohmic internal resistance R1, polarization resistance R2And polarization capacity C2Structure
At wherein ideal constant source voltage is 3.7V, ohmic internal resistance is 0.072 Ω, polarization resistance is 0.01 Ω, polarization capacity is
634F.Referring to Fig. 6, Morlet small echo used by the present embodiment is formed by stacking by Gaussian function and SIN function, and Fig. 6 (a) is
Used Morlet wavelet function curve, Fig. 6 (b) and Fig. 6 (c) be respectively Gaussian function it is several with corresponding to SIN function item
Curve.The UDDS current data used in the present embodiment emulation is shown in Fig. 7 (a), its application is obtained it with above-mentioned single order RC model
Corresponding voltage data is shown in that Fig. 7 (b), frequency spectrum corresponding to electric current and voltage data are shown in Fig. 7 (c) and Fig. 7 (d) respectively.By Fig. 7
(c) know although the voltage and current data under battery actual condition are non-stationary signals with Fig. 7 (d), but it includes all frequencies
Under information, therefore can be used for EIS measurement to realize the on-line measurement of battery EIS.Using designed Morlet small echo, according to
Process shown in Fig. 4 analyzes above-mentioned voltage and current data to obtain the single order RC of the NCR18650 battery of the present embodiment use
The impedance spectrum of model and its true inferential impedance spectrum are shown in Fig. 8.The small wave energy of Morlet as shown in Figure 8 designed by the present invention is effective
Ground carries out online EIS measurement to battery, and precision is higher, therefore can be used for proposed by the invention based on online electrochemical impedance spectroscopy
The cell health state estimation method of measurement.
Claims (8)
1. a kind of cell health state estimation method based on online electrochemical impedance spectrometry, which is characterized in that including following
Step:
The first step, using the electrochemical workstation battery different to same batch degree of aging in identical environment temperature and identical
It is tested under SOC, obtains its EIS;
Second step analyzes the battery EIS of acquisition, it is known that projection of the battery EIS low frequency inflection point on real axis and its aging
Degree is positively correlated, to diagnose the SOH of battery by the real part of battery EIS low frequency inflection point;
Third step emulates the single order RC model that Gary road state of cyclic operation current data is applied to mesuring battary,
The voltage data under mesuring battary UDDS operating condition is obtained, to mesuring battary both end voltage current data under UDDS operating condition obtained
Time frequency analysis is carried out respectively and obtains corresponding frequency spectrum, to it includes the components of each Frequency point known to the spectrum analysis of acquisition, therefore
The measurement of mesuring battary impedance spectrum is carried out using mesuring battary both end voltage current data under actual condition;
4th step carries out mesuring battary both end voltage current data under UDDS operating condition obtained using Morlet small echo respectively
Morlet wavelet transformation extracts the impedance information under its different frequency, can be obtained with transformed voltage data than upper current data
Obtain mesuring battary EIS;
The real part of the EIS low frequency inflection point of mesuring battary is normalized according to second step data acquired for 5th step
Obtain the mesuring battary SOH value to be estimated.
2. a kind of cell health state estimation method based on online electrochemical impedance spectrometry according to claim 1,
It is characterized in that, battery is lead-acid battery.
3. a kind of cell health state estimation method based on online electrochemical impedance spectrometry according to claim 1,
It is characterized in that, battery is nickel-metal hydride battery.
4. a kind of cell health state estimation method based on online electrochemical impedance spectrometry according to claim 1,
It is characterized in that, battery is nickel-cadmium cell.
5. a kind of cell health state estimation method based on online electrochemical impedance spectrometry according to claim 1,
It is characterized in that, battery is lithium ion battery.
6. a kind of cell health state estimation method based on online electrochemical impedance spectrometry according to claim 1,
It is characterized in that, true electric car row can be replaced with by emulating resulting battery both end voltage current data according to UDDS operating condition
It sails and acquires resulting voltage and current data under operating condition.
7. a kind of cell health state estimation method based on online electrochemical impedance spectrometry according to claim 1,
It is characterized in that, Morlet small echo can replace with Fourier transformation.
8. a kind of cell health state estimation method based on online electrochemical impedance spectrometry according to claim 1,
It is characterized in that, Morlet small echo can replace with Hilbert-Huang transformation.
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