CN116087794A - Battery failure grading early warning method and system - Google Patents
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 31
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
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- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
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Abstract
The invention discloses a battery failure grading early warning method and system, which build fractional order equivalent circuit models of 3 overcharge stages according to the electrical impedance characteristics of different stages of overcharge of a lithium ion battery. And training the characteristics of the electrochemical impedance spectrum curve by combining a least square method and a sparse self-encoder to obtain characteristic parameters of different overcharge stages. And decoupling electrochemical impedance spectrum curves of different frequency bands, wherein the magnitude of the deduced impedance circular arcs can be reflected by the magnitude of parallel resistors corresponding to the model, and finally, the change of the two impedance circular arcs along with the charge state is reflected by adopting the load transmission impedance and SEI film impedance. Based on W related to damage of internal structure of battery ct And W is SEI The parameter increment index adopts 3 sigma criterion and inflection point judgment to identify the abrupt change point of the battery resistance increment curve, and a lithium ion is providedCompared with the early warning method with voltage and temperature as characteristics, the three-level safety early warning method for the battery is more superior.
Description
Technical Field
The invention belongs to the field of battery safety early warning, and relates to a battery failure grading early warning method and system.
Background
With the continuous exhaustion of fossil energy and the increasing increase of atmospheric pollution, the new energy automobile field represented by electric automobiles obtains rapid development by virtue of the unique performance advantages and environmental advantages, and the development of the new energy automobile field avoids the problems of numerous environmental pollution and excessive carbon emission caused by excessive consumption of fossil fuel. The lithium ion battery has the advantages of high energy density, long cycle life, low self-discharge rate, small environmental pollution and the like, and is a main power energy source of the electric automobile at present and one of key technologies of the electric automobile.
While the lithium battery industry is rapidly developed, lithium battery safety accidents also frequently occur, and especially the loss caused by the new energy automobile and energy storage power station industries is immeasurable. Due to the high energy density of the battery, the thermal stability of the battery tends to be lowered. The battery has safe operating voltage and temperature range, and once the voltage and temperature range are out of the limit range, the battery is abused, and faults are extremely easy to occur.
Common thermal runaway causes for new energy automobiles and energy storage power stations are overcharging, mainly due to battery management system and charging equipment anomalies and battery inconsistencies. During the overcharging process of the battery, a series of chained side reactions are generated, and the side reactions consume chemical substances in the battery to destroy the internal structure, and generate a large amount of heat and gas to rapidly expand the battery, so that the thermal runaway of the battery is triggered. Therefore, the safety performance of the battery is improved, and early warning is very important.
The extraction of fault characteristics is a key step in the fault diagnosis of the battery, and a great deal of researches on the selection of fault characteristic parameters before the failure are carried out on the problem of battery failure caused by the overcharge of the lithium ion battery. It is generally difficult to directly determine a battery fault by measuring current, voltage, surface temperature, and the like, and instead, the fault characteristics are extracted from abnormal responses caused by the fault by signal processing.
In recent years, electrochemical impedance spectroscopy has been widely used to analyze internal parameters of a battery, such as estimating internal temperature of the battery. The electrochemical impedance spectrum reflects the internal electrode dynamics, the electric double layer, the diffusion and other processes by measuring the change of impedance along with the sine wave frequency, and can intuitively and accurately reflect the change of the inside of the battery. The impedance spectrum is used as an important index of battery fault early warning through the on-line impedance spectrum technology, so that the current situations of untimely fault early warning and misdiagnosis can be solved.
Disclosure of Invention
The invention mainly solves the problem that the existing fault characteristics cannot timely and accurately reflect the safety state inside the battery and the reserved safety time is short, and therefore provides a battery failure grading early warning method and system.
A battery failure grading early warning method is established, which comprises the following steps:
a battery failure grading early warning method,
establishing a corresponding fractional equivalent circuit model according to the characteristics of electrochemical impedance spectrum in 3 stages of pre-overcharging, slight overcharging and severe overcharging of the battery;
fitting an impedance spectrum curve by using a least square method through the established fractional equivalent circuit model, and identifying characteristic parameter load transfer impedance W ct And SEI film resistance W SEI 。
And (3) adding a constraint condition of sparse representation into a self-encoder model based on an impedance spectrum analysis step of the sparse self-encoder to form the sparse self-encoder, and adding useful features of sparse penalty term learning data. So that the characteristics and the structure of the sample can be extracted under the condition of more hidden layer neurons.
And combining the sparse self-encoder to take the electrochemical impedance spectrum curve of the lithium ion battery as a sample set, dividing the sample set into a training set and a testing set according to a sample sampling method, taking the electrochemical impedance spectrum curve of the lithium ion battery in the training set as input, and training the sparse self-encoder. Obtaining the load transfer impedance W with characteristic parameters from the impedance spectrum curve ct And SEI film resistance W SEI (solid phase imaging device) Fractional order equivalent circuit model.
The electrochemical impedance spectrum curve of the lithium ion battery in the test set is used as input to detect the accuracy of the algorithm, the electrochemical impedance spectrum curve is trained based on a least square method and a sparse self-encoder through an established fractional order equivalent circuit model, and the characteristic parameter load transfer impedance W in the overcharge stage is identified ct And SEI film resistance W SEI。
The electrochemical impedance spectrum decoupling of different frequency bands is adopted to build the damage relation curve between the Arc-MLF and Arc-MHF of the middle frequency band and the inside of the battery, and the load transmission impedance W is used ct And SEI film resistance W SEI After replacing Arc-MLF and Arc-MHF, establishing a relation curve between the Arc-MLF and Arc-MHF and the damage degree inside the battery;
establishing load transfer impedance W based on model parameters based on established relation curve ct And SEI film resistance W SEI Is provided for the three-level early warning of incremental changes.
In the battery failure grading early warning method,
dividing the full frequency band of the electrochemical impedance spectrum curve from 0.1Hz to 2kHz into three sections which are respectively a high frequency section, a medium frequency section and a low frequency section, and corresponding the impedance changes of different frequency bands to the internal load transmission process and the reaction process of the battery;
the method comprises the steps of fully setting a battery to 3 stages according to an electrochemical impedance spectrum curve in an overcharging process, and establishing 3 types of fractional order equivalent electric models corresponding to the electrochemical impedance spectrum by utilizing the characteristics of the electrochemical impedance spectrum;
fitting an impedance spectrum curve by using a least square method through the established fractional equivalent circuit model, and identifying characteristic parameter load transfer impedance W ct And SEI film resistance W SEI 。
And combining a sparse self-encoder, establishing an unsupervised deep learning algorithm model, and improving the generalization capability of the model.
And taking the electrochemical impedance spectrum curve of the lithium ion battery as a sample set, dividing the sample set into a training set and a testing set according to a sample sampling method, taking the electrochemical impedance spectrum curve of the lithium ion battery in the training set as input, and training the sparse self-encoder. Obtaining the load transfer impedance W with characteristic parameters from the impedance spectrum curve ct And SEI film resistance W SEI (solid phase imaging device) Fractional order equivalent circuit model.
The electrochemical impedance spectrum curve of the lithium ion battery in the test set is used as input to detect the accuracy of the algorithm, the electrochemical impedance spectrum curve is trained based on a least square method and a sparse self-encoder through an established fractional order equivalent circuit model, and the characteristic parameter load transfer impedance W in the overcharge stage is identified ct And SEI film resistance W SEI。
In the battery failure grading early warning method,
decoupling the electrochemical impedance spectrum curves according to the fitted model parameters to obtain impedance curves of high frequency, medium frequency and low frequency;
establishing a mapping relation between a battery damage state and a battery electrochemical impedance spectrum curve change condition, extracting characteristic frequency band impedance Arc-MLF and characteristic frequency band impedance Arc-MHF which are sensitive to battery damage, and establishing a relation between Arc-MLF and Arc-MHF change in an overcharging process and the battery internal damage degree;
will transmit the load impedance W ct And SEI film resistance W SEI And after replacing the characteristic frequency band impedance Arc-MLF and the characteristic frequency band impedance Arc-MHF, establishing a mapping curve of the impedance and the damage degree inside the battery.
In the battery failure grading early warning method,
according to the parallel resistance increment dW ct And dW SEI And (5) a curve changing along with the SOC. A data window with the size of 6 data points is adopted, one point is slid at a time, and the average value of the group of data is obtained
And standard deviation->
And judging whether the 7 th point is a mutation point or not by utilizing a 3 sigma criterion.
In W ct Start to increase rapidly, i.e. beforeiMean value of individual resistance data
And 3 times of the frontiStandard deviation of individual resistance data 3->
The addition is smaller than the firstiWhen the resistance of +1 data is used as a first-level early warning sign, the charge transfer structure between the battery electrolyte and the electrode is considered to be damaged, and the interval is defined as an interval 1;
in W SEI Start to increase rapidly, i.e. beforeiMean value of individual resistance data
And 3 times of the frontiStandard deviation of individual resistance data 3->
The addition is smaller than the firstiWhen the resistance of +1 data is used as a sign of secondary early warning, the charge transfer structure between the battery electrolyte and the electrode is considered to be destroyed, and the interval is defined as interval 2;
in W ct The inflection point occurs, i.e. dW ct When zero crossing points occur, the zero crossing points serve as marks of three-level early warning, a series of chain side reactions occur in the battery, electrolyte and electrode materials are continuously consumed, the battery is possibly invalid and even out of control, and the interval is defined as interval 3.
The 3 sigma criterion is used as a method for determining the primary and secondary warning boundaries.
Will W ct Is the inflection point dW of (2) ct The zero crossing point of the curve is used as a method for determining the three-level early warning boundary, so that three-level safety early warning is carried out on the battery.
The battery failure grading early warning method comprises the following steps: the battery can be divided into three safety levels by three boundary indexes determined by 3 sigma criteria and inflection point judgment, so that safety early warning is carried out on the battery.
A battery failure grading early warning system comprises
A first module: is configured to establish a fractional equivalent circuit model of 3 stages of pre-battery overcharging, slight overcharging and severe overcharging; based on a least square method and a sparse self-encoder, training an electrochemical impedance spectrum curve through an established fractional order equivalent circuit model, and identifying characteristic parameter load transfer impedance W in an overcharge stage ct And SEI film resistance W SEI。
A first module: is configured to establish a mid-band Arc-MLF and Arc-MHF and a battery internal damage relation curve by decoupling electrochemical impedance spectra of different frequency bands and uses the load transmission impedance W ct And SEI film resistance W SEI After replacing the characteristic frequency band impedance Arc-MLF and the characteristic frequency band impedance Arc-MHF, establishing a relation curve between the characteristic frequency band impedance Arc-MLF and the damage degree inside the battery;
a first module: configured to be based on the established parallel resistance delta dW ct And dW SEI The 3 sigma criterion is used as a method for determining the primary early warning and secondary early warning boundaries along with the SOC variation curve. Will W ct Is the inflection point of dW ct The zero crossing point of the curve is used as a method for determining the three-level early warning boundary.
In the above-described system, the system,
dividing the full frequency band of the electrochemical impedance spectrum curve from 0.1Hz to 2kHz into three sections which are respectively a high frequency section, a medium frequency section and a low frequency section; corresponding the change of the impedance of different frequency bands to the internal load transmission process and the reaction process of the battery;
the method comprises the steps of fully setting a battery to 3 stages according to an electrochemical impedance spectrum curve in an overcharging process, and establishing 3 types of fractional order equivalent circuit models corresponding to the battery;
fitting an impedance spectrum curve by using a least square method through the established fractional equivalent circuit model, and identifying characteristic parameter load transfer impedance W ct And SEI film resistance W SEI 。
And combining the sparse self-encoder to establish an unsupervised deep learning algorithm model. Taking an electrochemical impedance spectrum curve of the lithium ion battery as a sample set, and dividing the sample set into training according to a sample sampling methodAnd the set and the test set take the electrochemical impedance spectrum curve of the lithium ion battery in the training set as input to train the sparse self-encoder. Obtaining the load transfer impedance W with characteristic parameters from the impedance spectrum curve ct And SEI film resistance W SEI (solid phase imaging device) Fractional order equivalent circuit model.
The electrochemical impedance spectrum curve of the lithium ion battery in the test set is used as input to detect the accuracy of the algorithm, the electrochemical impedance spectrum curve is trained based on a least square method and a sparse self-encoder through an established fractional order equivalent circuit model, and the characteristic parameter load transfer impedance W in the overcharge stage is identified ct And SEI film resistance W SEI。
In the above-described system, the system,
decoupling the electrochemical impedance spectrum curves according to the fitted model parameters to obtain impedance curves of high frequency, medium frequency and low frequency;
establishing a mapping relation between a battery damage state and a battery electrochemical impedance spectrum curve change condition, extracting characteristic frequency band impedance Arc-MLF and characteristic frequency band impedance Arc-MHF which are sensitive to battery damage, and establishing a relation between Arc-MLF and Arc-MHF change in an overcharging process and the battery internal damage degree;
will transmit the load impedance W ct And SEI film resistance W SEI And after replacing the characteristic frequency band impedance Arc-MLF and the characteristic frequency band impedance Arc-MHF, establishing a mapping curve of the impedance and the damage degree inside the battery.
In the above-described system, the system,
according to the parallel resistance increment dW ct And dW SEI And (5) a curve changing along with the SOC. A data window with the size of 6 data points is adopted, one point is slid at a time, and the average value of the group of data is obtained
And standard deviation->
And judging whether the 7 th point is a mutation point or not by utilizing a 3 sigma criterion.
In W ct Start to increase rapidly, i.e. currentlyiMean value of individual resistance data
And 3 times of the frontiStandard deviation of individual resistance data 3->
Less than the first one when addediWhen the resistance of +1 data is used as a first-level early warning sign, the charge transfer structure between the battery electrolyte and the electrode is considered to be damaged, and the interval is defined as an interval 1;
in W SEI Start to increase rapidly, i.e. currentlyiMean value of individual resistance data
And 3 times of the frontiStandard deviation of individual resistance data 3->
Less than the first one when addediWhen the resistance of +1 data is used as a sign of secondary early warning, the charge transfer structure between the battery electrolyte and the electrode is considered to be destroyed, and the interval is defined as interval 2;
in W ct The inflection point appears, i.e. when dW ct When zero crossing points occur, the zero crossing points serve as marks of three-level early warning, a series of chain side reactions occur in the battery, electrolyte and electrode materials are continuously consumed, the battery is possibly invalid and even out of control, and the interval is defined as interval 3.
The 3 sigma criterion is used as a method for determining the primary and secondary warning boundaries.
Will W ct Is the inflection point of dW ct The zero crossing point of the curve is used as a method for determining the three-level early warning boundary, so that three-level safety early warning is carried out on the battery.
In the system, the battery can be divided into three safety levels by three boundary indexes determined by 3 sigma criteria and inflection point judgment, so that the safety of the battery is pre-warned.
Compared with the prior art, the invention has the following beneficial effects: the invention mainly establishes the impedance spectrum characteristics of different SOC stages, establishes the corresponding fractional equivalent circuit order model in stages, and is based on the least square method and the sparsenessThe self-encoder trains the electrochemical impedance spectrum curve through the established fractional equivalent circuit model and identifies the characteristic parameter load transmission impedance W in the overcharge stage ct And SEI film resistance W SEI The method comprises the steps of carrying out a first treatment on the surface of the Decoupling the high, medium and low frequency processes according to the electrochemical impedance spectrum curve; the characteristic that the arc size of each frequency band is consistent with the corresponding parallel resistance value change of the model is verified through simple model derivation, system detection is facilitated, and the method has practical value; and establishing a resistance increment curve by taking a 3 sigma criterion as a method for determining a primary early warning and secondary early warning boundary. Will W ct Is the inflection point of dW ct The zero crossing point of the curve is used as a method for determining the boundary of three-stage early warning, and the voltage of the third-stage early warning is advanced by about 5% of the SOC compared with the voltage of the overcharging process. The method adopted by the invention has more predictability for early warning of the failure of the battery, so that sufficient time is available for maintenance or starting protection measures.
Drawings
FIG. 1 is a graph of electrochemical impedance spectra measured using an overfill test in accordance with the present invention.
Fig. 2 is a battery impedance spectrum versus corresponding fractional equivalent circuit model.
Fig. 3 is a sparse self-encoder training flowchart.
Fig. 4a shows the result of decoupling the electrochemical impedance spectrum according to the invention (parasitic inductance impedance).
Fig. 4b shows the result of decoupling the electrochemical impedance spectrum (internal cell resistance) according to the present invention.
Fig. 4c shows the result of decoupling the electrochemical impedance spectrum (interfacial charge transfer impedance) according to the present invention.
Fig. 4d shows the result of decoupling the electrochemical impedance spectrum according to the invention (diffusion impedance).
FIG. 5a is a graph of the medium frequency two Arc variations (Arc-MLF variations at different SOCs) referred to in the present invention.
FIG. 5b is a graph of the medium frequency two circular Arc variations (Arc-MHF variations at different SOCs) referred to in the present invention.
Fig. 6a is a fractional equivalent circuit order model.
Fig. 6b is an electrochemical impedance spectrum corresponding to the fractional equivalent circuit model.
FIG. 7 is a view of the different phases of W mentioned in the present invention ct And W is SEI Is a change curve of (a).
FIG. 8a is a graph showing the parallel resistance delta (dW) of the experimental data of the battery according to the present invention ct And dW SEI ) Curve with SOC (6 data point size data window).
FIG. 8b is a graph showing the parallel resistance delta (dW) of the experimental data of the battery according to the present invention ct And dW SEI ) And (3) grading and early warning according to the SOC change curve (set dW threshold value).
Fig. 9 is a method flow diagram.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
The embodiment provides a battery failure grading early warning method, which comprises the following steps:
performing overcharging experiments by adopting a soft-packed battery, measuring electrochemical impedance spectrum data at different stages so as to obtain a change rule of an electrochemical impedance spectrum curve, and establishing fractional order circuit models of 3 stages of overcharging, slight overcharging and heavy overcharging of the battery;
fitting an impedance spectrum curve by using a least square method through the established fractional equivalent circuit model, and identifying characteristic parameter load transfer impedance W ct And SEI film resistance W SEI 。
And taking the electrochemical impedance spectrum curve of the lithium ion battery as a sample set, dividing the sample set into a training set and a testing set according to a sample sampling method, taking the electrochemical impedance spectrum curve of the lithium ion battery in the training set as input, and training the sparse self-encoder. Completion ofObtaining load transfer impedance W with characteristic parameters from impedance spectrum curve ct And SEI film resistance W SEI (solid phase imaging device) Fractional order equivalent circuit model.
The electrochemical impedance spectrum curve of the lithium ion battery in the test set is used as input to detect the accuracy of the algorithm, the electrochemical impedance spectrum curve is trained based on a least square method and a sparse self-encoder through an established fractional order equivalent circuit model, and the characteristic parameter load transfer impedance W in the overcharge stage is identified ct And SEI film resistance W SEI。
2. Based on the corresponding relation between the electrochemical impedance spectrum and the fractional equivalent circuit model, decoupling the electrochemical impedance spectrum curve according to the impedance expression of the fractional equivalent circuit model and the acquired model parameters, and researching the impedance curve change of each part. The formulas specifically used are as follows (7), (8), (9):
wherein W is SEI Represents the SEI film resistance,T CPE representing fractional order capacitance in units of
。P CPE Reflecting the fractional order of the capacitance,P CPE =1 denotes that the polarization capacitance is ideal; if 0 is<P CPE <1, the capacitance is a constant phase element.fFor the frequency of the excitation signal,jis a complex number unit. W (W) ct Representing the load transfer impedance.R w 、P w 、T w Is a parameter of the Warburg element.
According to the change rule of the electrochemical impedance spectrum curve, the change generated by the influence of overcharge on the medium-frequency arc region is found to be obvious.
Decoupling the electrochemical impedance spectrum curve by adopting the method described in the above 1, and independently researching the change rule of the medium-frequency arc region.
The Arc-MLF and Arc-MHF in the intermediate frequency region of the electrochemical impedance spectrum curve are obviously changed along with the overcharge of the battery, so that the actual damage condition of the battery can be reflected.
3. It was found that when f→0, the impedance z=w 0 +W 1 The method comprises the steps of carrying out a first treatment on the surface of the When f→infinity, the impedance z=w 0 The method comprises the steps of carrying out a first treatment on the surface of the The value of the intersection point of the arc extension line on the real axis (namely W 0 And W is 0 +W 1 ) The arc chord length is the resistance W connected with the CPE element in parallel 1 The magnitude of the parallel resistor can reflect the magnitude of the circular arc thereof.
According to the related theory described in the above 2, the present invention adopts the load transfer impedance W ct Reflecting the size change of Arc-MLF, SEI film impedance W SEI Reflecting the size change of Arc-MHF.
4. Taking SOC of a battery as X axis, W SEI And W is ct For the Y axis, SOC is equal to W SEI And W is ct Establishing a relation curve, W in the relation curve ct First from a smooth gradual acceleration to an increase, then W SEI Also starts to increase from a steady acceleration and does not drop, finally W ct The inflection point appears to begin to gradually decrease.
Based on the description in 3 above, the present invention is based on W ct Start to increase rapidly, i.e. currentlyiMean value of individual resistance data
And 3 times of the frontiStandard deviation of individual resistance data 3->
Less than the first one when addediWhen the resistance of +1 data is used as a first-level early warning sign, the charge transfer structure between the battery electrolyte and the electrode is considered to be damaged, and the interval is defined as an interval 1;
based on the description in 3 above, in W SEI Start to increase rapidly, i.e. currentlyiMean value of individual resistance data
And 3 times of the frontiStandard deviation of individual resistance data 3->
Less than the first one when addediWhen the resistance of +1 data is used as a sign of secondary early warning, the charge transfer structure between the battery electrolyte and the electrode is considered to be destroyed, and the interval is defined as interval 2; />
Based on the description in 3 above, in W ct The inflection point appears, i.e. when dW ct When zero crossing points occur, the zero crossing points serve as marks of three-level early warning, a series of chain side reactions occur in the battery, electrolyte and electrode materials are continuously consumed, the battery is possibly invalid and even out of control, and the interval is defined as interval 3.
The battery can be divided into three safety levels by three boundary indexes determined by 3 sigma criteria and inflection point judgment, so that safety early warning is carried out on the battery.
The invention carries out a plurality of groups of test experiments with different multiplying powers (0.2C, 0.5C and 1C), and the obtained electrochemical impedance spectrum curves have consistent rules.
The invention carries out Kramers-Kronig (K-K) test on the measured electrochemical impedance spectrum data, and the results of the Kramers-Kronig (K-K) test accord with the conditions of linearity and time invariance.
3 sigma criterion and W set by the invention ct The inflection point judgment is determined through a plurality of groups of experimental results, and the method has the characteristic of universal applicability.
The electrochemical impedance spectrum curve of the battery in the overcharging process is obtained through experiments as shown in figure 1, the battery is divided into three stages of overcharging before, slight overcharging and severe overcharging according to the change of each frequency band of the electrochemical impedance spectrum curve, and a corresponding fractional equivalent circuit model is established according to the characteristics of the electrochemical impedance spectrum curve as shown in figure 2.
Fitting an impedance spectrum curve by using a least square method through the established fractional equivalent circuit model, and identifying characteristic parameter load transfer impedance W ct And SEI film resistance W SEI 。
And combining the sparse self-encoder, taking the electrochemical impedance spectrum curve of the lithium ion battery as a sample set, dividing the sample set into a training set and a testing set according to a sample sampling method, taking the electrochemical impedance spectrum curve of the lithium ion battery in the training set as input, and training the sparse self-encoder. Obtaining the load transfer impedance W with characteristic parameters from the impedance spectrum curve ct And SEI film resistance W SEI (solid phase imaging device) Fractional order equivalent circuit model.
The electrochemical impedance spectrum curve of the lithium ion battery in the test set is used as input to detect the accuracy of the algorithm, the electrochemical impedance spectrum curve is trained based on a least square method and a sparse self-encoder through an established fractional order equivalent circuit model, and the characteristic parameter load transfer impedance W in the overcharge stage is identified ct And SEI film resistance W SEI， The training flow of the least square method and the sparse self-encoder is shown in figure 3 。
According to the impedance expression of each part of the model, the electrochemical impedance spectrum curve can be decoupled by substituting model parameters and setting the frequency range to be 0.1Hz-2kHz, and the electrochemical impedance spectrum curve under the condition of 90% SOC is decoupled as shown in figures 4 a-4 d.
Specific examples are described below with reference to the drawings.
According to fig. 1, it can be found that the frequency band arc in the electrochemical impedance spectrum curve changes obviously with the increase of the SOC, the frequency band arc is divided into two by one arc, then the size of the arc changes, and the low-frequency straight line disappears.
All electrochemical impedance spectrum curves are decoupled, and the change condition of the circular arcs of the frequency bands in the study is studied, wherein the change condition is shown in fig. 5a and 5 b. The arc is translated to the same starting point to compare the arc sizes at different SOCs. FIG. 5a shows the Arc-MLF change law, and it is obvious that Arc-MLF increases slowly from 110% SOC to 120% SOC, and after 120% SOC, the Arc increases greatly and the Arc after the Arc is significantly larger than before; the Arc-MLF is not always expanded, reaches a maximum value around 140% SOC, and then gradually tapers down in Arc, which is still larger in size than the initial overcharge stage. FIG. 4b shows the Arc-MHF change law, starting to increase significantly after 130% SOC, with the moment when the Arc-MHF increases significantly lagging the Arc-MLF, and no tendency for Arc reduction before battery failure.
The Arc-MLF and Arc-MHF have obvious change rules for identifying battery faults, but are not easy to quantify.
In the study of the significance of the semi-arc parameters of the electrochemical impedance spectrum, the influence of parasitic inductance on the impedance spectrum is ignored, a simple circuit model is taken as an example in fig. 6a, and the electrochemical impedance spectrum curve is shown in fig. 6 b. The impedance model expression is shown as (10):
wherein W is 0 Representing the series resistance of the circuit, W 1 Representing the resistance in parallel with the CPE element,R w 、P w 、T w is a parameter of the Warburg element.
And when the high-frequency band half arc is studied, the influence of low-frequency diffusion is ignored. When (when) f At 0, impedance z=w 0 +W 1 The method comprises the steps of carrying out a first treatment on the surface of the When (when)fAt →infinity, impedance z=w 0 The method comprises the steps of carrying out a first treatment on the surface of the The value of the intersection point of the arc extension line on the real axis (namely W 0 And W is 0 +W 1 ) The arc chord length is the resistance W connected with the CPE element in parallel 1 The magnitude of the parallel resistor can reflect the magnitude of the circular arc thereof.
Thus, the invention adopts W ct And W is SEI Size replaces the Arc-MLF and the Arc-MHF variation.
W SEI And W is ct The variation curve with battery SOC is shown in fig. 7. Parallel resistor W ct The change in size of Arc-MLF was characterized, starting to increase rapidly after 120% soc, and it was thought that the charge transfer structure between the battery electrolyte and the electrode began to be destroyed. Parallel resistor W SEI The change in Arc-MHF was characterized, starting to increase rapidly after 130% soc, and it is believed that the charge transfer structure between the battery electrolyte and the electrode also began to be destroyed. Is consistent with the change trend of the electrochemical impedance spectrum curves Arc-MLF and Arc-MHF.
According to the parallel resistance increment dW ct And dW SEI And (5) a curve changing along with the SOC. A data window with the size of 6 data points is adopted, one point is slid at a time, and the average value of the group of data is obtained
And standard deviation->
And judging whether the 7 th point is a mutation point or not by utilizing a 3 sigma criterion. Mutation Point (first)iResistance value of +1 data) W i+1 Satisfy the constraint of equation (11):
In W ct Start to increase rapidly (dW ct >0.0014Ω), i.e. currentlyiMean value of individual resistance data
And 3 times of the frontiStandard deviation of individual resistance data 3->
Less than the first one when addediWhen the resistance of +1 data is used as a first-level early warning sign, the charge transfer structure between the battery electrolyte and the electrode is considered to be damaged, and the interval is defined as an interval 1;
in W SEI Start to increase rapidly (dW SEI >0.0004Ω), i.e. currentlyiMean value of individual resistance data
And 3 times of the frontiStandard deviation of individual resistance data 3->
Less than the first one when addediWhen the resistance of +1 data is used as a sign of secondary early warning, the charge transfer structure between the battery electrolyte and the electrode is considered to be destroyed, and the interval is defined as interval 2;
in W ct The inflection point appears, i.e. when dW ct When zero crossing points occur, the zero crossing points serve as marks of three-level early warning, a series of chain side reactions occur in the battery, electrolyte and electrode materials are continuously consumed, the battery is possibly invalid and even out of control, and the interval is defined as interval 3.
And identifying abrupt points of the resistance increment curve of the experimental battery by adopting a 3 sigma criterion. In FIG. 8a dW is marked ct And dW SEI Mutation positions and accurate results.
The 3 sigma criterion is used as a method for determining the primary and secondary warning boundaries.
Will W ct Is the inflection point of dW ct The zero crossing point of the curve is used as a method for determining the three-level early warning boundary.
The battery can be divided into three safety levels by three boundary indexes determined by 3 sigma criteria and inflection point judgment, so that safety early warning is carried out on the battery. The grading early warning method and W ct And W is SEI The analysis results were consistent as shown in fig. 8 b.
The battery management system can detect dW ct And dW SEI And (3) a curve, and early warning is carried out on the safety state of the battery by using a 3 sigma criterion and an inflection point judging method.
The embodiment also provides a battery failure grading early warning system, which comprises
A first module: is configured to establish a fractional equivalent circuit model of 3 stages of pre-battery overcharging, slight overcharging and severe overcharging; determining the parameter load transfer impedance W of the fractional equivalent circuit model in a data fitting mode ct And SEI film resistance W SEI 。
A first module: is configured to establish mid-band Arc-MLF and Arc-MHF with internal damage of battery by decoupling electrochemical impedance spectra of different frequency bandsThe relation curve and load-transmitting impedance W ct And SEI film resistance W SEI Instead of the characteristic band impedance Arc-MLF and the characteristic band impedance Arc-MHF, a relation curve of the characteristic band impedance Arc-MLF and the damage degree inside the battery is established.
A first module: is configured to use the 3σ criterion as a method of determining primary and secondary warning boundaries based on the established resistance delta curve. Will W ct Is the inflection point of dW ct The zero crossing point of the curve is used as a method for determining the three-level early warning boundary.
With the above-described preferred embodiments according to the present application as a teaching, the related workers can make various changes and modifications without departing from the scope of the technical idea of the present application. The technical scope of the present application is not limited to the contents of the specification, and must be determined according to the scope of claims.
Claims (10)
1. A battery failure grading early warning method is characterized in that:
acquiring electrochemical impedance spectrum curves of the lithium ion battery to be tested in 3 stages of pre-overcharging, slight overcharging and severe overcharging, and establishing fractional order equivalent circuit models of different overcharging stages of the lithium ion battery according to the characteristics of the electrochemical impedance spectrum;
training the characteristics of the electrochemical impedance spectrum curve through the established fractional equivalent circuit model according to the least square method and the sparse self-encoder, and classifying and identifying characteristic parameter load transfer impedance W of different overcharge stages ct And SEI film resistance W SEI ；
The electrochemical impedance spectrum decoupling of different frequency bands is adopted to build the damage relation curve between the Arc-MLF and Arc-MHF of the middle frequency band and the inside of the battery, and the identified load transmitting impedance W is used ct And SEI film resistance W SEI After replacing Arc-MLF and Arc-MHF, establishing a relation curve between the Arc-MLF and Arc-MHF and the damage degree inside the battery;
based on the established relation curve, establishing load transfer impedance W based on model parameters ct And SEI film resistance W SEI Is used for increasing the resistance of the battery by adopting 3 sigma criterion and inflection point judgmentAnd identifying the curve mutation points.
2. The battery failure grading early warning method according to claim 1, wherein the method comprises the following steps:
dividing the full frequency band of the electrochemical impedance spectrum curve from 0.1Hz to 2kHz into three sections which are respectively a high frequency section, a medium frequency section and a low frequency section, and corresponding the impedance changes of different frequency bands to the internal load transmission process and the reaction process of the battery;
the method comprises the steps of fully overcharging a battery for 3 stages before overcharging, slightly overcharging and heavily overcharging according to an electrochemical impedance spectrum curve in an overcharging process, and establishing a fractional equivalent circuit model corresponding to the electrochemical impedance spectrum curve by utilizing the characteristics of the electrochemical impedance spectrum curve;
fitting an impedance spectrum curve by using a least square method through the established fractional equivalent circuit model, and identifying characteristic parameter load transfer impedance W ct And SEI film resistance W SEI ；
Taking an electrochemical impedance spectrum curve of the lithium ion battery as a sample set by combining a sparse self-encoder, dividing the sample set into a training set and a testing set according to a sample sampling method, taking the electrochemical impedance spectrum curve of the lithium ion battery in the training set as input, training the sparse self-encoder, and obtaining load-carrying impedance W with characteristic parameters from the impedance spectrum curve ct And SEI film resistance W SEI (solid phase imaging device) A fractional order equivalent circuit model;
the electrochemical impedance spectrum curve of the lithium ion battery in the test set is used as input to detect the accuracy of the algorithm, the electrochemical impedance spectrum curve is trained based on a least square method and a sparse self-encoder through an established fractional order equivalent circuit model, and the characteristic parameter load transfer impedance W of the overcharge stage of the lithium ion battery is identified ct And SEI film resistance W SEI。
3. The battery failure grading early warning method according to claim 1, wherein the method comprises the following steps:
decoupling the electrochemical impedance spectrum curves according to the fitted model parameters to obtain impedance curves of high frequency, medium frequency and low frequency;
establishing a mapping relation between a battery damage state and a battery electrochemical impedance spectrum curve change condition, extracting characteristic frequency band impedance Arc-MLF and characteristic frequency band impedance Arc-MHF which are sensitive to battery damage, and establishing a relation between Arc-MLF and Arc-MHF change in an overcharging process and the battery internal damage degree;
will transmit the load impedance W ct And SEI film resistance W SEI And after replacing the characteristic frequency band impedance Arc-MLF and the characteristic frequency band impedance Arc-MHF, establishing a mapping curve of the impedance and the damage degree inside the battery.
4. The battery failure grading early warning method according to claim 1, wherein the method comprises the following steps:
in W ct Start to increase rapidly, i.e. beforeiMean value of individual resistance data
And 3 times of the frontiStandard deviation of individual resistance data 3->
The addition is smaller than the firstiWhen the resistance of +1 data is used as a first-level early warning sign, the charge transfer structure between the battery electrolyte and the electrode is considered to be damaged, and the interval is defined as an interval 1;
in W SEI Start to increase rapidly, i.e. beforeiMean value of individual resistance data
And 3 times of the frontiStandard deviation of individual resistance data 3->
The addition is smaller than the firstiWhen the resistance of +1 data is used as a sign of secondary early warning, the charge transfer structure between the battery electrolyte and the electrode is considered to be destroyed, and the interval is defined as interval 2;
in W ct The inflection point appears, i.e. when dW ct When zero crossing occurs, the zero crossing is used as a sign of three-level early warning, a series of chain side reactions occur in the battery, and the electrolyte are continuously consumedElectrode material, which would likely lead to failure of the cell and even thermal runaway, defines this interval as interval 3.
5. The battery failure grading early warning method according to claim 4, wherein the method comprises the following steps: the battery can be divided into three safety levels by three boundary indexes determined by 3 sigma criteria and inflection point judgment, so that safety early warning is carried out on the battery.
6. A battery failure grading early warning system is characterized in that: comprising
A first module: the method comprises the steps of acquiring electrochemical impedance spectrum curves of a lithium ion battery to be detected in 3 stages of slight overcharging and severe overcharging before overcharging, and establishing fractional order equivalent circuit models of different overcharging stages of the lithium ion battery according to characteristics of the electrochemical impedance spectrum;
a second module: is configured to train the characteristics of the electrochemical impedance spectrum curve according to the least square method and the sparse self-encoder through the established fractional equivalent circuit model, and to classify and identify the characteristic parameter load transfer impedance W of different overcharge stages ct And SEI film resistance W SEI ；
And a third module: is configured to establish a mid-band Arc-MLF and Arc-MHF and a battery internal damage relation curve by decoupling electrochemical impedance spectra of different frequency bands and to use the identified load transmission impedance W ct And SEI film resistance W SEI After replacing Arc-MLF and Arc-MHF, establishing a relation curve between the Arc-MLF and Arc-MHF and the damage degree inside the battery;
a fourth module: is configured to establish a model-based parametric load transfer impedance W based on the established relationship ct And SEI film resistance W SEI And (3) identifying the abrupt change point of the battery resistance incremental curve by adopting a 3 sigma criterion and inflection point judgment.
7. The system according to claim 6, wherein:
dividing the full frequency band of the electrochemical impedance spectrum curve from 0.1Hz to 2kHz into three sections which are respectively a high frequency section, a medium frequency section and a low frequency section, and corresponding the impedance changes of different frequency bands to the internal load transmission process and the reaction process of the battery;
the method comprises the steps of fully overcharging a battery for 3 stages before overcharging, slightly overcharging and heavily overcharging according to an electrochemical impedance spectrum curve in an overcharging process, and establishing a fractional equivalent circuit model corresponding to the electrochemical impedance spectrum curve by utilizing the characteristics of the electrochemical impedance spectrum curve;
fitting an impedance spectrum curve by using a least square method through the established fractional equivalent circuit model, and identifying characteristic parameter load transfer impedance W ct And SEI film resistance W SEI ；
Taking an electrochemical impedance spectrum curve of the lithium ion battery as a sample set by combining a sparse self-encoder, dividing the sample set into a training set and a testing set according to a sample sampling method, taking the electrochemical impedance spectrum curve of the lithium ion battery in the training set as input, training the sparse self-encoder, and obtaining load-carrying impedance W with characteristic parameters from the impedance spectrum curve ct And SEI film resistance W SEI (solid phase imaging device) A fractional order equivalent circuit model;
the electrochemical impedance spectrum curve of the lithium ion battery in the test set is used as input to detect the accuracy of the algorithm, the electrochemical impedance spectrum curve is trained based on a least square method and a sparse self-encoder through an established fractional order equivalent circuit model, and the characteristic parameter load transfer impedance W of the overcharge stage of the lithium ion battery is identified ct And SEI film resistance W SEI。
8. The system according to claim 6, wherein:
decoupling the electrochemical impedance spectrum curves according to the fitted model parameters to obtain impedance curves of high frequency, medium frequency and low frequency;
establishing a mapping relation between a battery damage state and a battery electrochemical impedance spectrum curve change condition, extracting characteristic frequency band impedance Arc-MLF and characteristic frequency band impedance Arc-MHF which are sensitive to battery damage, and establishing a relation between Arc-MLF and Arc-MHF change in an overcharging process and the battery internal damage degree;
will transmit the load impedance W ct And SEI film resistance W SEI Replace characteristic frequency band impedance Arc-MLF and characteristic frequency band impedanceAfter Arc-MHF resistance, a mapping curve of impedance and damage degree inside the battery is established.
9. The system according to claim 6, wherein:
in W ct Start to increase rapidly, i.e. beforeiMean value of individual resistance data
And 3 times of the frontiStandard deviation of individual resistance data 3->
The addition is smaller than the firstiWhen the resistance of +1 data is used as a first-level early warning sign, the charge transfer structure between the battery electrolyte and the electrode is considered to be damaged, and the interval is defined as an interval 1;
in W SEI Start to increase rapidly, i.e. beforeiMean value of individual resistance data
And 3 times of the frontiStandard deviation of individual resistance data 3->
The addition is smaller than the firstiWhen the resistance of +1 data is used as a sign of secondary early warning, the charge transfer structure between the battery electrolyte and the electrode is considered to be destroyed, and the interval is defined as interval 2;
in W ct The inflection point appears, i.e. when dW ct When zero crossing points occur, the zero crossing points serve as marks of three-level early warning, a series of chain side reactions occur in the battery, electrolyte and electrode materials are continuously consumed, the battery is possibly invalid and even out of control, and the interval is defined as interval 3.
10. The system according to claim 6, wherein: the battery can be divided into three safety levels by three boundary indexes determined by 3 sigma criteria and inflection point judgment, so that safety early warning is carried out on the battery.
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