CN108896913A - A kind of evaluation method of health state of lithium ion battery - Google Patents
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- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
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Abstract
The invention discloses a kind of evaluation methods of health state of lithium ion battery, carry out accelerated aging tests under different multiplying, condition of different temperatures to battery, obtain aging data；It is excavated based on aging data Develop Data, is fitted using Differential Capacity curve of the pseudo- voigt linear function to battery, obtain the area of linear function curve main peak as characteristic parameter；With characteristic parameter, temperature, multiplying power, adds corresponding SOH state and collectively form four-dimensional aging character curved surface.It is tabled look-up according to the characteristic parameter that actual working conditions and lithium ion battery charging process obtain, obtains battery currently corresponding SOH.The present invention can accurately estimate different multiplying in actual condition, under different temperatures lithium ion battery health status, with feature charging section evident characteristics, charge in the state that battery is not vented, also SOH can be estimated, estimation is all an individual process every time, and the battery external characteristics data of part charging process are only taken, precision is good.
Description
Technical field
The invention belongs to battery management system field, especially a kind of LiFePO based on aging character parameter extraction4
Battery SOH evaluation method realizes the evaluation method to health state of lithium ion battery.
Background technique
In recent years, as the main energy storage means and power source in New Energy Industry, battery technology development is swift and violent.It is whole
From body, batteries to store energy technology can be divided into two large divisions, and a part is battery material and technique, and another part is battery
Management system (BMS, Battery Management System)；It is imperative in view of electric car and generation of electricity by new energy, it is above
Two big technical fields are current research hotspots.The health status (SOH, state of health) of lithium ion battery represents
The number of remaining battery active volume, it is directly related with economic performance, it is specific to calculate such as formula (1)：
QageRepresent present battery monomer residue active volume, QallRepresent rated capacity when battery factory.
The ageing process of lithium battery is analyzed, and finally realizes and the diagnosis of aging of lithium battery state and health status is estimated
It calculates, needs to seek a kind of effective method, on the one hand it is desirable that this method thinking is clear, can more fully embody lithium
Mechanism of Electrochemistry during cell degradation；On the other hand, we it is expected that this method is simple and easy again, are unlikely to introduce excessively
Professional electrochemical parameter and corresponding electrochemical analysis process；The third aspect is exactly to require this method that should also have good essence
Degree.
Summary of the invention
It is an object of that present invention to provide one kind to be avoided that accumulated error, preferable, the feature charging zone with single estimation precision
Between identify characteristic, can different multiplying and at a temperature of identify SOH in lithium ion battery charging process based on aging
The LiFePO of characteristic parameter extraction4Battery SOH evaluation method realizes the evaluation method to health state of lithium ion battery.
To achieve the above object, following technical scheme is used：Spy of the method for the invention based on Differential Capacity curve
The SOH evaluation method of parameter extraction is levied, SOH estimation can be carried out using temperature, rate of charge as relevant parameter,
Include the following steps：
Step 1, it for selected lithium ion battery sample, designs and carries out within the temperature range of -20~40 DEG C, more stress
Accelerated aging test, in battery entirety ageing process, aging node is chosen in the health status aging every 5%, obtains not
Synthermal lower each node normal capacity and more multiplying power charging voltage characteristics curves；
Step 2, the aging initial data in previous step is excavated, differential is fitted using pseudo- Voigt linear function
Capacity curve obtains characteristic parameter, four-dimensional aging is established according to the relationship between characteristic parameter, temperature, rate of charge and SOH
Characteristic surface；
Step 3, based on four-dimension SOH estimation curved surface, in conjunction with mesuring battary charging process in voltage response, to reality
Lithium ion battery in the application of border is estimated.
Further, in step 1, more stress accelerated aging tests are charge-discharge magnification, charge and discharge blanking voltage adds
Fast degradation.
Compared with prior art, the method for the present invention has the following advantages that：
The health status that can accurately determine lithium ion battery, will not generate accumulated error, have single estimation precision compared with
Good, feature charging section identification characteristic, while can identify different multiplying, the SOH under different temperatures charged state.
Detailed description of the invention
Fig. 1 (a) is the variation diagram of line style when β takes different numerical value；
Fig. 1 (b) is the variation diagram of line style when A takes different numerical value；
Fig. 1 (c) is the variation diagram of line style when S takes different numerical value；
Fig. 2 is characterized curve matching figure；
Fig. 3 is matched curve exploded view；
Fig. 4 is simple curve peak area schematic diagram；
Fig. 5 is curve matching figure；
Fig. 6 (a) is more multiplying power aging flow charts；
Fig. 6 (b) is that more multiplying power constant-current charge characteristics obtain flow chart；
Fig. 6 (c) is node standard active volume test flow chart；
Fig. 6 (d) is four-dimension SOH estimated data's Aging Step figure；
Fig. 7 is four-dimension SOH estimation curve flow chart；
Fig. 8 is that total SOH estimates flow chart.
Specific embodiment
The present invention will be further described with reference to the accompanying drawing：
The mathematical description of 1 linear function
Current many researchs show that the ageing process of battery can be by its cyclic voltammetric (CV, Cyclic
Voltammogram) characteristic curve more clearly embodies.For example, when the electrode surface environment for participating in electrochemical reaction occurs
When variation, the peak value sharpness of corresponding CV curve can occur significantly to change：From microcosmic, peak value line style is more sharp, can be with
It is more to be interpreted as the existing effect to attract each other between each central point of redox reaction；On the contrary, peak value line style radian
Bigger, i.e., the peak value the gentle, illustrates existing mutually exclusive effect between each oxygen also reaction center point to a certain extent
It is more.Certainly, in addition to peak value sharpness, other peak value profiles such as peak point voltage, peak value degree of asymmetry, crest voltage
The parameters such as offset and peak separation can also embody the process of battery aging from different angles.It is generally believed that CV
The peak point voltage of curve is related with the activity substance content in electrode material especially positive electrode, the reduction of CV peak of curve
It can be understood that may participate in the reduction of the active material of electrochemical reaction in electrode, the research also having is by active material in battery
Variation described with the area that CV curve is surrounded；In addition, the degree of asymmetry of CV peak of curve voltage and line style can also be by
To the influence of electrode reaction degree of reversibility, the corresponding relationship between them can be carried out by mass transfer rate and charge transport rate
It derives.
Based on the above analysis, the main thought of this programme be exactly extract it is relevant to aging of lithium battery process in CV curve
Characteristic parameter Pf, and aging of lithium battery mechanism is analyzed by these key parameters, and then complete battery pair SOH estimates
It calculates.For entirety, the current characteristics in lithium battery CV test be can be described as：
Wherein i is electric current, and Q is battery remaining power, and V is battery terminal voltage, and t is the time.In C-V characteristic test process
In, it is considered that electrode potential sweep speed in each cycle is steady state value, it may thus be appreciated that the shape of the CV curve of battery
Curve shape with dQ/dV vs.V be it is identical, the two difference be only a constant coefficient.And the dQ/dV vs.V curve of battery
The Differential Capacity DC curve being exactly concerned at present, therefore, the Analysis on ageing mechanism based on CV characteristic in this programme is just converted
At the analysis to battery DC characteristic.
It is noted that conventional DC or IC characteristic curve is directly obtained by ampere-hour method, in the present solution, in order to
The precision of curve is improved, improves the overall performance of SOH estimation, the acquisition of DC curve is realized based on SOC estimation method：
It is said from this angle, this project SOH estimation is also based on adaptive model and SOC estimation to realize.
It realizes to LiFePO4The DC characteristic of/C battery clearly mathematical description, it is necessary first to design function appropriate and retouch
Form is stated, on the one hand it is expected that the complexity of the mathematical description is unsuitable excessively high；It is simultaneously it is also contemplated that related to aging of lithium battery mechanism
Characteristic parameter definition and easy extractability, in order to subsequent Analysis on ageing mechanism and SOH estimation work expansion.Based on
The Differential Capacity characteristic of lithium battery is described in upper consideration, the pseudo- Voigt linear function that this programme designs a kind of deformation.
The it is proposed of Voigt linear function is derived from the research of spectrum line style, is generally described as lorentzian curve function and Doppler's line style letter
Several convolution：
Wherein fLIt (v) is lorentzian curve, fD(v) it is Doppler's line style, and has：
Wherein αLIt is Lorentz half-breadth；αDIt is Doppler's half-breadth；V is radiation frequency；v0It is migration frequency.But Voigt line style
Function is an integrated form, not the analytical form convenient for calculating.For the ease of analyzing aging of lithium battery mechanism, just
In Differential Capacity characteristic parameter is analyzed and extracted, a kind of pseudo- Voigt linear function pair of modification is used in this programme
The Differential Capacity characteristic of lithium battery is described, and specific mathematical description is provided by following expression formula：
As V < VPWhen+Δ V：
As V >=VPWhen+Δ V：
Additionally meet：
The Differential Capacity curvilinear characteristic parameter being related in the above expression formula includes β, S, VPAnd A, they with electrification
The phase transition process of active material is related in electrode when learning reaction.Wherein β is the parameter for describing peak of curve sharpness, also referred to as
For the full width at half maximum (FWHM) of peak value line style, it can reflect the state of mutual stress between each electrochemical reaction central point；β-/ 2 refer to peak
It is worth the main peak half breadtgh of line style low voltage side, β+/ 2 refer to the main peak half breadtgh of peak value line style high-voltage side, when peak value line style not
When symmetrical, the main peak half breadtgh values of peak value two sides can difference；S is the degree of asymmetry parameter of peak value line style, with electrode reaction
Degree of reversibility it is related；VPIt is the corresponding electromotive force of peak of curve point, A is the area that peak region is surrounded, the two parameters
It is related with the content of active material actually available in electrode, such as during cell degradation, lithium metal deposition and crystalline substance
Lattice deform the loss that can all lead to lithium ion, so that the decaying of battery active volume and output power ability is further resulted in, this
A little aging mechanism can be embodied by the two parameters, some researchs can directly be filled using this two parameters as battery is measured
Put the foundation of charge capacity；Δ V is the offset of the peak point potential generated with cell degradation, the parameter and cell degradation
Ever-increasing SEI film and grain boundary resistivity are related in the process, and the formation of SEI film and its increase of thickness can directly result in electricity
The increase of pond internal resistance.
In addition, there are also some other parameters in above-mentioned mathematical description, η is the integrated intensity of Lorentzian and Gaussian function
The ratio between；P is parameter relevant to area A；It is further noted that in the above description, q refers to the charge that positive or negative pole can be filled with
Capacity, the charge capacity Q that it can be filled with integral battery are different；In addition, above several expression formulas can only be used to one
The mathematical description of single peak line style needs the algebraical sum using multiple single peak when entire characteristic curve has multiple peak values
To describe entire characteristic curve.
The above mathematical description and wherein several characteristic feature parameter PfInfluence for peak value line style, such as Fig. 1 (a), Fig. 1
(b), (wherein remaining parameter is set as in addition to the running parameter tested shown in Fig. 1 (c)：VP=0.5V；A=1Ah；β=0.2；
η=0.5；S=1)：
It is above the mathematical description designed by this project for single peak line style, for the ease of the fitting to curve,
Facilitate characteristic parameter PfExtraction, formula (6) and (7) are now subjected to abbreviation.
Enable β-=β+, approximation takes peak symmetry, so S=1；
After simplification of a formula, available preferable curve-fitting results obtain higher essence convenient for the processing to data
Spend effect.In Fig. 2, it may be seen that the fitting form of actual curve, the data point in figure is that lithium ion battery charged
Dq/dV distribution situation in journey, the lines in figure are the result being fitted according to data point, it can be seen that fitting precision compared with
It is good, meet the charging process of lithium ion battery, the interior change situation in lithium ion battery charging process can be represented.
2 LiFePO4The mathematical description of/C battery Differential Capacity characteristic and feature extraction
Phase transformation and other complicated variations of the actual lithium ion battery due to multiple element, differential characteristics curve is not
It is a unimodal value function, but multi peak value, concrete form are as shown in Figure 2.
In fig. 2 it is possible to observe three obvious characteristic peaks, the curve peak in left side mainly with the cathode material of battery
Material is related, reacts the phase transformation situation of the active material near cathode, is indicated with symbol C1；Intermediate curve peak is mainly and lithium ion
The dynamics of inside battery is related, reacts the oxidation-reduction process near the anode in charge and discharge process, is that anode refers to
Mark standard is indicated with symbol C2；Right peak value is mainly related to the active lithium content in lithium ion battery, corresponds mainly to charging knot
Electrochemical process when beam discloses nested procedure of the lithium on graphite cathode, is indicated with symbol C3；So total matched curve is such as
Shown in formula (9), by three curve C1, C2, C3 are formed by stacking.
In FIG. 3, it is seen that actual capacity estimation situation decomposition, total matched curve by three curve combinings and
At the curve of each is fitted by formula (8), and in practice, it is old that each matched curve all represents inside battery
A kind of mechanism changed approximate can represent the structure change situation of inside battery after all curve combinings.
Because the characteristic have multiple peak values, calculation amount is larger, for convenient under actual condition to the SOH of lithium ion battery into
Row estimation, need to only consider a most important peak value in Differential Capacity characteristic in the present invention.Simultaneously as the feature of the fitting
Parameter of curve is more, such as β, S, VP, η and A etc., situation is complex, so we select the peak region of representative matter
The area A that domain is surrounded carries out SOH estimation, because A is related with the content of active material actually available in electrode, Ke Yiyou
Effect represents the degree of aging of inside battery, and only selects the area in peak value section, fills when can not deplete to avoid battery capacity
Electricity and bring error.In conclusion in the present invention, we carry out curve according to data point of the formula (8) to dq/dV and intend
It closes, selects the highest curve C2 of peak value as parameter extraction curve, and the peak area for taking the curve to include is estimated as SOH
Characteristic parameter Pf, as shown in figure 4, concrete mode is the packet selected at the 1/10 of peak height between peak of curve and voltage axis
Envelope surface product.
3 curve matchings and error validity
Choose the aging data that charges under the 0.5C multiplying power of 26650 ferric phosphate lithium cells of certain brand, and according to foregoing description,
It carries out curve fitting to dq/dV data point, the peak area for obtaining principal curve is characterized parameter, and a pair of according to characteristic parameter one
The SOH answered carries out curve fitting, as shown in figure 5, obtaining practical SOH estimation curve and being：Y=-0.0003334 × x2+0.4291
× x-35.74, linear fit goodness are：R2=0.8925.Curve matching precision is verified in table 1, verify data choosing
What is selected is the battery that other two sections have neither part nor lot in aging curve fitting, and extraction section data progress error is tested from its aging data
Card finds its precision within 10%, and estimation effect is more accurate, therefore, should be based on the Differential Capacity feature song of agine mechaism
Line method can be used as one of the method for ferric phosphate lithium cell health status estimation.
The verifying of 1 SOH estimation error of table
More than 4 curve of double curvature fittings are estimated with SOH
It is emphasized that the extraction process of features above table is the standard multiplying power charge data based on capacity calibration node
Come what is realized, therefore SOH estimation is carried out to application this feature table, it is necessary to constant current first be carried out using standard multiplying power to mesuring battary
Charging, could obtain desired aging character parameter Pf, and then table look-up to obtain corresponding SOH.And in engineering battery in practice
Rate of charge not necessarily standard multiplying power, temperature condition be not necessarily room temperature, for the most common CCCV charge mode,
The rate of charge in CC stage may have with different charging equipments, different battery brands and different charge rate requirements
Institute's difference.In order to adapt to the difference of different rate of charge, operating ambient temperature that charging equipment may use, this patent is accelerating
The more multiplying power constant-current charge tests of multi-temperature are increased in ageing process Plays volume test step, purpose is exactly to establish electricity
Pond aging character table corresponding under different temperatures difference rate of charge, to adapt to charging different in actual condition times
Rate.Specific step is as follows：
(1) more multiplying power aging processes：
Accelerated aging tests main part is the charge and discharge cycles of Covering samples battery life cycle management, is opened by new battery
Begin to test, thinks battery end of life when battery active volume is down to the 70% of rated capacity.Fig. 6 (a) is more multiplying power agings
Process is divided into accelerated ageing process and volume test process.
During accelerated ageing, the charging voltage upper limit and discharge voltage lower limit are respectively 3.65V and 2.5V, charge and discharge times
Rate is 4C, and in accelerated ageing cyclic process, 10 circulations of every experience need to carry out primary more multiplying power constant-current charge tests and mark
Quasi- volume test (i.e. capacity calibration), more multiplying power constant-current charge tests and capacity demarcation flow are shown in Fig. 6 (b) and Fig. 6 (c), two
In figure, charge and discharge blanking voltage is 3.65/2.5V, and multiplying power of the two only in charging process is different, the charging times in Fig. 6 (c)
Rate is 0.5C, the C in Fig. 6 (b)pDifferent rate of charge is represented, in this experiment, with reference to actual operating conditions, CpIt takes
0.5C, 1C, 2C, 3C carry out different multiplying charging experiment in order every time in the interval of accelerated ageing process, obtain different
Data under multiplying power, the ageing state consider in this 4 charge and discharge cycles, in addition to rate of charge is slightly larger, remaining stress intensity
It is standard level, capacity attenuation is very small, therefore is considered as SOH in this process approximation constant.
(2) master curve fitting process (as shown in Figure 7)：
1) primary condition in flow chart 6 (a) is considered into temperature element, as shown in Fig. 6 (d), obtained under different multiplying
The lithium-ion electric of (- 10 DEG C, -5 DEG C, 0 DEG C, 5 DEG C, 10 DEG C, 15 DEG C, 20 DEG C, 25 DEG C) under (0.5C, 1C, 2C, 3C) and different temperatures
The charging ageing process data in pond；
2) differential characteristics curve is fitted according to formula (8), obtains the characteristic parameter under different multiplying；
3) according to the characteristic parameter of acquisition, temperature is fitted the SOH estimation curve under corresponding multiplying power, obtains three-dimensional
SOH estimates curved surface；
4) four-dimensional SOH is obtained according to different rate of charge and estimates curved surface；
Specific estimated data's figure is as shown in table 2：
2 four-dimension SOH of table estimates schematic table
After obtaining four-dimensional SOH estimation curved surface, so that it may health status estimation is carried out to the lithium ion battery under actual condition,
As shown in figure 8, obtaining corresponding SOH-P from four-dimensional aging character curved surface by two factors of temperature and rate of charge firstf
Curve, herein PfThe as aging character parameter that is obtained using the scheme in this patent of mesuring battary；Again according to the feature of battery
Parameter PfInquire SOH-PfTable can be obtained mesuring battary SOH.
Claims (2)
1. a kind of evaluation method of health state of lithium ion battery, which is characterized in that described method includes following steps：
Step 1, it for selected lithium ion battery sample, designs and carries out within the temperature range of -20~40 DEG C, more stress accelerate
Degradation, in battery entirety ageing process, aging node is chosen in the health status aging every 5%, obtains in not equality of temperature
Each node normal capacity and more multiplying power charging voltage characteristics curves under degree；
Step 2, the aging initial data in previous step is excavated, Differential Capacity is fitted using pseudo- Voigt linear function
Curve obtains characteristic parameter, four-dimensional aging character is established according to the relationship between characteristic parameter, temperature, rate of charge and SOH
Curved surface；
Step 3, based on four-dimension SOH estimation curved surface, in conjunction with mesuring battary charging process in voltage response, to actually answering
Lithium ion battery in is estimated.
2. a kind of evaluation method of health state of lithium ion battery according to claim 1, it is characterised in that：In step 1,
More stress accelerated aging tests are charge-discharge magnification, charge and discharge blanking voltage accelerated aging test.
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