CN105576318B - Determine the multi-parameter comprehensive decision method of the retired lithium battery uniformity of electric automobile - Google Patents

Determine the multi-parameter comprehensive decision method of the retired lithium battery uniformity of electric automobile Download PDF

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CN105576318B
CN105576318B CN201610099213.3A CN201610099213A CN105576318B CN 105576318 B CN105576318 B CN 105576318B CN 201610099213 A CN201610099213 A CN 201610099213A CN 105576318 B CN105576318 B CN 105576318B
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battery
capacity
msup
retired
voltage
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CN105576318A (en
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廖强强
赵书奇
张利中
刘松慧
江涛
穆苗苗
聂凯斌
徐乐
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Jiangsu Jia Zhou energy conservation and Environmental Protection Technology Co., Ltd.
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Shanghai University of Electric Power
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • 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]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4228—Leak testing of cells or batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Abstract

The present invention relates to a kind of multi-parameter comprehensive decision method for determining the retired lithium battery uniformity of electric automobile, using the retired lithium battery of electric automobile as research object, characterized by many-sided performance indications such as visual examination, solid measure, pulse characteristicses curve and electrochemical impedance spectroscopy test, retired electrokinetic cell is subjected to Stepwise Screening classification, the uniformity of each retired battery performance is assessed, is that the echelon utilization of increasing retired electrokinetic cell postorder lays the foundation.

Description

Determine the multi-parameter comprehensive decision method of the retired lithium battery uniformity of electric automobile
Technical field
The present invention relates to a kind of battery detection method, more particularly to a kind of determination retired lithium battery uniformity of electric automobile Multi-parameter comprehensive decision method.
Background technology
With the progressively industrialization of electric automobile, the yield rapid growth of China's electric car, and electric automobile power battery Recoverable amount can also sharply increase therewith.Domestic new-energy automobile sales volume increases by 4 times on a year-on-year basis up to more than 330,000 within 2015.Generally In the case of, to ensure the security and performance of automobile, the requirement of electric automobile manufacturer works as the capacity attenuation of electrokinetic cell extremely It will be replaced when 70~80%., still can be with however, retired electrokinetic cell still has certain residual capacity and service life Further use to excavate its surplus value in other fields, be such as used for electric bicycle, the power supply of tourist coach, general life Mains lighting supply, or for power energy storage, including regenerative resource power output is smooth, distributed power supply from far-off regions, fills and changes The fields such as power station energy storage, quality of power supply regulation.Because environment residing when electrokinetic cell is in-service is more complicated, cause the property of lithium battery Energy attenuation degree is different, so that the inconsistency between adding battery.Therefore, if to be carried out to retired electrokinetic cell again sharp With, it is necessary to the performance to retired electrokinetic cell is studied, and assesses the uniformity between battery, and is screened and be grouped, To maximally utilise the residual capacity of retired battery on the premise of safety.
At present, research of the lot of domestic and foreign scholar to retired electrokinetic cell is concentrated mainly on cell decay Analysis on Mechanism, electricity Pond performance test and battery echelon are utilized in terms of Technical Economy model.Imperial court peak and Tan Li etc. are with retired electrokinetic cell It is research object with electrokinetic cell is scrapped, finds because the dissolving of electrode active material and conductive agent is with coming off, electrode material is brilliant Grain change, and negative terminal surface SEI film repeated reproducibility cause power lithium-ion battery performance degradation.Matthieu Dubarry etc. Tested by dynamic response, quantify this kind of non-damage type analysis method of capacity attenuation under capacity attenuation and peak power draw it is retired Dynamic lithium battery capacity attenuation main cause is the loss of lithium in electrode.The research such as Xu Jing compares mixed pulses power characteristic (HPPC) method of testing, electrochemical impedance method of testing and electric current transformation approach measure retired electrokinetic cell inner resistance advantage and disadvantage and Correlation.Jeremy Neubauer etc. from the secondary necessity utilized of the high analyzing electrokinetic cell of electrokinetic cell initial cost, Think that this measure will extend electrokinetic cell life cycle, reduce battery cost, be conducive to the marketing of accumulator car without environment pollution.
Electric automobile power battery applying working condition differs greatly, and single is difficult that correct judge is electric from internal resistance, the assessment of electrical property How uniformity inside pond, carry out Stepwise Screening classification to retired electrokinetic cell, assess the uniformity of each retired battery performance, So far without good ground solution, but the key that retired electrokinetic cell complementary energy is recycled.
The content of the invention
The problem of being recycled the present invention be directed to the retired lithium battery of electric automobile, it is proposed that one kind determines that electric automobile is retired The multi-parameter comprehensive decision method of lithium battery uniformity, using retired lithium dynamical battery as research object, passes through exterior appearance, capacity Many-sided performance indications such as measure, pulse characteristicses curve and electrochemical impedance spectroscopy test are characterized, by retired electrokinetic cell Stepwise Screening classification is carried out, the uniformity of each retired battery performance is assessed.
The technical scheme is that：A kind of multi-parameter comprehensive judgement side for determining the retired lithium battery uniformity of electric automobile Method, it is electronic from visual examination, volume test, pulse characteristic tracing analysis, electrochemical impedance spectroscopy four part synthetic determinations of test The uniformity of the retired lithium battery of automobile is specific to judge as follows：
1) visual examination：Any of which situation is damaged in the presence of deformation, bulge, breakage, leakage, serious corrosion or pole Battery be removed, it is non-reusable；
2) volume test：The electrokinetic cell come out through external morphology Analysis and Screening carries out capacity check, capacity test method First to use 1xI3Constant-current charge is reduced to 0.1x I to constant-voltage charge is carried out after 3.65V when electric current reduces3When battery stop charging, Then 1 hour is stood, finally uses 1x I3Discharged, until final discharging voltage reaches 2.70V, according to 1x I3Current value Battery capacity is calculated with discharge time data, capacity is in terms of Ah, wherein I3For 1/3C multiplying power electric currents；
I3Demarcation：Do not decay by hypothesis battery capacity, decay to 80%, decay to 67% 3 kind of demarcation condition, use State capacity test method to test the capacity of battery, the capacity of test substitutes into formula below and calculates each battery capacity averagely relatively by mistake Rate δ,
For the capacity average value under the conditions of three kinds of demarcation, △ is absolute value poor between average value and each class value, is obtained Each battery capacity average relative error rate δ, takes the electricity under the conditions of the minimum demarcation of the capacity average relative error rate scope measured Tankage is calibrated capacity, and I is demarcated with this capacity3Current value；
3) pulse characteristic tracing analysis：Battery presses different multiplying pulse discharge and recharge, compares the charging/discharging voltage of each battery Curve, charge and discharge process is：Lithium battery is according to progress constant-voltage charge after 1/3C constant-current charges to 3.65V to 0.1xI3, stand 2 small When；1C electric discharge 10s, stand 40s；3C electric discharge 10s, stand 40s；5C electric discharge 10s, stand 40s；1C charging 10s, stand 40s；Most Afterwards, according to progress constant-voltage charge after 1/3C constant-current charges to 3.65V to 0.1xI3, pulse discharge and recharge terminates；Obtain pulse charge and discharge Piezoelectric voltage curve, judges that battery is consistent with voltage during 5C multiplying power dischargings more than 2.7V, between 2.7-2.5V, less than 2.5V Property, the battery that voltage is more than 2.7V is classified as one group, and voltage is classified as another group between 2.7-2.5V battery, and voltage is less than 2.5V's Battery is rejected, and 2.7V is battery testing final discharging voltage, and 2.5V is the minimum electric discharge safe voltage of battery manufacturer setting；
4) electrochemical impedance spectroscopy：Retired battery is carried out using the type electrochemical workstations of Switzerland Autolab PGSTAT 302 Electrochemical impedance is tested, and electrochemical impedance test frequency is between 0.01Hz~100kHz, using ZSimpWin softwares to electrification The test data for learning impedance carries out Equivalent Circuit Fitting, analyzes inside battery electrochemical impedance characteristic by fitting parameter, uses Europe Nurse internal resistance Rs, charge transfer resistance RctWith lithium ion diffusion coefficient DLi +Come to battery group, wherein lithium ion diffusion coefficient DLi + Reflect the size of concentration polarization impedance, DLi +Value is smaller, and concentration polarization is bigger, lithium ion diffusion coefficient DLi +Calculation formula For：
Wherein ideal gas constant R=8.314J/ (molK), absolute temperature T=298.15K, A is the cross section of electrode Product, n is electron transfer number, and F is Faraday constant F=96487C/mol, and C is the concentration of lithium ion in electrode, and σ is Warburg The real part Z of the weber factor, σ and impedance spectrumreRelation it is as follows：Zre=Rs+Rct+σω-1/2, ω is progress electrochemical impedance test During angular frequency, ω=2 π f, f are the frequencies in EIS tests.
The beneficial effects of the present invention are：Present invention determine that the multi-parameter comprehensive of the retired lithium battery uniformity of electric automobile is sentenced Determine method, suitable screening technique is provided for the recycling of retired electrokinetic cell, be present increasing retired power electric The echelon of pond postorder is utilized and laid the foundation.
Brief description of the drawings
Fig. 1 is the qualified retired battery actual capacity figure of 20 outward appearances of the invention；
Fig. 2 is the average actual capacity distribution map of the qualified retired lithium battery of 20 outward appearances of the invention；
Fig. 3 is the pulse charging/discharging voltage curve map of the retired battery in part of the present invention；
Fig. 4 is the electrochemical impedance spectrogram of the representational retired lithium battery of the present invention；
Fig. 5 is the electrochemical impedance spectroscopy equivalent-circuit model figure of retired lithium battery of the invention；
Fig. 6 is retired battery capacity of the invention and ohmic internal resistance Rs, charge transfer resistance RctDistribution map；
Fig. 7 is diffusion coefficient D of the present inventionLi +Value and capacity relationship figure.
Embodiment
Exemplified by eliminating 60 retired lithium iron phosphate dynamic batteries from certain electric automobile, its nominal capacity is 15Ah.
Determine that the multi-parameter comprehensive decision method of the retired lithium battery uniformity of electric automobile, including visual examination, capacity are surveyed Examination, pulse characteristic tracing analysis, electrochemical impedance spectroscopy test four parts, are specifically described as follows：
1st, not available a part of retired lithium dynamical battery is rejected after visual examination, the retired battery of three classes can not enter below Row echelon is recycled, and can only disassemble recycling：(1) there is the battery of deformation or bulge situation；(2) exist it is damaged or The battery of leakage；(3) there is the battery that serious corrosion or pole are damaged.
Lithium dynamical battery problem of inconsistency after retired is highlighted.Battery physical and chemical performance changes possibly through external appearance characteristic just It can show, situations such as such as deformation, bulge, breakage, leakage, corrosion, pole are damaged, the retired lithium battery that there are these features can not Recycle.20 preferable batteries of exterior appearance are filtered out in this 60 retired batteries, and are respectively labeled as No. 1-20.
2nd, volume test：
Using U.S.'s Bitrode MCV 2-200-5 type cell test systems to being come out through visual examination Analysis and Screening Electrokinetic cell carry out capacity check, first use 1xI3(I3For 1/3C multiplying powers electric current) constant-current charge to carrying out constant-voltage charge after 3.65V, 0.1x I are reduced to when electric current reduces3When battery stop charging, then stand 1 hour, finally use 1x I3Discharged, Zhi Daofang Electric final voltage reaches 2.70V, according to 1x I3(A) current value and discharge time data calculates battery capacity (in terms of Ah).
Retired electrokinetic cell actual capacity must have a certain degree of decay, it is therefore desirable to which its capacity is re-scaled. However, due to not knowing which kind of degree is retired battery capacity decay to, the charging and discharging currents 1xI set during solid measure3Also It cannot set.Reference《Energy-storage battery Performance Testing Technology specification used for intelligent electric network》Test request, we assume battery respectively Capacity does not decay (15Ah), decays to 80% (12Ah), decays to 67% (10Ah) these three situations to demarcate the reality of battery Capacity, i.e., now by I3It is set as 5A, 4A, 3.3A to carry out volume test, looks at same battery in the case of above-mentioned three kinds Actual capacity otherness.The qualified retired battery actual capacity of obtained 20 outward appearances is as shown in Figure 1.
Entered by each battery capacity average relative error rate δ of tri- kinds of capacity demarcation of 10Ah, 12Ah, 15Ah using formula (1) Row is calculated.
For the capacity average value under the conditions of three kinds of demarcation, △ is absolute value poor between average value and each class value.By Calculate, -6.93 are respectively interposed in by each battery capacity average relative error rate δ of tri- kinds of capacity of 10Ah, 12Ah, 15Ah demarcation~ 3.61%th, -1.30%~4.85%, -3.02%~3.55, it can be seen that the volume error scope measured under the conditions of 12Ah compared with It is small.Fig. 2 is the average actual capacity distribution map of the qualified retired lithium battery of 20 outward appearances.By these batteries, grade is divided into by measure 3 groups, 12-14Ah groups have 1,2,3,4,8,9,10,12,15,16,17,19, No. 20 batteries, totally 13；10-12Ah groups have 5th, 7, No. 14 batteries, totally 3；8-10Ah groups have 6,11,13,18, totally 4, in order to follow-up Performance Evaluation and classification.Together When, using this 20 retired dynamic lithium batteries to be overall, it have studied the distribution character of its capacity.By the way that " statistical product is solved with service Certainly " calculating of software (Statistical Product and Service Solutions, SPSS), we obtain scheme：Electricity The average of tankage is 12.06Ah, and standard deviation (arithmetic square root of variance) is 1.71.20 sample size data are carried out non- Parametric test, it is assumed that the capacity Normal Distribution of sample, illustrates that data are obeyed when sig (notable property coefficient) is more than 0.05 and refers to Fixed distribution, i.e. normal distribution.Due to this sample size N<2000, examine to enter this 20 sample size data using S-W Row non-parametric test, the result drawn is：Sig=1.151>0.05, illustrate that this 20 sample size distributions meet normal distribution. Normal distribution is to illustrate that battery capacity is distributed in bell, and when sample size is increasing, sample averages out to be close to one Fixed value, the desired value being exactly distributed, here it is the content of the law of large numbers or central limit law；It can finally send out in the sample Existing, the sample frequency occurred near desired value is higher, and the frequency from the more remote appearance of desired value is smaller.
3rd, pulse characteristic tracing analysis：
It is that a kind of assessment battery is consistent that heavy current pulse discharge and recharge is carried out to retired lithium dynamical battery and studies its characteristic curve The accurate method directly perceived of property.Using the feedback of battery to high magnification electric current in itself, by retired electrokinetic cell by a series of After discharge and recharge and standing step, the charging and discharging curve measured can truly reflect the change of battery voltage in real work Situation.Testing procedure is as follows：Optional 2 lithium batteries are according to progress constant-voltage charge after 1/3C constant-current charges to 3.65V to 0.1xI3, Stand 2 hours；1C electric discharge 10s, stand 40s；3C electric discharge 10s, stand 40s；5C electric discharge 10s, stand 40s；1C charge 10s, it is quiet Put 40s；Finally, according to progress constant-voltage charge after 1/3C constant-current charges to 3.65V to 0.1xI3, pulse discharge and recharge terminates.Now 1/3C be to be charged by 4A, hereafter all tested by the capacity newly demarcated.
Battery is pressed into different multiplying pulse discharge and recharge, compares the charging/discharging voltage curve of each battery.Fig. 3 is that part is retired The pulse charging/discharging voltage curve of battery.Although from Fig. 3 it can be found that this 5 battery (1,3,4,9,12) when being grouped by capacity Divide at one group, capacity is closer to, and in low range discharge and recharge, voltage is also consistent substantially, but in the big multiplying power discharging such as 3C and 5C When, No. 1 battery shows obvious inconsistency with other 4 cell voltages, and discharge-rate is bigger, and its inconsistency is more obvious.
With the increase of discharge current, because the degradation difference of retired battery causes its degree of polarization (or in polarization Resistance) it is different, the inconsistency of battery is also just highlighted.In figure 3, No. 1 battery and other 4 batteries during 1C multiplying power dischargings Maximum voltage difference is 0.013V；In 3C and 5C multiplying power dischargings, the maximum voltage difference of No. 1 battery and other 4 batteries is respectively 0.101V And 0.23V；When 1C multiplying powers charge, the maximum voltage difference of No. 1 battery and other 4 batteries is reduced to 0.02V again.This explanation battery exists During real work, even if ohmic internal resistance is consistent, the polarization resistance otherness caused by the complicated physicochemical change of inside battery can show Write the uniformity of influence battery operating voltage.Table 1 is the voltage under the different pulse charge-discharge magnifications of retired battery, and unit is V,
Table 1
Table 1 is the voltage (voltage value for taking pulse 5s) under the different charge-discharge magnifications of retired lithium battery pulse.Can from table 1 To find out, this maximum voltage difference of 20 batteries under discharge scenario during 1C multiplying powers is 0.263V, maximum voltage during 3C multiplying powers Difference is 0.41V, and maximum voltage difference when maximum voltage difference during 5C multiplying powers is 1C multiplying powers under 0.505V, charge condition is 0.081V, with the increase of electric current, voltage difference is bigger between battery, and voltage difference reduces therewith when the current decreases.With 5C multiplying powers Voltage is the foundation for judging battery consistency more than 2.7V, between 2.7-2.5V, less than 2.5V during electric discharge, is divided into 3 groups.From Table 1 as can be seen that the battery that voltage is more than 2.7V have 1,2,3,5,7,8,9,11,12,13,14,16,18, No. 19, voltage between Between 2.7-2.5V have 4,6,10,15, No. 17, what voltage was less than 2.5V has No. 20 batteries.2.7V is that our battery testings are put Electric final voltage, 2.5V is the minimum electric discharge safe voltage of battery manufacturer setting.
4th, electrochemical impedance spectroscopy：
Electrochemical impedance test is carried out to retired battery using the type electrochemical workstations of Switzerland Autolab PGSTAT 302. Electrochemical impedance test frequency is between 0.01Hz~100kHz.Utilize test data of the ZSimpWin softwares to electrochemical impedance Equivalent Circuit Fitting is carried out, inside battery electrochemical impedance characteristic is studied by fitting parameter.
In order to further inquire into retired battery with two side terminals problem, electrochemical impedance spectroscopy is carried out to this 20 batteries and ground Study carefully.Fig. 4 is the electrochemical impedance spectrogram of representational retired lithium battery.In Fig. 4, the straight line portion of the 4th quadrant is by electricity There is the embodiment of delayed electric current, as induction reactance effect in battery system caused by sense, it can be inferred that being tested retired lithium battery Should be with the presence of an inductive reactive element L in chemical impedance equivalent circuit；Correspond to Z in high bandimFor 0 when ZreValue is and mass transfer Relevant ohmic internal resistance Rs, ZimFor the imaginary part in electrochemical impedance spectroscopy, the i.e. longitudinal axis, ZreFor the real part in electrochemical impedance spectroscopy, i.e., Transverse axis, RsFor ohmic internal resistance；Low-frequency range reflects solid diffusion process of the lithium ion inside active material particle, is characterized as one Oblique line, the oblique line of low-frequency range is by weber (Warburg) impedance ZWElement is represented.Because the slope for the battery low frequency range oblique line surveyed It is not 45 °, is not the weber impedance of standard, therefore, the Z in equivalent circuitWReplace with general normal phase angle element QZw。 Mid Frequency and the intersection of low-frequency range do not have clear and definite point of interface because in this region battery simultaneously exist concentration polarization and Activation polarization, high frequency capacity reactance arc corresponds to charge transfer resistance RctWith electrode double layer capacitance QCdl.Therefore, retired lithium battery Electrochemical impedance spectroscopy equivalent-circuit model as shown in figure 5, often phase angle element QZwWith charge transfer resistance RctWith electricity after series winding Pole electric double layer capacitance QCdlParallel connection, then contact ohmic internal resistance RsWith inductance L.
In Fig. 4,7,12 and No. 14 batteries are divided into one group in pulsed discharge experiment, are considered as uniformity preferable.So And, it is special from still having between No. 7 batteries of electrochemical impedance spectroscopy it can be seen from the figure that and 12 and No. 14 batteries than larger otherness It is not the low frequency diffusion part in impedance spectrum.By Fig. 5 equivalent circuit by the equivalent-circuit component of this 20 retired lithium batteries Parameter analysis of electrochemical comes out, and obtains ohmic internal resistance RsValue and charge transfer resistance RctValue, by the capacity of this 20 batteries, RsValue and RctValue Drafting pattern 6.We are with ohmic internal resistance Rs, charge transfer resistance RctValue is respectively less than 7m Ω, between 8-10m Ω, is more than 10m Ω Judge that the foundation of battery consistency is grouped.From fig. 6, it can be seen that RsAnd RctValue be respectively less than 7m Ω battery by 1,2,4,7, 8th, 9,10,11,12,13,14,15,16,17,19, No. 20, have 3 between 8-10m Ω battery, 6, No. 18, more than 10m Ω electricity Pond has No. 5.
Except ohmic internal resistance Rs, charge transfer resistance RctBeyond value, concentration polarization impedance is influence battery capacity decay More key factor, and lithium ion diffusion coefficient DLi +The size of concentration polarization impedance, D can be reflectedLi +It is worth smaller, concentration polarization It is bigger.Lithium ion diffusion coefficient DLi +Calculation formula be：
Wherein：Ideal gas constant R=8.314J/ (molK), absolute temperature T=298.15K, the cross-sectional area of electrode A=0.01m3, electron transfer number=1, Faraday constant F=96487C/mol, C are the concentration (ferric phosphate of lithium ion in electrode The concentration of lithium is 7.69 × 103mol/m3), σ is the Warburg webers of factors.And σ and ZreWith following relation：
Zre=Rs+Rct+σω-1/2 (3)
Wherein：ω is carries out the angular frequency in electrochemical impedance test process, and ω=2 π f, f are the frequencies in EIS tests, ZreFor the real part of impedance spectrum corresponding with ω, RsFor ohmic internal resistance, RctFor charge transfer resistance.According to formula (3), with ω-1/2 For abscissa, ZreMapped for ordinate, the slope of obtained straight line is Warburg factor sigmas, then σ is substituted into formula (2) and calculated Draw lithium ion diffusion coefficient.Table 2 is the σ values and diffusion coefficient D of lithium ion in 20 retired lithium batteriesLi +Value, its diffusion coefficient DLi +Value is as shown in Figure 7 with capacity relationship.From figure 7 it can be seen that battery capacity is proportionate with lithium ion diffusion coefficient.To expand Dissipate coefficient DLi +Value is more than 6 × 10-14cm2/ s is the foundation for judging battery consistency.On this basis, from table 2 it can be seen that 1, 2nd, 3,4,5,7,8,9,10,11,12,14,15,16,17,19, No. 20 battery with two side terminals preferably, and 6,13, No. 18 batteries DLi +Value is respectively less than 4 × 10-14cm2/s。
Table 2
After being parsed to the electrochemical impedance modal data of this 20 retired lithium batteries, respectively to its Rs、RctAnd DLi +Carry out Non-parametric test, analyzes Rs、RctAnd DLi +With the correlation of battery capacity.Because retired lithium battery sample number is smaller, accurate inspection is taken Value under the conditions of testing, wherein RsSig=0.862>0.05, RctSig=0.186>0.05, DLi +Sig=0.834> 0.05, it is believed that Rs、RctAnd DLi +Value meets normal distribution, and understands that retired battery capacity is also complied with just by Such analysis State is distributed, and is satisfied by the application conditions to its Pearson correlation coefficient, R is weighed with Pearson correlation coefficients、RctAnd DLi + Degree of relevancy between battery capacity.The positive and negative positive negativity for indicating correlation of the Pearson correlation coefficient of variable, but Correlation is invalid when its conspicuousness Sig values are more than 0.05, and correlation is set up during less than 0.05.It is computed drawing capacity and RsIt Between Pearson correlation coefficient be 0.364, but Sig=0.114>0.05, without notable sexual intercourse；Capacity and RctBetween value Peason coefficient correlations are -0.538, Sig=0.014<0.05, therefore capacity and RctBetween in notable moderate negative correlation, Illustrate RctValue is bigger, and battery capacity is smaller；Capacity and DLi +Between Peason coefficient correlations be 0.729, Sig=0.00< 0.05, therefore capacity and DLi +Between be strong positive correlation, illustrate DLi +Value is bigger, and battery capacity is bigger.Therefore, retired lithium electricity is influenceed Tankage attenuation factor, understands it is primarily concentration polarization impedance from impedance angle analysis, next to that charge transfer resistance, and ohm The influence of internal resistance is smaller.
Comprehensive battery capacity, pulse discharging voltage, resistance, the consistency analysis of diffusion coefficient, this 20 retired lithium batteries 3 groups can be divided into, capacity is more than 2.7V between 12-14Ah, pulse discharging voltage, and ohmic internal resistance and charge transfer resistance are respectively less than 7m Ω and lithium ion diffusion coefficient are more than 6 × 10-14cm2s-1Have 1,2,8,9,12,14,16, No. 19 batteries, be the 1st group；Capacity is situated between In 10-14Ah, pulse discharging voltage is more than 2.5V, and ohmic internal resistance and charge transfer resistance are respectively less than 10m Ω and lithium ion spreads Coefficient is more than 6 × 10-14cm2/ s has 3,4,7,10,15, No. 17 batteries, is the 2nd group；Remaining 5,6,11,13,18, No. 20 electricity Pond is the 3rd group, there is that battery capacity is relatively low or pulse discharging voltage is smaller or charge transfer resistance is larger or lithium ion diffusion The less situation of coefficient.For the 1st or 2 Battery packs, from security standpoint its battery in groups after discharge and recharge system can be by Designed according to the minimum battery of capacity in the Battery pack.And for the 3rd Battery pack, because the decline of its battery performance is larger, Uniformity is also bad, it is not recommended that recycle in groups.

Claims (1)

1. a kind of multi-parameter comprehensive decision method for determining the retired lithium battery uniformity of electric automobile, it is characterised in that from outward appearance Inspection, volume test, pulse characteristic tracing analysis, electrochemical impedance spectroscopy test four retired lithiums of part synthetic determination electric automobile Battery with two side terminals, it is specific to judge as follows：
1) visual examination：The electricity of any of which situation is damaged in the presence of deformation, bulge, breakage, leakage, serious corrosion or pole Pond is removed, non-reusable；
2) volume test：The electrokinetic cell come out through external morphology Analysis and Screening carries out capacity check, and capacity test method is first Use 1xI3Constant-current charge is reduced to 0.1xI to constant-voltage charge is carried out after 3.65V when electric current reduces3When battery stop charging, then 1 hour is stood, 1xI is finally used3Discharged, until final discharging voltage reaches 2.70V, according to 1xI3Current value and electric discharge Time data calculates battery capacity, and capacity is in terms of Ah, wherein I3For 1/3C multiplying power electric currents；
I3Demarcation：Do not decay by hypothesis battery capacity, decay to 80%, decay to 67% 3 kind of demarcation condition, use above-mentioned capacity Method of testing tests the capacity of battery, and the capacity of test substitutes into formula below and calculate each battery capacity average relative error rate δ,
<mrow> <mi>&amp;delta;</mi> <mo>=</mo> <mfrac> <mi>&amp;Delta;</mi> <mover> <mi>X</mi> <mo>&amp;OverBar;</mo> </mover> </mfrac> <mo>&amp;times;</mo> <mn>100</mn> <mi>%</mi> </mrow>
For the capacity average value under the conditions of three kinds of demarcation, △ is absolute value poor between average value and each class value, obtains each battery Capacity average relative error rate δ, takes the battery capacity under the conditions of the minimum demarcation of the capacity average relative error rate scope measured For calibrated capacity, I is demarcated with this capacity3Current value；
3) pulse characteristic tracing analysis：Battery presses different multiplying pulse discharge and recharge, compares the charging/discharging voltage curve of each battery, Charge and discharge process is：Lithium battery is according to progress constant-voltage charge after 1/3C constant-current charges to 3.65V to 0.1xI3, stand 2 hours；1C Discharge 10s, stands 40s；3C electric discharge 10s, stand 40s；5C electric discharge 10s, stand 40s；1C charging 10s, stand 40s；Finally, press According to progress constant-voltage charge after 1/3C constant-current charges to 3.65V to 0.1xI3, pulse discharge and recharge terminates；Obtain pulse charging/discharging voltage Curve, battery consistency is judged with voltage during 5C multiplying power dischargings more than 2.7V, between 2.7-2.5V, less than 2.5V, electricity Battery of the pressure more than 2.7V is classified as one group, and voltage is classified as another group between 2.7-2.5V battery, and voltage is less than 2.5V battery Reject, 2.7V is battery testing final discharging voltage, 2.5V is the minimum electric discharge safe voltage of battery manufacturer setting；
4) electrochemical impedance spectroscopy：Electrification is carried out to retired battery using the type electrochemical workstations of Switzerland Autolab PGSTAT 302 Testing impedance is learned, electrochemical impedance test frequency is hindered electrochemistry between 0.01Hz~100kHz using ZSimpWin softwares Anti- test data carries out Equivalent Circuit Fitting, inside battery electrochemical impedance characteristic is analyzed by fitting parameter, with ohm Hinder Rs, charge transfer resistance RctWith lithium ion diffusion coefficient DLi +Come to battery group, wherein lithium ion diffusion coefficient DLi +Reflection The size of concentration polarization impedance, DLi +Value is smaller, and concentration polarization is bigger, lithium ion diffusion coefficient DLi +Calculation formula be：
<mrow> <msup> <msub> <mi>D</mi> <mrow> <mi>L</mi> <mi>i</mi> </mrow> </msub> <mo>+</mo> </msup> <mo>=</mo> <mfrac> <mrow> <msup> <mi>R</mi> <mn>2</mn> </msup> <msup> <mi>T</mi> <mn>2</mn> </msup> </mrow> <mrow> <mn>2</mn> <msup> <mi>A</mi> <mn>2</mn> </msup> <msup> <mi>n</mi> <mn>4</mn> </msup> <msup> <mi>F</mi> <mn>4</mn> </msup> <msup> <mi>C</mi> <mn>2</mn> </msup> <msup> <mi>&amp;sigma;</mi> <mn>2</mn> </msup> </mrow> </mfrac> <mo>,</mo> </mrow>
Wherein ideal gas constant R=8.314J/ (molK), absolute temperature T=298.15K, A is the cross-sectional area of electrode, n For electron transfer number, F is Faraday constant F=96487C/mol, and C is the concentration of lithium ion in electrode, and σ is Warburg webers The real part Z of the factor, σ and impedance spectrumreRelation it is as follows：
Zre=Rs+Rct+σω-1/2, ω is carries out the angular frequency in electrochemical impedance test process, and ω=2 π f, f are EIS tests In frequency.
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