CN107843846A - A kind of health state of lithium ion battery method of estimation - Google Patents

A kind of health state of lithium ion battery method of estimation Download PDF

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Publication number
CN107843846A
CN107843846A CN201711014776.9A CN201711014776A CN107843846A CN 107843846 A CN107843846 A CN 107843846A CN 201711014776 A CN201711014776 A CN 201711014776A CN 107843846 A CN107843846 A CN 107843846A
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discharge
mrow
lithium ion
ion battery
state
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CN107843846B (en
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尹鸽平
杨杰
杜春雨
高云智
左朋建
程新群
马玉林
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Harbin Institute of Technology
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Harbin Institute of Technology
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01RMEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R31/00Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
    • G01R31/36Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
    • G01R31/3644Constructional arrangements
    • G01R31/3648Constructional arrangements comprising digital calculation means, e.g. for performing an algorithm
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01RMEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R31/00Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
    • G01R31/36Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
    • G01R31/392Determining battery ageing or deterioration, e.g. state of health
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01RMEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R31/00Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
    • G01R31/36Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
    • G01R31/396Acquisition or processing of data for testing or for monitoring individual cells or groups of cells within a battery

Abstract

A kind of health state of lithium ion battery method of estimation, methods described are as follows:It is front and rear with discharge voltage during certain working system discharge and recharge, discharge circuit, discharge time data to obtain lithium ion battery aging;Intercept discharge voltage of the data in identical state-of-charge section, discharge current, discharge time data that the first step obtains;Define the health status indicator expression formula of lithium ion battery;Obtain the V in the 3rd steplower limitValue;The HI values in formula are obtained, obtain the health status of battery.It is an advantage of the invention that:The present invention from battery work when apparent data (discharge voltage, discharge current) discharge time that can measure in real time, there is the health state of lithium ion battery method of estimation of acquisition parameter easily to obtain, the pervasive general, characteristic that can apply in real time, it is easy to be embedded in the health status of battery management system estimation battery, the shortcomings that substantially improving existing work system or test equipment, practicality is very strong.

Description

A kind of health state of lithium ion battery method of estimation
Technical field
The present invention relates to a kind of health state of lithium ion battery method of estimation.
Background technology
The health status (State of Health, SOH) of lithium ion battery is often used in the aging journey for characterizing battery Degree, mainly there is two kinds of definition methods at present, and one:Maximum of the maximum available with battery when completely healthy after cell degradation can With the percentage of capacity;Two:The percentage of impedance of the impedance with battery when completely healthy after cell degradation.Accurately and timely estimate Meter cell health state is not only efficiently run to cell safety to be significant, and can be remaining battery probable life Prediction provide data support.
In existing health state of lithium ion battery method of estimation, the acquisition of capability value needs to adopt under isothermal condition Battery is charged into fullcharging electricity condition with constant current constant voltage method, then using constant flow method by battery discharge to by voltage, and circulate Discharge and recharge at least 3 times, the maximum available value averaged as battery current state, not only time-consuming, and most feelings Battery is all in dynamic discharge and recharge or shallow discharge and recharge under condition, therefore this method is difficult to real-time online application.Impedance value Acquisition mainly has impulse method and electrochemical impedance spectroscopy, but both approaches have the drawbacks of larger, on the one hand need to ensure State-of-charge and temperature before and after cell degradation is identical, and on the other hand the former needs test equipment to have sufficiently high measurement essence Degree, and the latter needs specific test equipment, further, since the amplitude of variation of its impedance value is smaller afterwards before ageing for battery, because This health status method of estimation based on impedance is difficult to practical application.
The content of the invention
The invention aims to solve existing health state of lithium ion battery method of estimation to need specific test real Test or the problem of specific test equipment causes parameter acquiring difficult and is unsuitable for online real-time application, there is provided a kind of lithium ion battery Health status method of estimation.
To achieve the above object, the technical scheme that the present invention takes is as follows:
A kind of health state of lithium ion battery method of estimation, the method for estimating state comprise the following steps:
Step 1:It is front and rear with discharge voltage during certain working system discharge and recharge, electric discharge to obtain lithium ion battery aging Electric current, discharge time data;Described working system includes charge and discharge system, charging and discharging currents and temperature;
Step 2:Discharge voltage in identical state-of-charge section of the data that obtain in interception step 1, discharge current, Discharge time data;
Step 3:It is proposed the health status indicator expression formula of lithium ion battery:
Wherein, the HI be lithium ion battery health status value, t01For its corresponding identical state-of-charge before cell degradation The initial time in section, t0For the initial time in its corresponding identical state-of-charge section after cell degradation, tend1Before cell degradation The end time in its corresponding identical state-of-charge section, tendFor the termination in its corresponding identical state-of-charge section after cell degradation Moment, VfreshAnd V (t)aged(t) be respectively before cell degradation and aging after in step 2 putting in identical state-of-charge section Piezoelectric voltage data, Vlower limitDischarge cut-off voltage value when taking the lithium ion battery to discharge completely, I (t) is identical in step 2 The discharge current of lithium ion battery in state-of-charge section;
Step 4:V is setlower limitValue;
Step 5:HI values are obtained according to formula (3), so as to obtain the health status of battery.
Health state of lithium ion battery method of estimation described in more than one is applied to the lithium-ion electric of all material system Pond monomer and battery pack.
It is of the invention to be relative to the beneficial effect of prior art:The apparent number that the present invention can measure in real time when being worked from battery Set out according to (discharge voltage, discharge current, discharge time), the health state of lithium ion battery method of estimation of acquisition has parameter easy Obtain, the pervasive general, characteristic that can apply in real time, be easy to be embedded in the health status of battery management system estimation battery, it is only necessary to Discharge voltage, discharge current when being worked using battery in identical state-of-charge section, discharge time data can be obtained in real time Battery health status estimate, overcome existing needs standard based on capacity or the health status method of estimation of impedance The shortcomings that work system or test equipment, practicality is very strong.And further influence of the temperature to cell discharge performance can be drawn Enter in this health state of lithium ion battery method of estimation, obtain the wider array of improved health state of lithium ion battery of the scope of application Method of estimation.Commented in addition, this health state of lithium ion battery method of estimation can be used in the quick of battery optimum working temperature Estimate, the performance of the quick screening of battery consistency and preliminary rapid evaluation electrode material etc..
Brief description of the drawings
Fig. 1 is constant-current discharge curve map of the lithium ion battery in different health status;
Represent that battery charge state is 100% at the time of baseline 1 represents, baseline 2 represents the electric discharge cut-off of lithium ion battery Voltage, represent battery discharge to same state-of-charge, square mark, circular mark, upper equilateral triangle note at the time of baseline 3 represents Number and the curve that is marked of lower equilateral triangle mark represent that cell health state is 100%, 91.7%, 85.3% and 80% respectively When constant-current discharge curve, here for being easy to compare, the discharge current before and after cell degradation takes steady state value.
Fig. 2 be using standard performance test obtain capability value as the health status factor health status and cycle-index it Between graph of a relation;
Fig. 3 is the relation between the health status and cycle-index obtained with health status method of estimation proposed by the present invention Figure.
Embodiment
Technical scheme is further described with reference to the accompanying drawings and examples, but is not limited thereto, It is every technical solution of the present invention to be modified or equivalent substitution, without departing from the spirit and scope of technical solution of the present invention, It all should cover in protection scope of the present invention.
Embodiment one:What present embodiment was recorded is a kind of health state of lithium ion battery method of estimation, described Method for estimating state comprises the following steps:
Step 1:It is front and rear with discharge voltage during certain working system discharge and recharge, electric discharge to obtain lithium ion battery aging Electric current, discharge time data;Described working system includes charge and discharge system, charging and discharging currents and temperature;
Step 2:Discharge voltage in identical state-of-charge section of the data that obtain in interception step 1, discharge current, Discharge time data;
Step 3:It is proposed the health status indicator expression formula of lithium ion battery:
Wherein, the HI be lithium ion battery health status value, t01For its corresponding identical state-of-charge before cell degradation The initial time in section, t0For the initial time in its corresponding identical state-of-charge section after cell degradation, tend1Before cell degradation The end time in its corresponding identical state-of-charge section, tendFor the termination in its corresponding identical state-of-charge section after cell degradation Moment, VfreshAnd V (t)aged(t) be respectively before cell degradation and aging after in step 2 putting in identical state-of-charge section Piezoelectric voltage data, Vlower limitDischarge cut-off voltage value when taking the lithium ion battery to discharge completely, I (t) is identical in step 2 The discharge current of lithium ion battery in state-of-charge section;
Step 4:V is setlower limitValue;
Step 5:HI values are obtained according to formula (3), so as to obtain the health status of battery.
Embodiment two:A kind of health state of lithium ion battery method of estimation described in embodiment one, step In rapid one, described working system for front and rear circulate when temperature and electric current is identical or its change is identical.
Embodiment three:A kind of health state of lithium ion battery method of estimation described in embodiment one, step Rapid one detailed process is:
Discharge and recharge is carried out to the lithium ion battery before and after aging using certain working system, obtains lithium ion battery not With the discharge voltage of ageing step, discharge current, discharge time data.As shown in figure 1, for lithium ion battery with constant current constant voltage method 100% state-of-charge is charged to, the exemplary plot of 70% state-of-charge is then discharged to constant flow method.Charge and discharge used by curve in figure Electric system keeps identical before and after lithium ion battery aging.
Embodiment four:A kind of health state of lithium ion battery method of estimation described in embodiment one, step Rapid two detailed process is:
Desired state-of-charge section initial value and stop value are set, intercepts data acquired in step 1 in this area Input data of the interior discharge voltage, discharge current, discharge time data as health status method of estimation.
Embodiment five:A kind of health state of lithium ion battery method of estimation described in embodiment one, institute State in step 3 obtain health state of lithium ion battery indicator expression formula concrete foundation be:
With cycle charge-discharge or long-term stand aging can occur for lithium ion battery, and solid electrolyte is generated on GND Interfacial film simultaneously persistently thickens, and causes the impedance of battery and increases, while consumes electrolyte and available lithium ion, therefore, works as battery During with identical working system discharge and recharge, its polarizing voltage gradually increases with aging, is closed in discharge curve and discharge time Shown as in system's figure (as shown in Figure 1):At identical state-of-charge, the discharge voltage profile of lithium ion battery is with the old of battery Change gradually moves down in y direction, that is to say, that in identical state-of-charge section, discharge curve and the electric discharge of battery originate The figure that discharge cut-off voltage axle (baseline 2) when axle (baseline 1), termination axle (baseline 3) and battery discharge completely is surrounded Area be gradually reduced with the aging of battery, as shown in Figure 1
Wherein, the SiDischarge curve when being discharged by battery ith surrounds the area of figure, such as Fig. 1 with b axis Shown, i is cycle-index, t0And tendAt the time of respectively corresponding to representated by baseline 1 in Fig. 1 and baseline 3, Vi(t) it is battery The data that the discharge voltage V of ith changes with time t, due to generally acknowledging that the discharge voltage of lithium ion battery is reduced to electric discharge in the industry During blanking voltage, battery can not continue externally to do work, therefore, Vlower limitWhen taking the lithium ion battery to discharge completely herein Discharge cut-off voltage value;
To introduce influences of the discharge current I (t) to lithium ion battery discharge curve, formula (2) is obtained,
Wherein, the WiIn t when being discharged for battery ith0And tendActing ability in section, it can be seen that this numerical value Reduce also with the aging of battery, i is cycle-index, t0And tendRespectively corresponding to representated by baseline 1 in Fig. 1 and baseline 3 At the time of, Vi(t) data changed over time for the discharge voltage of battery ith, Vlower limitLithium ion battery is taken herein Discharge cut-off voltage value when discharging completely.
The health status method of estimation of lithium ion battery is obtained based on formula (2), as shown in formula (3)
Wherein, the HI be lithium ion battery health status value, t01For its corresponding identical state-of-charge before cell degradation The initial time in section, t0For the initial time in its corresponding identical state-of-charge section after cell degradation, tend1Before cell degradation The end time in its corresponding identical state-of-charge section, tendFor the termination in its corresponding identical state-of-charge section after cell degradation Moment, VfreshAnd V (t)aged(t) be respectively before cell degradation and aging after in step 2 putting in identical state-of-charge section Piezoelectric voltage data, Vlower limitDischarge cut-off voltage value when taking the lithium ion battery to discharge completely, I (t) is identical in step 2 The discharge current of lithium ion battery in state-of-charge section.
Embodiment six:A kind of health state of lithium ion battery method of estimation described in embodiment one, step In rapid four, the Vlower limitValue requirement be:
Vlower limitValue can take different numerical value according to different lithium-ion battery systems, most simple universal and It is discharge cut-off voltage conduct when taking the lithium ion battery to discharge completely beneficial to the obtaining value method that HI in formula (3) changes is compared Vlower limitValue, discharge cut-off voltage when different lithium-ion battery system batteries discharges completely has different values, But the discharge cut-off voltage of the lithium-ion battery system of specific electrode materials is fixed, and such as cobalt acid lithium/graphite cell, its is complete The discharge cut-off voltage of electric discharge is 3V.In addition, the value of this parameter is not limited only to electric discharge cut-off when power taking pond is discharged completely Voltage, arbitrary value can be taken in theory, but for the ease of comparing, Vlower limitValue principle be taken Vlower limitValue It is required that more obvious change occurs when aging occurs for battery for the HI values in formula (3).
Embodiment seven:A kind of lithium-ion electric in embodiment one to six described in any embodiment Pond health status method of estimation is applied to all material system (such as LiMn2O4 system, lithium nickelate system, ternary system, cobalt acid lithium System etc.) lithium ion battery, monomer and battery pack.
Embodiment 1:
A kind of health state of lithium ion battery method of estimation, is comprised the following steps that:
Step 1:It is front and rear with discharge voltage during identical working system discharge and recharge, electric discharge electricity to obtain lithium ion battery aging Stream, discharge time data;
Cobalt acid lithium/graphite lithium ion battery that rated capacity is 1.2Ah is used to be used first before testing as experimental subjects The capability value of standard performance test (Reference Performance Test, RPT) demarcation battery, specific method are:Adopt Filled with constant current constant voltage method (0.6C constant current multiplying powers charge to 4.2V, keep constant pressure 4.2V to charge to current reduction to 0.05C) Electricity stands 2min, then 0.6C constant currents multiplying power discharging to 3V, circulated 3 times, the appearance averaged as battery to fullcharging electricity condition Value.Then, circulation degradation is carried out to battery, specific method is:Using constant current constant voltage method, (1.5C constant current multiplying powers charge to 4.2V, constant pressure 4.2V is kept to charge to current reduction to 0.05C) fullcharging electricity condition is charged to, 2min is stood, then 1.5C Constant current multiplying power discharging 12min, often circulate 100 times and standard performance test is carried out to battery, the capability value of battery is obtained, as battery The reference of aging, as shown in Figure 2.
Step 2:Intercept discharge voltage, electric discharge electricity of the data acquired in step 1 in identical state-of-charge section Stream, discharge time data:
The feasibility of a kind of health state of lithium ion battery method of estimation proposed by the present invention for convenience of description, step 1 In development of the circulation degradation between 100% state-of-charge and 70% state-of-charge, therefore intercept in step 1 When discharge voltage, discharge current (1.5C) between 100% state-of-charge (baseline 1) and 70% state-of-charge (baseline 3), electric discharge Between (12min, or 720s) data, as shown in Figure 1.
Step 3:Obtain the health status indicator expression formula of lithium ion battery;
Wherein, the HI be lithium ion battery health status value, t01For its corresponding identical state-of-charge before cell degradation The initial time in section, t0For the initial time in its corresponding identical state-of-charge section after cell degradation, tend1Before cell degradation The end time in its corresponding identical state-of-charge section, tendFor the termination in its corresponding identical state-of-charge section after cell degradation Moment, VfreshAnd V (t)aged(t) be respectively before cell degradation and aging after in step 2 putting in identical state-of-charge section Piezoelectric voltage data, Vlower limitDischarge cut-off voltage value when taking the lithium ion battery to discharge completely, I (t) is identical in step 2 The discharge current of lithium ion battery in state-of-charge section;
Step 4:To the V in step 3lower limitCarry out value;
For cobalt acid lithium/graphite lithium ion battery system, V is takenlower limit=3V, i.e., electric discharge when battery discharges completely Cutoff voltage value.
Step 5:According to Step 2: step 3 and step 4 obtain the HI values in formula (3), the healthy shape of battery is obtained State;
As shown in figure 3, for according to the lithium that a kind of health state of lithium ion battery method of estimation proposed by the present invention obtains from Sub- cell health state with cycle-index variation relation, as seen from the figure the method can be used for health state of lithium ion battery Estimation, and required input data (discharge voltage, discharge current, discharge time) can measure in real time, therefore can be used for Health state of lithium ion battery real-time online estimates that substantially improving existing health state of lithium ion battery method of estimation needs spy The shortcomings that determining rating test or needing fc-specific test FC equipment.

Claims (5)

  1. A kind of 1. health state of lithium ion battery method of estimation, it is characterised in that:The method for estimating state comprises the following steps:
    Step 1:Obtain lithium ion battery aging it is front and rear with discharge voltage during certain working system discharge and recharge, discharge current, Discharge time data;Described working system includes charge and discharge system, charging and discharging currents and temperature;
    Step 2:Discharge voltage in identical state-of-charge section of the data that obtain, discharge current, electric discharge in interception step 1 Time data;
    Step 3:It is proposed the health status indicator expression formula of lithium ion battery:
    <mrow> <mi>H</mi> <mi>I</mi> <mo>=</mo> <mfrac> <mrow> <msubsup> <mo>&amp;Integral;</mo> <msub> <mi>t</mi> <mn>01</mn> </msub> <msub> <mi>t</mi> <mrow> <mi>e</mi> <mi>n</mi> <mi>d</mi> <mn>1</mn> </mrow> </msub> </msubsup> <mo>&amp;lsqb;</mo> <msub> <mi>V</mi> <mrow> <mi>a</mi> <mi>g</mi> <mi>e</mi> <mi>d</mi> </mrow> </msub> <mrow> <mo>(</mo> <mi>t</mi> <mo>)</mo> </mrow> <mo>-</mo> <msub> <mi>V</mi> <mrow> <mi>l</mi> <mi>o</mi> <mi>w</mi> <mi>e</mi> <mi>r</mi> <mi>lim</mi> <mi>i</mi> <mi>t</mi> </mrow> </msub> <mo>&amp;rsqb;</mo> <mo>&amp;CenterDot;</mo> <mi>I</mi> <mrow> <mo>(</mo> <mi>t</mi> <mo>)</mo> </mrow> <mi>d</mi> <mi>t</mi> </mrow> <mrow> <msubsup> <mo>&amp;Integral;</mo> <msub> <mi>t</mi> <mn>0</mn> </msub> <msub> <mi>t</mi> <mrow> <mi>e</mi> <mi>n</mi> <mi>d</mi> </mrow> </msub> </msubsup> <mo>&amp;lsqb;</mo> <msub> <mi>V</mi> <mrow> <mi>f</mi> <mi>r</mi> <mi>e</mi> <mi>s</mi> <mi>h</mi> </mrow> </msub> <mrow> <mo>(</mo> <mi>t</mi> <mo>)</mo> </mrow> <mo>-</mo> <msub> <mi>V</mi> <mrow> <mi>l</mi> <mi>o</mi> <mi>w</mi> <mi>e</mi> <mi>r</mi> <mi>lim</mi> <mi>i</mi> <mi>t</mi> </mrow> </msub> <mo>&amp;rsqb;</mo> <mo>&amp;CenterDot;</mo> <mi>I</mi> <mrow> <mo>(</mo> <mi>t</mi> <mo>)</mo> </mrow> <mi>d</mi> <mi>t</mi> </mrow> </mfrac> <mo>&amp;times;</mo> <mn>100</mn> <mi>%</mi> <mo>-</mo> <mo>-</mo> <mo>-</mo> <mrow> <mo>(</mo> <mn>3</mn> <mo>)</mo> </mrow> </mrow>
    Wherein, the HI be lithium ion battery health status value, t01For its corresponding identical state-of-charge section before cell degradation Initial time, t0For the initial time in its corresponding identical state-of-charge section after cell degradation, tend1For its is right before cell degradation Answer the end time in identical state-of-charge section, tendFor the end time in its corresponding identical state-of-charge section after cell degradation, VfreshAnd V (t)aged(t) be respectively before cell degradation and aging after electric discharge electricity in step 2 in identical state-of-charge section Press data, Vlower limitDischarge cut-off voltage value when taking the lithium ion battery to discharge completely, I (t) is identical charged in step 2 The discharge current of lithium ion battery in state interval;
    Step 4:V is setlower limitValue;
    Step 5:HI values are obtained according to formula (3), so as to obtain the health status of battery.
  2. A kind of 2. health state of lithium ion battery method of estimation according to claim 1, it is characterised in that:In step 1, Described working system for front and rear circulate when temperature and electric current is identical or its change is identical.
  3. A kind of 3. health state of lithium ion battery method of estimation according to claim 1, it is characterised in that:The tool of step 1 Body process is:
    Discharge and recharge is carried out to the lithium ion battery before and after aging using certain working system, obtains lithium ion battery different old The discharge voltage in change stage, discharge current, discharge time data.
  4. A kind of 4. health state of lithium ion battery method of estimation according to claim 1, it is characterised in that:The tool of step 2 Body process is:
    Desired state-of-charge section initial value and stop value are set, intercepts data acquired in step 1 in this section Input data as health status method of estimation of discharge voltage, discharge current, discharge time data.
  5. 5. the health state of lithium ion battery method of estimation described in a kind of Claims 1 to 5 any claim is applied to all The lithium-ion battery monomer and battery pack of material system.
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