CN112595986A - Battery service life diagnosis method based on differential thermal voltammetry curve characteristics - Google Patents
Battery service life diagnosis method based on differential thermal voltammetry curve characteristics Download PDFInfo
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- CN112595986A CN112595986A CN202011356791.3A CN202011356791A CN112595986A CN 112595986 A CN112595986 A CN 112595986A CN 202011356791 A CN202011356791 A CN 202011356791A CN 112595986 A CN112595986 A CN 112595986A
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- 238000004832 voltammetry Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000003745 diagnosis Methods 0.000 title claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 30
- 238000007599 discharging Methods 0.000 claims abstract description 13
- 238000007600 charging Methods 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 9
- 238000004364 calculation method Methods 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 4
- 238000010277 constant-current charging Methods 0.000 claims description 4
- 238000006731 degradation reaction Methods 0.000 claims description 4
- 230000032683 aging Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
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- 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]
- G01R31/392—Determining battery ageing or deterioration, e.g. state of health
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K13/00—Thermometers specially adapted for specific purposes
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- 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]
- G01R31/385—Arrangements for measuring battery or accumulator variables
-
- 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]
- G01R31/396—Acquisition or processing of data for testing or for monitoring individual cells or groups of cells within a battery
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Abstract
The invention relates to a battery life diagnosis method based on differential thermal voltammetry curve characteristics, which comprises the following steps: 1) charging or discharging a lithium ion battery to be diagnosed; 2) synchronously measuring the voltage and the temperature of the battery in the process of charging or discharging the lithium ion battery; 3) acquiring a differential thermal voltammetry curve according to the measured battery voltage and battery temperature data; 4) extracting the characteristics of the differential thermal voltammetry curve, and taking the characteristics as the diagnosis basis of the attenuation degree of the battery; 5) and diagnosing the attenuation degree of the lithium ion battery to be diagnosed by utilizing the characteristics of the volt-ampere characteristic curve. Compared with the prior art, the method has the advantages of no need of additional test equipment, suitability for the high-rate charging process of the battery, simplicity, effectiveness and the like.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a battery life diagnosis method based on differential thermal voltammetry curve characteristics.
Background
Lithium ion batteries are widely applied to electric vehicles due to high energy density and power density, however, long-term operation and extreme environmental temperature can cause increase of internal resistance and capacity attenuation of the batteries, two main reasons of which are solid electrolyte interface growth and lithium precipitation at a negative electrode, and degradation of the batteries can affect the performance of the whole system or equipment, so that the service life of the batteries needs to be accurately diagnosed.
Traditional non-invasive methods of diagnosing battery life, such as electrochemical impedance spectroscopy and slow cyclic voltammetry, are only performed at the cell level and are not suitable for practical operation, for example, slow cyclic voltammetry requires a constant rate of voltage change to be maintained during use; the electrochemical impedance spectrum measurement needs a complex operation program and additionally added hardware; the capacity incremental method requires that battery life be diagnosed at very low current rates, which is best, but not possible in actual operation.
Disclosure of Invention
The present invention is directed to overcoming the above-mentioned drawbacks of the prior art and providing a method for diagnosing battery life based on differential voltammetry characteristics.
The purpose of the invention can be realized by the following technical scheme:
a battery life diagnosis method based on differential thermal voltammetry curve characteristics comprises the following steps:
1) charging or discharging a lithium ion battery to be diagnosed;
2) synchronously measuring the voltage and the temperature of the battery in the process of charging or discharging the lithium ion battery;
3) acquiring a differential thermal voltammetry curve according to the measured battery voltage and battery temperature data;
4) extracting the characteristics of the differential thermal voltammetry curve, and taking the characteristics as the diagnostic characteristics of the attenuation degree of the battery;
5) and diagnosing the attenuation degree of the lithium ion battery to be diagnosed by utilizing the characteristics of the volt-ampere characteristic curve.
In the step 1), the lithium ion battery to be diagnosed is subjected to constant current charging or constant current discharging.
And in the step 3), differential calculation is carried out on the battery voltage and the battery temperature data to obtain a differential thermal voltammetry curve.
In the step 3), the differential thermal voltammetry curve takes the battery voltage as a horizontal coordinate, and takes the differential thermal voltammetry as a vertical coordinate.
The expression of the differential thermal voltammetry eta is as follows:
where Δ T is a temperature difference and Δ V is a voltage difference.
In the step 4), the characteristics of the differential thermal voltammetry curve include peak position, peak height, distance between peaks, and height difference between peaks and valleys.
In the step 5), the method for diagnosing the attenuation degree of the battery specifically comprises the following steps:
and diagnosing the attenuation degree by comparing the difference between the characteristics of the aged lithium ion battery to be detected and the characteristics of the new lithium ion battery.
The characteristic difference between the aged lithium ion battery and the new lithium ion battery to be detected comprises offset of peak position, offset of peak height, distance between adjacent peaks, voltage difference between peak and valley and height difference between peak and valley.
The offset of the peak position, the offset of the peak height, the distance between adjacent peaks, the voltage difference between the peaks and the valleys, the height difference between the peaks and the valleys and the attenuation degree of the battery are in linear relation.
The priority sequence adopted by the characteristic difference between each aging lithium ion battery to be detected and the new lithium ion battery is as follows:
the offset of the peak position, the voltage difference between the peak and the valley, the distance between adjacent peaks, the height difference between the peak and the valley, and the offset of the peak height.
Compared with the prior art, the invention has the following advantages:
the differential thermal voltammetry-based non-invasive diagnosis method provided by the invention does not need to add extra test equipment, can be used for diagnosing the service life of the battery during high-rate charging of the battery or practical application of the battery, and overcomes the defects of the conventional nondestructive battery service life diagnosis method.
Drawings
FIG. 1 is a general flow diagram of the present invention.
Fig. 2 is a differential thermal voltammogram of different degrees of cell decay.
Fig. 3 is a graph of battery peak voltage versus battery capacity fade.
Fig. 4 is a graph of battery valley bottom voltage versus battery capacity fade.
Fig. 5 is a graph of peak to valley height difference versus battery capacity fade.
Fig. 6 is a graph of the peak to valley voltage difference versus the decay of battery capacity.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
In the actual use process, the battery is aged, the aging can cause the change of the components, the material structure and the like in the battery, and further cause the change of the electrical characteristics and the thermal characteristics of the battery, wherein the parameters which are the most common and easy to measure when the voltage, the current and the temperature of the battery are used, the existing non-destructive diagnosis technology, such as an electrochemical impedance spectrum, is used for analyzing and diagnosing the internal response of the battery by applying an exciting current or voltage from the outside, but the complicated operation and additional equipment are needed, compared with the capacity increment method, the capacity decrement of the battery can be inferred only by comparing the change rate of the voltage and the current during the constant current charging or discharging of the battery, but only the voltage and the current of the battery are concerned in the above way, the temperature is ignored, and the aging reaction in the battery can represent the external performance of the battery, namely, voltage, current and temperature are simultaneously influenced, so that the temperature and the voltage of the battery are analyzed by adopting differential voltammetry, and experimental analysis shows that the characteristics of a differential voltammetry curve, such as peak voltage, distance between peaks, peak height difference and the like, show obvious linear relation with the battery capacity attenuation, so that the invention utilizes the linear relation to diagnose the battery attenuation degree.
As shown in fig. 1, the present invention provides a battery life diagnosis method based on differential thermal voltammetry characteristics, which comprises the following steps:
1) discharging the battery, in this example, by constant current discharge;
2) during the discharge process of the battery, measuring the voltage and the temperature of the battery, and noting that the measurement of the voltage and the temperature of the battery in the step needs to be carried out synchronously;
3) carrying out differential calculation by using the measured voltage and temperature of the battery to obtain a differential thermal voltammetry curve, wherein the differential thermal voltammetry curve is obtained by carrying out differential calculation on the temperature and the voltage of the battery:
wherein Δ T is a temperature differential value, and Δ V is a voltage differential value;
4) extracting the characteristics of the differential thermal voltammetry curve, wherein the extracted characteristics comprise but are not limited to peak position, peak height, distance between peaks, height difference of valley peak and valley bottom;
5) the degree of battery degradation is diagnosed by comparing the difference in characteristics of the new battery and the aged battery, including but not limited to the offset of the peak position, the offset of the peak height, the distance between the peaks, the voltage difference between the peaks and the valleys, and the height difference between the peaks and the valleys.
The priority sequence adopted by the characteristic difference between each aging lithium ion battery to be detected and the new lithium ion battery is as follows:
the offset of the peak position, the voltage difference between the peak and the valley, the distance between adjacent peaks, the height difference between the peak and the valley, and the offset of the peak height.
For different types of aging lithium ion batteries to be detected, firstly, the battery attenuation degree is obtained according to a linear relation by adopting the offset of the peak value position, and if the battery attenuation degree cannot be judged, the voltage difference between the peak value and the valley value, the distance between adjacent peak values, the height difference between the peak value and the valley value and the offset of the peak value height are adopted for judgment in sequence.
Examples
The experimental object in the embodiment of the invention is a lithium ion battery, the battery is charged and discharged circularly at room temperature of 24 ℃, the charging process is charging to 4.2V at a constant current of 1.5A, then charging in a constant voltage mode until the current is reduced to 20mA, stopping the discharging process from 4A constant current discharging to 2.7V, and the battery capacity of the lithium ion battery can be attenuated in the circulation process, wherein FIG. 2 shows the change of the differential thermal voltammetry curve of the battery when the battery capacity is attenuated to different degrees, by characterizing the differential thermal voltammetry curve including peak voltage, peak height, voltage difference between peak and valley, height difference between peak and valley, compared with the battery capacity attenuation degree, the characteristics of the differential thermal voltammetry curve and the battery capacity attenuation present a linear relation, as shown in fig. 3-6, the linear relationship can be used to diagnose the attenuation degree of the battery by obtaining the characteristics of the differential thermal voltammetry curve of the battery.
The method only needs to measure the voltage and the temperature of the battery during the constant-current charging or discharging of the battery, and can realize the diagnosis of the service life of the battery monomer in the parallel battery pack as long as each battery has one temperature measurement value, the current does not need to be measured, and the voltage and the temperature required by the diagnosis and analysis can be obtained by using the data acquired by the data battery management system, so that extra instruments and equipment do not need to be added for data measurement.
The above description is only exemplary of the present invention, and not intended to limit the present invention, and all the modifications and variations are included within the spirit and scope of the present invention.
Claims (10)
1. A battery life diagnosis method based on differential thermal voltammetry curve characteristics is characterized by comprising the following steps:
1) charging or discharging a lithium ion battery to be diagnosed;
2) synchronously measuring the voltage and the temperature of the battery in the process of charging or discharging the lithium ion battery;
3) acquiring a differential thermal voltammetry curve according to the measured battery voltage and battery temperature data;
4) extracting the characteristics of the differential thermal voltammetry curve, and taking the characteristics as the diagnostic characteristics of the attenuation degree of the battery;
5) and diagnosing the attenuation degree of the lithium ion battery to be diagnosed by utilizing the characteristics of the volt-ampere characteristic curve.
2. The method for diagnosing the service life of the battery based on the differential thermal voltammetry curve characteristics as claimed in claim 1, wherein in the step 1), the lithium ion battery to be diagnosed is subjected to constant current charging or constant current discharging.
3. The method as claimed in claim 1, wherein in step 3), the differential voltammetry is obtained by performing a differential calculation on the battery voltage and the battery temperature data.
4. The method as claimed in claim 3, wherein in step 3), the differential voltammetry curve is plotted with the battery voltage as the abscissa and the differential voltammetry as the ordinate.
5. The method as claimed in claim 4, wherein the differential voltammetry η is expressed as:
where Δ T is a temperature difference and Δ V is a voltage difference.
6. The method as claimed in claim 1, wherein the characteristics of the differential voltammetry curve in step 4) include peak position, peak height, distance between peaks, and height difference between peaks and valleys.
7. The method for diagnosing battery life based on differential thermal voltammetry characteristics as claimed in claim 6, wherein in the step 5), the method for diagnosing the degree of battery degradation specifically comprises:
and diagnosing the attenuation degree by comparing the difference between the characteristics of the aged lithium ion battery to be detected and the characteristics of the new lithium ion battery.
8. The method as claimed in claim 7, wherein the characteristic difference between the aged lithium ion battery and the new lithium ion battery to be detected comprises an offset of a peak position, an offset of a peak height, a distance between adjacent peaks, a voltage difference between a peak and a valley, and a height difference between a peak and a valley.
9. The method as claimed in claim 8, wherein the offset of the peak position, the offset of the peak height, the distance between adjacent peaks, the voltage difference between the peaks and the valleys, and the height difference between the peaks and the valleys have a linear relationship with the degree of battery degradation.
10. The method for diagnosing the service life of the battery based on the differential thermal voltammetry characteristics as claimed in claim 9, wherein the priority order of the characteristic difference between each aged lithium ion battery to be detected and each new lithium ion battery is as follows:
the offset of the peak position, the voltage difference between the peak and the valley, the distance between adjacent peaks, the height difference between the peak and the valley, and the offset of the peak height.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113433467A (en) * | 2021-05-11 | 2021-09-24 | 天津力神电池股份有限公司 | Lithium ion battery cycle accelerated evaluation method |
| CN114675203A (en) * | 2022-03-25 | 2022-06-28 | 同济大学 | A method of battery safety assessment |
| CN114966416A (en) * | 2022-07-15 | 2022-08-30 | 东软睿驰汽车技术（沈阳）有限公司 | Method, device and electronic device for determining battery aging degree |
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- 2020-11-26 CN CN202011356791.3A patent/CN112595986A/en active Pending
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Cited By (5)
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| CN113433467A (en) * | 2021-05-11 | 2021-09-24 | 天津力神电池股份有限公司 | Lithium ion battery cycle accelerated evaluation method |
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