CN112180261B - Lithium analysis detection method for lithium iron phosphate power battery - Google Patents
Lithium analysis detection method for lithium iron phosphate power battery Download PDFInfo
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- CN112180261B CN112180261B CN202010974160.1A CN202010974160A CN112180261B CN 112180261 B CN112180261 B CN 112180261B CN 202010974160 A CN202010974160 A CN 202010974160A CN 112180261 B CN112180261 B CN 112180261B
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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]
- G01R31/378—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC] specially adapted for the type of battery or accumulator
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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
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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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Abstract
The invention discloses a lithium separation detection method for a lithium iron phosphate power battery, which relates to the technical field of lithium ion power battery detection and comprises the following steps: carrying out low-temperature floating charge and discharge cycles on the battery by adopting currents with different multiplying powers, measuring the charge constant current charge ratio and the discharge average voltage data of each cycle, and drawing a curve chart; standing the battery at low temperature; raising the floating charge voltage, performing low-temperature floating charge and discharge circulation on the battery after standing at low temperature, measuring the charge constant current charge ratio and the discharge average voltage data of each circulation, and drawing a curve chart; the low-temperature floating charge and discharge cycle adopts three-stage charge and discharge modes of step charge, floating charge and constant current discharge; and comparing the constant current charging ratio curve graph and the discharging average voltage curve graph before and after low-temperature standing, and judging whether the battery separates lithium according to the curve fluctuation range. The method is simple to operate, can accurately judge whether the lithium ion battery separates lithium without disassembling the battery, and can quickly establish a battery lithium separation window.
Description
Technical Field
The invention relates to the technical field of lithium ion power battery detection, in particular to a lithium separation detection method for a lithium iron phosphate power battery.
Background
Lithium ion batteries are the main energy source of current electric vehicles due to their advantages of high energy density, long life, and low self-discharge rate. When a lithium ion battery is used at low temperature, lithium ions in the graphite negative electrode may be reduced to metallic lithium, and lithium deposition may occur. After the lithium precipitation of the battery, the capacity is rapidly reduced; on the other hand, the precipitated lithium metal forms lithium dendrites which may pierce the separator to induce internal short circuit and cause serious safety accidents, so it is necessary to determine in advance whether the lithium ion battery precipitates lithium. The current common method is to disassemble the battery after charging and discharging circulation for dozens of weeks at low temperature and judge whether the lithium ion battery separates lithium or not through a negative electrode interface, and the method consumes manpower.
In addition, in the prior art, a detection tool is used for detecting the voltage between a metal shell and a negative electrode terminal of a lithium ion power battery to be detected so as to judge whether lithium precipitation occurs inside the lithium ion power battery, and coulombic efficiency data of charge-discharge cycles of the lithium ion battery before and after standing are compared so as to directly judge whether lithium precipitation occurs inside the lithium ion battery. In the above two determination methods, it is not always accurate to determine whether to analyze lithium by considering only a single factor.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a lithium analysis detection method for a lithium iron phosphate power battery, and whether lithium analysis exists in the lithium iron phosphate power battery can be accurately judged through the method.
The invention provides a lithium analysis detection method for a lithium iron phosphate power battery, which comprises the following steps:
s1, performing low-temperature floating charge and discharge cycles on the battery by adopting currents with different multiplying powers, measuring the charge constant current charge ratio and the discharge average voltage data of each cycle, and drawing a curve chart; the low-temperature floating charge and discharge cycle adopts three stages of charge and discharge modes of step charge, floating charge and constant current discharge;
s2, standing the battery which completes the low-temperature floating charge and discharge cycle at low temperature;
s3, improving the float charge voltage, performing low-temperature float charge and discharge circulation on the battery after standing at low temperature, measuring the charge constant current charge ratio and the discharge average voltage data of each circulation, and drawing a curve chart; the low-temperature floating charge and discharge cycle adopts three stages of charge and discharge modes of step charge, floating charge and constant current discharge;
and S4, comparing the constant current charging ratio curve chart and the discharging average voltage curve chart in S1 and S3 before and after low-temperature standing, and judging whether the battery separates lithium according to the curve fluctuation range.
In the present invention, in the above steps S1 and S3, when the curves of the charging constant current charging ratio and the discharging average voltage appear as relatively parallel straight lines, the low temperature floating charge-discharge cycle is completed.
Preferably, the low temperature ranges are: t is more than or equal to minus 30 ℃ and less than 5 ℃.
Preferably, the temperature of the low temperature floating charge and discharge cycle in S3 is lower than the temperature of the low temperature floating charge and discharge cycle in S1.
In the step S3 of the invention, the lithium separation of the battery is easier to occur by reducing the float charging temperature.
Preferably, the float charge voltage of the low-temperature float charge discharge cycle is 3.4V-3.65V.
Preferably, the float voltage in S3 is at least 0.1V higher than the float voltage in S1.
In the step S3, the float charge voltage of the battery is increased at a low temperature, i.e. the battery is kept at a high potential, the battery is easy to separate lithium, and once the battery separates lithium, a series of side reactions will occur, and the increase of the float charge voltage can accelerate the progress of the side reactions, and finally the constant current charge ratio and the average discharge voltage of the battery can be intuitively reflected, so as to determine whether the battery separates lithium.
Preferably, the cycle number of the low-temperature floating charge discharge cycle in S1 is 25 cycles, and the cycle number in S3 is equal to or greater than the cycle number in S1.
In the step S3 of the present invention, the longer the cycle count, the more significant the lithium deposition, and therefore the cycle count in the step S3 is increased.
Preferably, in S2, when the low temperature T is in the range of: t is more than or equal to minus 30 DEG C2Standing at-10 deg.C for 20 hr; when the temperature T is more than or equal to minus 10 ℃ and less than 0 ℃, standing for 10 hours; when the temperature T is more than or equal to 0 ℃ and less than 5 ℃, the standing time is 5 h.
Preferably, the fluctuation range of the charging constant current charging ratio curve and the fluctuation range of the discharging average voltage curve are both 0% -2%, if both are in the fluctuation range, the battery to be tested does not analyze lithium, if one of the two exceeds the fluctuation range, the battery to be tested may analyze lithium, and if both exceed the fluctuation range, the battery to be tested must analyze lithium.
Has the advantages that: the invention provides a lithium analysis detection method of a lithium ion power battery, which adopts low-temperature floating charge and discharge circulation, compares the charging constant current charge ratio and the discharging average voltage data of the battery before and after the floating charge voltage is improved, and synthesizes the fluctuation ranges of the charging constant current charge ratio and the discharging average voltage data to judge whether the battery analyzes lithium; and the low-temperature floating charge and discharge cycle adopts a three-section charging and discharging mode of 'step charging-floating charge-constant current discharging', the floating charge voltage value can be adjusted at will in the test process, and different floating charge voltage ranges are established to correspondingly determine whether to separate lithium. The method is simple to operate, can accurately judge whether the lithium ion battery analyzes lithium without disassembling the battery, and can quickly establish a battery lithium analysis window, so that a low-temperature charging strategy can be quickly established for energy storage.
Drawings
FIG. 1 is a schematic flow diagram of the present invention;
FIG. 2 is a constant current charge ratio graph in an embodiment of the present invention;
FIG. 3 is a graph of the average discharge voltage in an embodiment of the present invention.
Detailed Description
Examples
Referring to fig. 1, the lithium iron phosphate battery lithium precipitation detection method provided by the present invention includes the following steps (taking a lithium iron phosphate 25Ah battery as an example):
s1, carrying out floating charge circulation on the lithium iron phosphate battery at the temperature of 0 ℃, and adopting a three-stage charge-discharge mode of step charge-floating charge-constant current discharge;
step charging: charging to 3.2V at 5A constant current, charging to 3.3V at 2.5A constant current, charging to 3.4V at 1.25A constant current, and standing for 10 s;
floating charging: charging at a constant current of 5A until the float charging voltage is 3.5V, keeping constant voltage until the charging current is reduced to 0.01A, standing for 6h, discharging the battery at 0.5C, measuring charging constant current charging ratio data and discharging average voltage data of each cycle, circulating for 25 weeks, and drawing a constant current charging ratio curve L1 and a discharging average voltage curve L2;
s2, standing the lithium iron phosphate battery which completes the low-temperature floating charge and discharge cycle in the S1 at-20 ℃ for 20 h;
s3, carrying out floating charge circulation on the lithium ion battery in the S2 at the temperature of minus 20 ℃, and adopting a three-stage charge and discharge mode of step charge, floating charge and constant current discharge;
step charging: charging to 3.2V at a constant current of 5A, charging to 3.3V at a constant current of 2.5A, stopping charging at a constant current of 1.25A to 3.4V, and standing for 10;
floating charging: charging at a constant current of 5A until the float charging voltage is 3.6V, keeping constant voltage until the charging current is reduced to 0.01A, standing for 6h, discharging the battery at 0.5C, measuring charging constant current charging ratio data and discharging average voltage data of each cycle, circulating for 25 weeks, and drawing a constant current charging ratio curve L3 and a discharging average voltage curve L4;
s4, comparing the constant current charging ratio graphs obtained in S1 and S3, finding that the charging constant current charging ratio data obtained in S3 has a sudden change in about 42 weeks and the curve fluctuation range is greater than 2% (shown in figure 1) through comparison, continuing to compare the discharging average voltage graphs obtained in S1 and S3, finding that the discharging average voltage data obtained in S3 has a sudden change in about 42 weeks and the curve fluctuation range is greater than 2% (shown in figure 2), and both exceeding the fluctuation ranges, so that the lithium ion battery sample to be tested must analyze lithium.
S5, verification: and (4) disassembling the battery, and finding out serious lithium separation, which indicates that the lithium iron phosphate battery sample is easy to separate lithium during low-temperature charging. The method can be verified to be high in accuracy.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. A lithium analysis detection method for a lithium iron phosphate power battery is characterized by comprising the following steps:
s1, performing low-temperature floating charge and discharge cycles on the battery by adopting currents with different multiplying powers, measuring the charge constant current charge ratio and the discharge average voltage data of each cycle, and drawing a curve chart; the low-temperature floating charge and discharge cycle adopts three stages of charge and discharge modes of step charge, floating charge and constant current discharge;
s2, standing the battery which completes the low-temperature floating charge and discharge cycle at low temperature;
s3, improving the float charge voltage, performing low-temperature float charge and discharge circulation on the battery after standing at low temperature, measuring the charge constant current charge ratio and the discharge average voltage data of each circulation, and drawing a curve chart; the low-temperature floating charge and discharge cycle adopts three stages of charge and discharge modes of step charge, floating charge and constant current discharge;
s4, comparing a charging constant current charging ratio curve chart and a discharging average voltage curve chart in S1 and S3 before and after low-temperature standing, and judging whether the battery separates lithium according to the curve fluctuation range;
the fluctuation range of the charging constant current charging ratio curve and the fluctuation range of the discharging average voltage curve are both 0% -2%, if the charging constant current charging ratio curve and the discharging average voltage curve are both in the fluctuation ranges, the battery to be tested does not analyze lithium, if one of the charging constant current charging ratio curve and the discharging average voltage curve is beyond the fluctuation ranges, the battery to be tested can analyze lithium, and if both the charging constant current charging ratio curve and the discharging average voltage curve are beyond the fluctuation ranges, the battery to be tested can analyze lithium.
2. The lithium separation detection method for the lithium iron phosphate power battery according to claim 1, wherein the low-temperature range is as follows: t is more than or equal to minus 30 ℃ and less than 5 ℃.
3. The lithium separation detection method for the lithium iron phosphate power battery as claimed in claim 2, wherein the temperature of the low-temperature floating charge and discharge cycle in S3 is lower than the temperature of the low-temperature floating charge and discharge cycle in S1.
4. The lithium separation detection method for the lithium iron phosphate power battery according to claim 1, wherein the float charge voltage of the low-temperature float charge discharge cycle is 3.4V-3.65V.
5. The lithium separation detection method for lithium iron phosphate power battery according to claim 4, wherein the floating charge voltage in S3 is higher than the floating charge voltage in S1 by at least 0.1V.
6. The lithium separation detection method for the lithium iron phosphate power battery according to claim 1, wherein the cycle number of the low-temperature floating charge/discharge cycle in S1 is preferably 25 cycles, and the cycle number in S3 is preferably equal to or greater than the cycle number in S1.
7. The lithium analysis detection method for the lithium iron phosphate power battery as claimed in claim 1, wherein in S2, when the low temperature T is within the range: when the temperature T is more than or equal to minus 30 ℃ and less than minus 10 ℃, the standing time is 20 hours; when the temperature T is more than or equal to minus 10 ℃ and less than 0 ℃, standing for 10 hours; when the temperature T is more than or equal to 0 ℃ and less than 5 ℃, the standing time is 5 h.
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CN113161636B (en) * | 2021-02-10 | 2024-04-30 | 中国科学院金属研究所 | Low-temperature charging technology of lithium iron phosphate battery |
CN113036244B (en) * | 2021-03-04 | 2022-04-19 | 江西安驰新能源科技有限公司 | Low-temperature charging method of lithium iron phosphate battery |
CN113125974B (en) * | 2021-04-22 | 2023-06-16 | 远景动力技术(江苏)有限公司 | Method and device for detecting lithium precipitation of battery |
CN113193250B (en) * | 2021-04-29 | 2022-09-23 | 江西安驰新能源科技有限公司 | Evaluation method for low-temperature cycle lithium separation degree |
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