CN108363017B - Method for calibrating stable capacity value of retired lithium battery stored for long time - Google Patents
Method for calibrating stable capacity value of retired lithium battery stored for long time Download PDFInfo
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- CN108363017B CN108363017B CN201810159730.4A CN201810159730A CN108363017B CN 108363017 B CN108363017 B CN 108363017B CN 201810159730 A CN201810159730 A CN 201810159730A CN 108363017 B CN108363017 B CN 108363017B
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000012360 testing method Methods 0.000 claims abstract description 35
- 239000000178 monomer Substances 0.000 claims abstract description 28
- 230000008569 process Effects 0.000 claims abstract description 13
- 238000012545 processing Methods 0.000 claims abstract description 6
- 238000007599 discharging Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 4
- 238000003672 processing method Methods 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- 230000000007 visual effect Effects 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000010586 diagram Methods 0.000 claims 1
- 230000004913 activation Effects 0.000 abstract description 5
- 238000007689 inspection Methods 0.000 abstract 1
- 230000007774 longterm Effects 0.000 abstract 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 7
- 238000011084 recovery Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 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]
- G01R31/367—Software therefor, e.g. for battery testing using modelling or look-up tables
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Abstract
The invention belongs to the technical field of storage batteries, and provides a method for calibrating a stable capacity value of a retired lithium battery stored for a long time. After appearance inspection and information acquisition are carried out on the retired lithium battery monomer stored for a long time, small-rate activation processing is carried out on the battery monomer. Room temperature capacity testing was then performed. And acquiring capacity Q data and voltage V data in the room temperature capacity test process to draw a charging capacity increment curve dQ/dV-V graph. And (4) combining a charging capacity increment curve graph, subtracting the X-axis coordinate data corresponding to the highest peak value of the capacity increment curve in the previous and subsequent testing processes, and determining whether the capacity value in the current testing process is a stable value of the capacity of the retired battery according to the difference value. The method solves the problem that the traditional battery capacity calibration method is inaccurate in calibrating the capacity of the retired lithium battery in a long-term storage state, and lays a use foundation for safe and reliable echelon reuse of the subsequent retired battery.
Description
Technical Field
The invention belongs to the technical field of storage batteries, and particularly relates to a method for calibrating a stable capacity value of a retired lithium battery stored for a long time.
Background
Environmental pollution and energy exhaustion are two major problems facing human beings. In order to deal with the dual pressure of environment and energy, all countries around the world adopt the development and utilization of new energy as an important strategy for sustainable development, and in recent years, most countries around the world develop electric vehicles as an important way for energy conservation and emission reduction.
The power battery is one of the core components of the electric automobile, and the performance index of the power battery directly influences the overall performance of the electric automobile. In order to ensure the running and safety performance of the electric automobile, the retired lithium battery needs to be replaced after the electric automobile runs for a certain mileage. If the retired lithium battery is not properly treated, a series of environmental and safety problems are caused, including the problems of occupying a large amount of storage space, causing environmental pollution, forming potential safety hazards and the like.
The method for utilizing the lithium battery in the echelon mode improves a new idea for solving the problem that the retired battery is difficult to process, and the retired battery still generally has 70-80% of capacity. Because the power battery for the electric vehicle has quite high standards on the aspects of power battery density, stability and the like, the retired lithium battery can be completely and echelonly used in the fields of distributed energy storage, micro-grid energy storage, low-speed vehicles and the like which have not very high requirements on battery performance.
In the lithium battery industry, a safe and reliable method for utilizing retired batteries in a gradient manner is still in a research and test stage, so that a large number of currently retired lithium batteries are in a recovery and shelving state at the present stage. If the retired lithium battery is not used for a long time and is not subjected to periodic charging and discharging activation treatment in the storage process, the lithium battery can perform spontaneous chemical reaction, active lithium particles are consumed, and sediment is generated, so that the internal resistance of the retired lithium battery is continuously increased, and the capacity of the retired lithium battery is continuously attenuated.
After the lithium battery which is stored for a long time is activated by small current, the capacity of the lithium battery can be recovered to a certain extent. However, the health state of each retired single lithium battery, the length of the shelf storage time of the retired lithium battery and the storage environment are different, so that the health recovery state and the recovery time of the lithium battery are also different. In order to ensure that the capacity of the retired lithium battery which is stored for a long time does not have rapid fluctuation change in the echelon utilization process. It is necessary to measure the stable capacity value of the retired lithium battery which is stored for a long time. Therefore, the safe and reliable echelon utilization of the retired lithium battery in the storage state in other fields can be guaranteed.
Disclosure of Invention
The invention aims to provide a method for calibrating a stable capacity value of a retired lithium battery in a long-time storage state.
The technical scheme of the invention is as follows:
a method for calibrating a stable capacity value of a retired lithium battery stored for a long time comprises the following steps:
the method comprises the following steps: under good light conditions, the appearance of the retired lithium battery monomer is detected by a visual method, and if deformation, cracks, liquid leakage and the like exist, the capacity of the retired lithium battery monomer is not tested;
step two: observing the label on the appearance of the retired lithium battery monomer, and collecting basic information of the retired lithium battery monomer, such as nominal voltage (Un) and nominal capacity (C)n) Or nominal energy (W)n) Etc.;
step three: the method for activating the retired lithium battery monomer selected by the appearance detection comprises the following steps:
3.1) at a constant temperature of 25 ℃ at 0.01CnCharging the monomer to a specified monomer charging cut-off voltage by current constant current, and standing for 30-60 min;
3.2) at 0.01CnDischarging the mixture to a specified monomer discharge cut-off voltage by constant current, and standing for 30-60 min;
3.3) repeating the steps 3.1) to 3.2)3 times;
step four: the method for testing the battery capacity of the activated retired lithium battery monomer comprises the following steps:
4.1) at a constant temperature of between 23 and 27 ℃ and at a temperature of 0.02CnCharging with constant current to a predetermined charge cut-off voltage, and charging with constant voltage until the current is reduced to 0.05CnStopping and standing for 60 min;
4.2) at 0.02CnDischarging with constant current to the specified monomer discharge cut-off voltage, and standing for 60 min;
4.3) calculating the discharge capacity;
4.4) repeating the steps 4.1) to 4.3), when the range of the results of the three consecutive tests is less than 3% of the rated value, ending the test, and taking the average value of the results of the last three tests;
step five: in the process of testing the battery capacity in the fourth step, battery capacity (Q) data and voltage (V) data of the retired lithium battery are sampled by the battery charging and discharging equipment at a certain sampling frequency; carrying out differential processing on the acquired capacity (Q) data and voltage (V) data to obtain dQ and dV;
step six: using the collected voltage (V) data as X-axis data, using a ratio of dQ/dV as Y-axis data, and performing filtering processing on the ratio of dQ/dV by using a Gaussian filtering data processing method to obtain a charging capacity increment curve (dQ/dV-V) graph with three obvious peak values;
step seven: repeating the fourth step and the sixth step, and drawing a charging capacity increment curve corresponding to each battery capacity test according to the fifth step and the sixth step;
step eight: and according to the obtained charging capacity increment curve, performing difference on X-axis coordinate data corresponding to the highest peak value in the charging capacity increment curve. And in the adjacent testing processes, if the difference of the X-axis voltage data of the charging capacity increment curve corresponding to the highest peak value is between 0 and 30mv, outputting the discharging capacity measured in the last step four, namely the stable capacity value of the retired lithium battery stored for a long time. Otherwise, returning to the third step.
The invention has the beneficial effects that: the invention provides a solution to the problem that the stable value of the residual capacity of the retired lithium battery is difficult to detect when the retired lithium battery is used in a echelon manner if the retired lithium battery is in a storage and resting state for a long time. And a use foundation is laid for safe and reliable echelon reuse of the subsequent battery.
Drawings
FIG. 1 is a flow chart of the operation of the present invention.
Fig. 2 is a graph of the increase in charge capacity of a lithium iron phosphate battery.
Fig. 3 is a graph showing the increment of the charge capacity obtained in five tests.
Detailed Description
The invention is further explained by combining the attached drawings and the specific embodiment, the invention adopts the retired lithium iron phosphate battery which is stored for one year as a research object, and the invention is further explained by combining the flow chart and the specific embodiment, and the specific process is as follows:
the method comprises the following steps: and disassembling the retired old lithium iron phosphate battery pack to obtain the lithium iron phosphate battery monomer. Under good light conditions, the appearance of the power lithium battery monomer is detected by a visual method, and batteries without cracks, deformation and leakage are selected for capacity detection.
Step two: through information acquisition, the batteries of the batch are known to have the nominal voltage of 3.2V and the nominal capacity (C)n) Is 10Ah lithium iron phosphate battery.
Step three: carrying out activation treatment on the lithium iron phosphate battery selected by appearance detection, wherein the method for the activation treatment comprises the following steps:
a) at a constant temperature of 25 deg.C, at a temperature of 0.1Ah (0.01C)n) Charging with constant current until the monomer charging cut-off voltage specified in the enterprise technical conditions is 3.65V, and standing for 60 min;
b)0.1Ah(0.01Cn) Discharging the current at constant current to the monomer discharge cut-off voltage 2.7V specified in the enterprise technical conditions, and standing for 60 min;
c) repeating the steps a) to b)3 times.
Step four: and testing the capacity of the retired power lithium battery monomer subjected to activation treatment at room temperature. The battery capacity testing method comprises the following steps:
a. charging at constant temperature of 25 + -2 deg.C with 0.02Cn current until the charge cut-off voltage is 3.65V, and charging at constant voltage until the current is reduced to 0.5Ah (0.05C)n) Stopping and standing for 60 min;
b. at 0.2Ah (0.02C)n) Discharging the current at constant current to the monomer discharge cut-off voltage 2.7V specified in the enterprise technical conditions, and standing for 60 min;
c. calculating the discharge capacity;
d. repeating the steps a to c for five times, and finishing the test in advance when the range of the results of three consecutive tests is less than 3% of the rated value, and taking the average value of the results of the last three tests.
Step five: and in the process of testing the battery capacity in the step four, the battery charging and discharging equipment is set to sample the battery capacity (Q) data and the voltage (V) data when the lithium battery is charged at the sampling frequency of 10 HZ. And carrying out differential processing on the acquired capacity (Q) data and the acquired voltage (V) data to obtain dQ and dV.
Step six: the collected voltage (V) data is used as X-axis data, the ratio of dQ/dV is used as Y-axis data, and a charging capacity increment curve (dQ/dV-V) graph with three obvious peak values is obtained after filtering processing is carried out on the ratio of dQ/dV by using a Gaussian filtering data processing method, and the graph is shown as a charging capacity increment curve graph of the retired lithium iron phosphate battery. In this test, peak II is the highest peak.
Step seven: and repeating the test tests in the fourth step and the sixth step, drawing a charging capacity increment curve corresponding to each battery capacity test according to the fifth step and the sixth step, and drawing a charging capacity increment curve chart by five times of measurement in sequence as shown in the third figure.
Step eight: and according to the obtained charging capacity increment curve, subtracting X-axis coordinate data corresponding to the highest peak value, namely the No. II peak in the charging capacity increment curve. In this experiment, it is found that in the first four test processes of the peak No. ii, the difference between the X-axis voltage data corresponding to two adjacent times is greater than 30mv, and the corresponding deviation values are 53, 92, and 59, respectively. The deviation of the X-axis voltage data corresponding to the No. II peak is 3mv between the charging capacity increment curve measured in the 5 th test and the charging capacity increment curve measured in the 4 th test, and the discharging capacity corresponding to the step four in the 5 th test is output in the test, namely 7584 mah.
Claims (1)
1. A method for calibrating a stable capacity value of a retired lithium battery stored for a long time is characterized by comprising the following steps:
the method comprises the following steps: under good light conditions, the appearance of the retired lithium battery monomer is detected by a visual method, and if deformation, cracks or liquid leakage exists, the capacity of the retired lithium battery monomer is not tested;
step two: observing the label on the appearance of the retired lithium battery monomer, and collecting the information of the retired lithium battery monomer;
step three: the method for activating the retired lithium battery monomer selected by the appearance detection comprises the following steps:
3.1) at a constant temperature of 25 ℃ at 0.01CnCharging the monomer to a specified monomer charging cut-off voltage by current constant current, and standing for 30-60 min;
3.2) at 0.01CnDischarging the mixture to a specified monomer discharge cut-off voltage by constant current, and standing for 30-60 min;
3.3) repeating the steps 3.1) to 3.2)3 times;
step four: the method for testing the battery capacity of the activated retired lithium battery monomer comprises the following steps:
4.1) at a constant temperature of between 23 and 27 ℃ and at a temperature of 0.02CnCharging with constant current to a predetermined charge cut-off voltage, and charging with constant voltage until the current is reduced to 0.05CnStopping and standing for 60 min;
4.2) at 0.02CnDischarging with constant current to the specified monomer discharge cut-off voltage, and standing for 60 min;
4.3) calculating the discharge capacity;
4.4) repeating the steps 4.1) to 4.3), when the range of the results of the three consecutive tests is less than 3% of the rated value, ending the test, and taking the average value of the results of the last three tests;
step five: in the process of testing the battery capacity in the fourth step, battery charging and discharging equipment is set to sample battery capacity Q data and voltage V data when the retired lithium battery is charged at a certain sampling frequency; carrying out differential processing on the acquired capacity Q data and voltage V data to obtain dQ and dV;
step six: using the collected voltage V data as X-axis data, using the ratio of dQ/dV as Y-axis data, and filtering the ratio of dQ/dV by using a Gaussian filtering data processing method to obtain a charging capacity increment curve dQ/dV-V diagram with three obvious peak values;
step seven: repeating the fourth step and the sixth step, and drawing a charging capacity increment curve corresponding to each battery capacity test according to the fifth step and the sixth step;
step eight: according to the obtained charging capacity increment curve, performing difference on X-axis coordinate data corresponding to the highest peak value in the charging capacity increment curve graph; in the adjacent testing processes, if the difference of the X-axis voltage data of the charging capacity increment curve corresponding to the highest peak value is between 0 and 30mv, outputting the discharging capacity measured in the last step four, namely the stable capacity value of the retired lithium battery stored for a long time; otherwise, returning to the third step.
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| CN109164146B (en) * | 2018-11-12 | 2023-06-09 | 桑顿新能源科技(长沙)有限公司 | Method for judging water content through formation curve |
| CN110190348B (en) * | 2019-06-11 | 2020-12-11 | 泰州纳新新能源科技有限公司 | Activation method of lithium ion battery |
| CN110501650A (en) * | 2019-07-10 | 2019-11-26 | 广州供电局有限公司 | Battery performance measurement method and device |
| CN110850323A (en) * | 2019-11-29 | 2020-02-28 | 国网河南省电力公司电力科学研究院 | Method and device for evaluating accelerated attenuation of retired ternary lithium battery |
| CN111106402B (en) * | 2020-01-03 | 2021-01-08 | 天能电池集团股份有限公司 | Method for recovering capacity of over-term storage battery |
| CN111693884B (en) * | 2020-06-19 | 2023-04-28 | 北京嘀嘀无限科技发展有限公司 | Battery pack consistency detection method and device, readable storage medium and electronic equipment |
| CN111751732B (en) * | 2020-07-31 | 2021-09-28 | 中国汽车工程研究院股份有限公司 | Electric quantity calculation method based on self-adaptive Gaussian convolution integral method |
| CN112255549B (en) * | 2020-09-08 | 2024-03-19 | 广州市香港科大***研究院 | Filtering method, system, device and medium for battery capacity increment |
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