CN113219360B - Lithium battery cycle life testing method based on float strategy - Google Patents
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 51
- 238000012360 testing method Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 66
- 238000007600 charging Methods 0.000 claims abstract description 57
- 230000008569 process Effects 0.000 claims abstract description 46
- 238000007599 discharging Methods 0.000 claims abstract description 18
- 238000010998 test method Methods 0.000 claims abstract description 14
- 238000010280 constant potential charging Methods 0.000 claims abstract description 12
- 239000007774 positive electrode material Substances 0.000 claims abstract description 6
- 230000032683 aging Effects 0.000 abstract description 9
- 238000011161 development Methods 0.000 abstract description 3
- 230000018109 developmental process Effects 0.000 abstract description 3
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 14
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 14
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 10
- 238000010277 constant-current charging Methods 0.000 description 9
- 125000004122 cyclic group Chemical group 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 7
- 238000012795 verification Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000004904 shortening Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 3
- 230000006399 behavior Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000284 resting effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000033366 cell cycle process Effects 0.000 description 1
- 238000011217 control strategy Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
Classifications
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- General Physics & Mathematics (AREA)
Abstract
The invention provides a lithium battery cycle life test method based on a float charging strategy, which comprises the following steps: s1, charging: charging the battery with constant current and constant voltage, wherein the upper limit voltage is 4.35V, and the cut-off current is 0.05C; s2: discharging: discharging the battery with constant current, wherein the lower limit voltage is 3.0V; taking S1 to S2 as a cycle, keeping constant voltage charging for 24 hours at 4.35V after the charging process is finished at intervals, and finishing the cycle for 100 times or 1000 hours. The invention has simple operation process, simple equipment and simple method, and can greatly shorten the test period and save the test channel resources by adopting the charging strategy method for keeping 24 hours under high voltage every 2 cycles. Particularly, the aging behavior of LCO and NCM cells in the circulating process can be accelerated, a simple and effective method is developed for the accelerated test of the circulating life of the lithium battery, and a new development mode is provided for researching failure analysis of different positive electrode materials.
Description
Technical Field
The invention relates to the technical field of lithium battery testing, in particular to a lithium battery cycle life testing method based on a float charging strategy.
Background
Lithium ion batteries are secondary batteries capable of being repeatedly charged and discharged, and in recent years, under the continuous stimulation of policies such as consumer electronics, new energy automobiles and the like, the lithium ion batteries have widely entered a popular popularization stage as new energy. However, the requirements of customers on lithium batteries are not only safety and endurance mileage, but also service life and charging time, which is also the key of whether electric automobiles can be popularized or not. At present, a standard cycle life test method of GB/T31484-2015 is generally adopted for the cycle life test of the battery, namely 1C constant current and constant voltage charge is adopted, and after standing, 1C constant current discharge is adopted. As the battery ages, the battery impedance increases, and the constant voltage phase during constant current and constant voltage charging increases significantly. The slow charging strategy of the general whole vehicle battery pack is basically low-rate constant-current charging, no constant-voltage stage exists, and the charging time is generally longer than 6 hours. On one hand, long-time cycle life evaluation influences the development period of the battery, and long-time charging brings inconvenience to a plurality of clients; on the other hand, lithium ion batteries in consumer electronics and electric vehicles typically remain high potential for long periods of time after charging, which means that charge-discharge protocols that always discharge immediately after charging are impractical in predicting life and failure of lithium ion batteries. Therefore, developing a realistic lithium ion battery using charge-discharge strategy is critical to fully understand the performance of a lithium battery.
In the prior art, the invention patent CN109061513A discloses a test method for improving the cycle life of a lithium iron phosphate power lithium battery, and the polarization of the battery is reduced by a cycle test method for converting high-current constant-current charging into low-current constant-current charging, so that effective advice is provided for a charging control strategy of the whole vehicle; the method uses multi-step constant current to charge the battery, and changes the current value of constant current charging, so that the method is more complex; moreover, the purpose of reducing the current at the charging terminal is to reduce polarization, and the purpose of floating charge and accelerated aging under high potential cannot be achieved;
the invention patent CN106124997B discloses a high-temperature life test method of a lithium iron phosphate battery, which is characterized in that a small-current floating charge cycle is carried out for a specific time under a high-temperature condition after the lithium iron phosphate battery is filled. After a plurality of cycles, the method takes 3 times of capacity under the set temperature condition, compares the capacity with 75% of the nominal capacity to judge whether the capacity is qualified or not, has short test period, can not reach an ideal level for LCO and NCM battery float aging, has no obvious effect of accelerating attenuation, and is more complex;
the invention patent CN111106404A provides a float charge optimization method of a lithium iron phosphate battery, wherein a three-stage charge-float charge-constant current discharge charge-discharge mode is adopted in the float charge cycle use process of the lithium iron phosphate battery, so that the degradation of active substances is reduced, and the cycle service life of the lithium iron phosphate battery is prolonged. The method is complex, can improve the circulation of the LFP battery, and can not achieve the opposite effects of shortening the verification period and accelerating the service life of the circulation. Meanwhile, accelerated verification of cyclic aging of different materials in different systems is not performed.
In the technical scheme disclosed in the prior art, the method of the invention for accelerating the cyclic attenuation of the lithium battery floating charge with different materials aiming at different systems is not provided, and particularly, the research on the accelerated aging of the battery core of the LCO and NCM anode materials is not provided. The accelerated life test is mainly simulated by increasing the temperature and the current; in the prior art, the scheme mainly aims at floating charge and cyclic attenuation, namely a step charge strategy, namely current is gradually reduced, polarization is eliminated, and the cycle life of a lithium battery, in particular a lithium iron phosphate battery, is improved. Therefore, there is currently a few simple and effective solutions for accelerating the cycle life research and shortening the verification period of LCO and NCM battery float strategy.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a lithium battery cycle life testing method based on a floating charge strategy, which is a way for obtaining higher average voltage, representing worst charging condition and providing higher energy density aging rate.
In order to solve the technical problems, the invention adopts the following technical scheme: a lithium battery cycle life test method based on a float strategy comprises the following steps:
s1, charging: charging the battery with constant current and constant voltage, wherein the upper limit voltage is 4.35V, and the cut-off current is 0.05C;
s2: discharging: discharging the battery with constant current, wherein the lower limit voltage is 3.0V;
taking S1 to S2 as a cycle, keeping constant voltage charging for 24 hours at 4.35V after the charging process is finished at intervals, and finishing the cycle for 100 times or 1000 hours.
Further, the lithium battery cycle temperature is not greater than 35 ℃ during the charging and discharging processes.
Further, after the charging or discharging process is finished, the lithium battery is placed for 5min, and the placing environment temperature is not more than 35 ℃.
Further, during the charging or discharging process, the lithium battery is in an environment of 2-5 standard atmospheres.
Further, the lithium battery has a remaining capacity of not more than 30% before the charging process or after the discharging process is completed.
Further, at least one cycle of S1 to S2 is provided before the constant voltage charge of 4.35V is maintained for 24 hours.
Further, the lithium battery cycle life testing method based on the float strategy is used for a lithium battery cell taking LCO or NCM as a positive electrode material.
Compared with the prior art, the invention has the beneficial effects that:
1. the floating charging strategy that the floating charging is kept for 24 hours under high voltage every 2 cycles at normal temperature is innovatively provided, and the method has the advantages of simple cycle process, simple equipment and simple operation;
2. the method for accelerating the cycle life of the float strategy based on CV24h is developed, and can greatly shorten the test verification period, save the test channel and develop a simple and effective method for accelerating the cycle life of the lithium battery;
3. the method has strong applicability and portability, is applicable to aging behaviors in the cell cycle process of LCO and NCM different material systems, and provides an innovative thought for researching failure analysis of different positive electrode materials.
Drawings
The disclosure of the present invention is described with reference to the accompanying drawings. It is to be understood that the drawings are designed solely for the purposes of illustration and not as a definition of the limits of the invention. In the drawings, like reference numerals are used to refer to like parts. Wherein:
FIG. 1 is a flowchart of a first embodiment of a method for testing cycle life based on a float strategy according to the present invention;
FIG. 2 is a flow chart of a second embodiment of a method for testing cycle life based on a float strategy according to the present invention;
FIG. 3 is a schematic diagram of the capacity retention of LCO cycle in comparative example 1 of example 1;
fig. 4 is a graph showing capacity retention of NMC622 cycles in comparative example 2;
Detailed Description
It is to be understood that, according to the technical solution of the present invention, those skilled in the art may propose various alternative structural modes and implementation modes without changing the true spirit of the present invention. Accordingly, the following detailed description and drawings are merely illustrative of the invention and are not intended to be exhaustive or to limit the invention to the precise form disclosed.
A lithium battery cycle life test method based on a float strategy comprises the following steps:
s1, charging: charging the battery with constant current and constant voltage, wherein the upper limit voltage is 4.35V, and the cut-off current is 0.05C;
s2: discharging: discharging the battery with constant current, wherein the lower limit voltage is 3.0V;
taking S1 to S2 as a cycle, keeping constant voltage charging for 24 hours at 4.35V after the charging process is finished at intervals, and ending the cycle 150 times or 1000 hours later.
In the charging or discharging process, the circulation temperature of the lithium battery is not more than 35 ℃, and the lithium battery is in a positive pressure environment of 2-5 standard atmospheres, so that the attenuation speed of an electric core in the lithium battery is improved by improving the circulation temperature of the lithium battery, but the gas is easy to generate in the lithium battery due to the improvement of the circulation temperature, so that the gas generation in the lithium battery can be effectively prevented in the positive pressure environment of 2-5 standard atmospheres, and the lithium is separated.
Before the charging process or after the discharging process is finished, the residual electric quantity in the lithium battery to be tested is ensured to be not more than 30%, so that the service life of the lithium battery is accelerated.
And after the charging or discharging process is finished, the lithium battery is placed for 5min, and the placing environment temperature is not more than 35 ℃.
As shown in connection with fig. 1, according to an embodiment of the present invention, the lithium battery being tested underwent one cycle of S1 to S2, and was maintained for 24 hours at a constant voltage of 4.35V after the end of the charging process during the second cycle; after every other S1 to S2 cycle, the CV24h charging process is performed.
According to another embodiment of the present invention, as shown in connection with fig. 2, the lithium battery being tested underwent two cycles S1 to S2, and during the second cycle, after the end of the charging process, a constant voltage charge of 4.35V was maintained for 24 hours; after every second cycle S1 to S2, the CV24h charging process is performed.
In the above implementation process, i in fig. 1 to 2 is the number of cycles that the lithium battery undergoes S1 to S2, and n is a natural number (excluding 0). The number of the cyclic processes of S1 to S2 spaced between the charging processes of adjacent CVs 24h is a natural number (excluding 0), and the lithium battery should be subjected to at least one cyclic process of S1 to S2 before the first charging process of CV24h is performed, but the number of the cyclic processes of S1 to S2 performed is not greater than the number of the cyclic processes of S1 to S2 spaced between the charging processes of adjacent CV24 h.
The following will specifically describe with reference to the examples, in which the cycle process of S1 to S2 is separated once in the adjacent CV24h charging process, and the constant voltage charging of 4.35V is maintained for 24h or less, abbreviated as CV24 h.
[ example 1 ]
Application of floating strategy cycle life test method on Lithium Cobalt Oxide (LCO) cell: taking an LCO soft-package battery cell, carrying out constant-current and constant-voltage charging CCCV at 1C, and limiting the voltage to 4.35V and the cut-off current to 0.05C; standing for 5min;1C, constant-current discharge DC is carried out, and the lower limit voltage is 3.0V; standing for 5min;1C, constant-current charging CC is carried out, the cutoff voltage is 4.35V, then constant-voltage charging CV is carried out for 24 hours, and the constant-voltage cutoff current is set to be 0V, namely, the constant-voltage charging CV is cut off at 24 hours; standing for 5min;1C, constant-current discharge DC is carried out, and the lower limit voltage is 3.0V; standing for 5min; a normal constant-current constant-voltage charge CCCV, constant-current discharge DC (such as 1C) cycle; the above cycle ends 50 times (or 1000 hours). The cycling process and the resting process were all completed at room temperature and positive pressure of 3 standard atmospheres was applied to the lithium battery being tested. Through the floating charging strategy that the floating charging voltage is kept for 24 hours at high voltage every 2 cycles at normal temperature, the effect of accelerating attenuation is achieved for LCO, and the test result is shown in FIG. 3: compared with a normal CCCV charging strategy without CV24h, the floating charging strategy has capacity water jump phenomenon in less than 1000h, the cycle 700h is lower than 80% retention rate, the normal CCCV cycle of the control group has no CV24h, and the 1000h retention rate is higher than 90%. Therefore, in the circulation process, the floating charge strategy circulation life test method has the effects of accelerating attenuation and shortening the verification period on the Lithium Cobalt Oxide (LCO) battery cell.
[ example 2 ]
Application of floating strategy cycle life test method on soft package ternary material (NMC 622) battery core: taking a ternary NMC622 soft-package battery cell, carrying out constant-current and constant-voltage charging CCCV on 1C, wherein the upper limit voltage is 4.35V, and the cut-off current is 0.05C; standing for 5min;1C, constant-current discharge DC is carried out, and the lower limit voltage is 3.0V; standing for 5min;1C, constant-current charging CC is carried out, the cutoff voltage is 4.35V, then constant-voltage charging CV is carried out for 24 hours, and the constant-voltage cutoff current is set to be 0V, namely, the constant-voltage charging CV is cut off at 24 hours; standing for 5min;1C, constant-current discharge DC is carried out, and the lower limit voltage is 3.0V; standing for 5min; then a normal constant-current constant-voltage charge CCCV and constant-current discharge DC (such as 1C) cycle is carried out; the above cycle ends 50 times (or 1000 hours). The cycling process and the resting process were all completed at 35 ℃ and a positive pressure of 5 standard atmospheres was applied to the lithium battery being tested. The NMC622 was accelerated and attenuated by a float charging strategy that was maintained at high voltage for 24h every 2 cycles at normal temperature, and the test results are shown in fig. 4: compared with a normal CCCV charging strategy without CV24h, the floating charging strategy has capacity water jump phenomenon at 900h, and the retention rate is less than 80%; the control group has no CV24h and 900h retention of about 95% in normal CCCV circulation. For ternary materials, CV continues at high voltage levels, such that the destructive active lithium of the negative electrode SEI film is consumed and the structural collapse of the positive electrode material results in accelerated capacity decay aging. Therefore, the floating strategy cycle life test method has the effects of accelerating attenuation and shortening the verification period on the soft package ternary (NMC 622) battery core.
Comparative example 1
This example differs from example 1 in that the LCO cycle process does not use the CV24h float strategy, i.e., normal 1C CCCV charging. The cycle capacity retention rate was higher than that of example 1, and the effect of accelerating the decay was not as good as that of example 1.
Comparative example 2
The difference between this example and example 2 is that the NMC622 cycle process does not use the CV24h float strategy, i.e., normal 1C CCCV charging. The cycle capacity retention rate was higher than that of example 2, and the effect of accelerating the decay was not as good as that of example 2.
Comparative example 3
The present embodiment differs from embodiment 1 in that the cyclic process uses a longer CV float strategy, i.e., charging process CV 48h. Its cycle capacity retention ratio was compared to comparative example 1. The CV was longer, time wasted, acceleration was less effective than comparative example 1, and retention was comparable to CV24 h.
From the above, the charging strategy method that the charging strategy is kept for 24 hours under high voltage every 2 cycles is adopted for cycle, so that the test period can be greatly shortened, and the test channel resources can be saved. Particularly, the aging behavior of LCO and NCM cells in the circulating process can be accelerated, a simple and effective method is developed for the accelerated test of the circulating life of the lithium battery, and a new development mode is provided for researching failure analysis of different positive electrode materials.
The technical scope of the present invention is not limited to the above description, and those skilled in the art may make various changes and modifications to the above-described embodiments without departing from the technical spirit of the present invention, and these changes and modifications should be included in the scope of the present invention.
Claims (6)
1. The lithium battery cycle life testing method based on the float charging strategy is characterized by comprising the following steps of:
s1, charging: charging the battery with constant current and constant voltage, wherein the upper limit voltage is 4.35V, and the cut-off current is 0.05C;
s2: discharging: discharging the battery with constant current, wherein the lower limit voltage is 3.0V;
taking S1 to S2 as a cycle, keeping constant voltage charging for 24 hours at 4.35V after the charging process is finished at intervals, and finishing the cycle for 100 times or 1000 hours; wherein,,
during the charge or discharge process, the lithium battery is in an environment of 2-5 standard atmospheres.
2. The float strategy based lithium battery cycle life test method of claim 1, wherein the lithium battery cycle temperature is no greater than 35 ℃ during the charging and discharging process.
3. The float strategy based lithium battery cycle life test method of claim 2, wherein after the charging or discharging process is completed, the lithium battery is left for 5min, and the leaving ambient temperature is not greater than 35 ℃.
4. The float strategy based lithium battery cycle life test method of claim 1, wherein the lithium battery has a remaining charge of no more than 30% before the charging process or after the discharging process is completed.
5. The method for testing the cycle life of a lithium battery based on a floating charge strategy according to claim 1, wherein the cycle of S1 to S2 is provided at least once before the constant voltage charge of 4.35V is maintained for 24 hours.
6. The method for testing the cycle life of the lithium battery based on the float strategy according to any one of claims 1 to 5, wherein the method for testing the cycle life of the lithium battery based on the float strategy is used for testing a lithium battery cell by taking LCO or NCM as a positive electrode material.
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