CN113433467B - Lithium ion battery cycle accelerated evaluation method - Google Patents
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- G—PHYSICS
- G01—MEASURING; TESTING
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- 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
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- 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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Abstract
The invention discloses a lithium ion battery circulation accelerated evaluation method, which is used for accelerating circulation of a battery to be tested under a certain SOC, wherein the circulation system of the battery is consistent with the corresponding charging current and discharging current under the corresponding SOC in the actual circulation system; the performance of the battery before and after the accelerated cycle test is characterized and analyzed to achieve the purpose of analyzing the cycle performance of the battery. The method is suitable for the development of lithium ion battery products, is used for rapid comparative analysis of the cycle performance of the battery when screening materials and optimizing a system, effectively shortens the development period of the battery, improves the working efficiency, indirectly reduces the development cost of the battery by reducing the energy consumption of cycle testing, and has good application prospect and popularization value.
Description
Technical Field
The invention relates to the technical field of lithium battery testing, in particular to a lithium ion battery cycle accelerated evaluation method.
Background
The lithium ion battery has the remarkable advantages of high energy density, long cycle life, greenness, no pollution and the like, and is widely popularized and applied in the fields of portable electronic products, energy storage systems and electric automobiles. Along with the technical progress, the cycle performance of the current lithium ion battery is further improved, particularly in the field of energy storage systems and electric automobiles, the cycle life of the battery reaches thousands of times or even tens of thousands of times, so that the development progress of the battery product is greatly prolonged by a long cycle test process, and meanwhile, the development cost of the product is increased due to the problems of high test resource investment and high energy consumption caused by a long evaluation period.
At present, in the field of cycle accelerated evaluation of lithium ion batteries, the cycle performance of the batteries is accelerated by mainly changing stress conditions such as temperature, pressure, voltage, current, depth of discharge and the like of the batteries, but the attenuation of the batteries in the cycle process due to complex chemical and electrochemical reactions and the like in the lithium ion batteries is a very complex nonlinear time-varying system, and the corresponding transformation relationship between the changed stress conditions and the actual cycle system is difficult to accurately quantify and characterize, so that the rapid and accurate evaluation of the cycle performance of the lithium ion batteries is still a difficult problem.
Disclosure of Invention
In view of this, the invention provides a lithium ion battery cycle accelerated evaluation method, which performs accelerated cycle on a battery to be tested under a certain SOC, wherein the cycle system of the battery is consistent with the corresponding charging current and discharging current under the corresponding SOC in the actual cycle system, and the performance of the battery before and after the accelerated cycle test is characterized and analyzed to achieve the purpose of analyzing the cycle performance of the battery, thereby greatly shortening the evaluation period of the cycle performance of the battery.
The invention provides a lithium ion battery cycle accelerated evaluation method, which comprises the following steps:
accelerating circulation is carried out on the battery to be tested under a certain SOC, and the circulation system of the battery is consistent with the corresponding charging current and discharging current under the corresponding SOC in the actual circulation system;
the performance of the battery before and after the accelerated cycle test is characterized and analyzed to achieve the purpose of analyzing the cycle performance of the battery.
The method specifically comprises the following steps:
the first step is as follows: taking a battery to be tested and a reference battery, testing the lithium salt concentration of the battery and the reference battery by using an in-situ testing device, and obtaining the onset temperature T of the battery to be tested after data processing i Onset temperature T of reference cell si ；
The second step is that: taking the battery to be tested and the reference battery to perform a circulation acceleration test by using charge and discharge equipment;
the third step: taking the battery to be tested and the reference battery, testing the lithium salt concentration by using the in-situ testing device again, and obtaining the onset temperature T of the battery to be tested after data processing e Reference cell onset temperature T se ；
The fourth step: and (5) carrying out cyclic accelerated evaluation analysis on the battery to be tested.
Wherein the content of the first and second substances,
the reference cell was a fresh cell of the same type and system of cells that had passed cycle validation and did not undergo cycle testing.
The method specifically comprises the following steps:
step 1, setting a low-current charging and discharging process to obtain the charging capacity C of the battery to be tested under the low-current charging and discharging c0 And discharge capacity C d0 Reference cell charge capacity C at the same low current charge and discharge sc0 And discharge capacity C sd0 The small current is generally set to be 0.05C-0.5C, the charging and discharging cut-off voltage is consistent with the charging and discharging cut-off voltage of the battery in the circulating system to be evaluated, and the constant-voltage charging stage takes the current reduced to 0.02-0.05C as the cut-off condition;
step 2, charging the battery to a certain SOC with a small current, and standing for 10-30 minutes;
step 3, selecting a charging current Ic and a discharging current Id corresponding to the battery to be tested under the corresponding SOC in the actual circulation system, and performing charging and discharging circulation on the battery within a certain SOC range, wherein the SOC range is 5-20% of SOC, the circulation times are set to be 100-500 times, and the charging and discharging time is cut off to ensure that the charging and discharging capacity is the same, namely Ic < tc = Id < td >;
standing for 10-30 minutes after the charging and discharging are stopped respectively;
and step 4, continuously charging the battery to a cut-off voltage by using a small current, keeping the voltage constant until the current is reduced to 0.02-0.05C, continuously discharging, charging and discharging by using the small current, and acquiring the charging capacity C of the battery to be tested which is charged by using the small current after pulse circulation ce And discharge capacity C of small current discharge de Reference charge capacity C of the cell after pulse cycling sce And discharge capacity C sde 。
Wherein, the fourth step comprises the analysis of the capacity fading in the process of accelerating circulation,
the reference cell has a small current charge capacity of C before accelerated cycling sci After circulation is C sce The charge capacity retention ratio of the reference cell after accelerated cycling is P sc ＝C sce /C sci ；
The small current charging capacity of the battery to be tested before accelerated circulation is C ci After circulation is C ce The retention rate of the charging capacity of the battery to be tested after accelerated circulation is P c ＝C ce /C ci ；
The small-current discharge capacity of the reference cell before accelerated cycling is C sdi After circulation is C sde The discharge capacity retention rate of the reference cell after accelerated cycling is P sd ＝C sde /C sdi ；
The small-current discharge capacity of the battery to be tested before accelerated circulation is C di After circulation is C de And the discharge capacity retention rate of the battery to be tested after pulse circulation is P d ＝C de /C di ；
When P is present c <P sc And P is d <P sd When the current battery is in the accelerated cycle, the capacity attenuation of the battery to be tested in the accelerated cycle period is higher than that of the reference battery, namely the cycle performance of the battery to be tested is inferior to that of the reference battery;
when P is c >＝P sc And P is d >＝P sd This indicates that the capacity fade of the test cell during accelerated cycling is lower than or equal to that of the reference cell, and the following further analysis is required.
Wherein, after the capacity fading analysis, the lithium salt consumption in the accelerating circulation process is compared,
the in-situ testing device is utilized to test the lithium salt concentration of the battery, the onset temperature corresponds to the lithium salt concentration in the battery, and when the onset temperature deviates to the high-temperature direction, the lithium salt concentration in the battery is correspondingly reduced, so that the lithium salt concentration change in the battery can be correspondingly known by calculating the variation condition of the onset temperature;
the onset temperature variation of the reference cell during the acceleration cycle is Δ T s ＝T se -T si ，
The onset temperature change value of the battery to be tested in the accelerating circulation process is delta T = T e -T i ，
When Δ T>△T s When it is determined that the measurement is to be performedThe amount of lithium salt consumed by the cell during accelerated cycling is higher than in the reference cell, the cell under test may jump ahead during cycling due to insufficient active lithium,
when Δ T<＝△T s And then, the lithium salt consumed by the battery to be tested during the accelerated cycle is less than or equal to that of the reference battery, so that the cycle performance of the battery to be tested is better than that of the reference battery. The lithium ion battery circulation accelerated evaluation method provided by the invention is used for accelerating the circulation of the battery under a certain SOC in a charge-discharge mode which is the same as the actual circulation mode, and respectively testing the concentration of lithium salt in the battery and the low-current charge and discharge capacity retention rate of the battery before and after the accelerated circulation.
The method is suitable for the development of lithium ion battery products, is used for rapid comparative analysis of the battery cycle performance when screening materials and optimizing a system, effectively shortens the battery development period, improves the working efficiency, indirectly reduces the battery development cost by reducing the energy consumption of cycle testing, and has good application prospect and popularization value.
Compared with a reference battery with known cycle performance, when the low-current charging and discharging capacity retention rate of the battery to be tested is smaller than that of the reference battery, the capacity attenuation of the battery to be tested in the accelerated cycle period is higher than that of the reference battery, namely the cycle performance of the battery to be tested is inferior to that of the reference battery.
When the retention rates of the small current charging and discharging capacities of the battery to be tested are higher than (or equal to) that of the reference battery, the consumption of the lithium salt during the accelerated cycling of the battery needs to be further analyzed.
When the amount of lithium salt consumed by the battery to be tested during accelerated cycling is higher than that of the reference battery, it indicates that the battery to be tested may have a rapid degradation of the cycling performance of the battery in advance due to insufficient active lithium during cycling.
And when the lithium salt consumed by the battery to be tested during the accelerated circulation is lower than or equal to that of the reference battery, and the circulation performance of the battery to be tested is better than that of the reference battery.
Drawings
Fig. 1 is a schematic diagram showing comparison between actual cycle results of a battery to be tested and a reference battery in the embodiment of the present application.
Detailed Description
It should be noted that, in the present application, the embodiments and features of the embodiments may be combined with each other without conflict.
The invention is described in further detail below with reference to the figures and specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
The specific meaning of the above terms in the present application can be understood by those skilled in the art according to specific situations.
Examples
In this example, the test specimen was a 21700 cylindrical lithium ion experimental battery with a 1C capacity of 4.7Ah. The cell to be tested is of the same type as the reference cell, but with a different negative electrode.
The battery testing device is a conventional charge and discharge instrument, and the device adopted in the embodiment is an Arbin BT2000 charge and discharge testing system.
The first step is as follows: taking the battery to be tested and the reference battery, testing the lithium salt concentration of the battery to be tested and obtaining the onset temperature T of the battery to be tested after data processing i Onset temperature T of reference cell si 。
The second step is that: and (3) carrying out circulation acceleration test on the battery to be tested and the reference battery by using charge and discharge equipment, wherein the test flow is set as follows.
In the step 1, the battery is charged and discharged by 0.2C =0.94A with low current, the constant-current charging cut-off voltage is 4.2V, the constant-voltage charging is carried out until the current is reduced to 0.05C =0.235A, and the discharging cut-off voltage is 2.5V. The charging capacity C of the battery to be tested at 0.2C charging and discharging is recorded in Table 1 c0 And discharge capacity C d0 Reference charge capacity C of the cell at 0.2c =0.94a charge and discharge sc0 And discharge capacity C sd0 。
Step 2 charge the battery to 10% soc with a small current of 0.2c =0.94a, rest for 10 minutes.
Step 3, selecting the battery to be testedCharging current I corresponding to 10% SOC in actual-cycle System c And discharge current I d ，I c ＝I d Charge and discharge cycles of 10% soc (4.7 × 360/3600/4.7 × 100% = 10%) were performed on the battery with charge and discharge time of 360 seconds, and the number of cycles was 200, and the charge and discharge capacities of the battery in this cycle were the same.
Standing for 10-30 min after the above-mentioned charge and discharge are cut off.
Step 4, the battery is charged to a cut-off voltage of 4.2V by 0.2c =0.94a, the battery is charged at a constant voltage until the current is reduced to 0.05c =0.235a, the discharging, the charging (the small current charging capacity after the accelerated cycle) and the discharging (the small current discharging capacity after the accelerated cycle) under the condition of 0.2c =0.94a are continued, and the charging capacity C of the battery to be tested which is charged and discharged by 0.2c =0.94a after the accelerated cycle is recorded in table 1 ce And discharge capacity C de Reference charge capacity C of the cell charged and discharged at 0.2c =0.94a after accelerated cycling sce And discharge capacity C sde 。
The third step: taking the battery to be tested and the reference battery, testing the lithium salt concentration of the battery to be tested and the reference battery by using the in-situ testing device again, and obtaining the onset temperature T of the battery to be tested after data processing e Onset temperature T of reference cell se Recorded in table 1.
TABLE 1 Charge-discharge capacity conservation rate and Onset temperature before and after accelerated cycling of the battery
The fourth step: cyclic accelerated evaluation analysis of battery to be tested
Capacity fade analysis during step 1 acceleration cycle
The small current charge capacity of the reference cell before accelerated cycling is C sci =4.812, C after cycling sce =4.744, the charge capacity of the reference cell after accelerated cycling remains P sc ＝C sce /C sci ＝4.744/4.812*100％＝98.6％。
The charging capacity of the battery to be tested before accelerated circulation is C ci =4.866Ah, C after circulation ce If =4.803Ah, the charge capacity retention ratio of the battery to be tested after accelerated cycling is P c ＝C ce /C ci ＝4.803/4.866*100％＝98.7％。
The discharge capacity of the reference cell before accelerated cycling was C sdi =4.757Ah, C after circulation sde If =4.730Ah, the discharge capacity of the reference cell after accelerated cycling is maintained at P sd ＝C sde /C sdi ＝4.730/4.757*100％＝99.4％。
The discharge capacity of the battery to be tested before accelerated circulation is C di =4.815Ah, C after circulation de And= 4.797Ah, the discharge capacity retention rate of the battery to be tested after accelerated circulation is P d ＝C de /C di ＝4.797/4.815*100％＝99.6％。
Due to (P) c ＝98.7％)>(P sc = 98.6%) and (P) d ＝99.6％)>(P sd = 99.4%), indicating that the cell to be tested has a slightly lower capacity fade during accelerated cycling than the reference cell, and the following further analysis is required.
Comparison of lithium salt consumption during accelerated cycling in step 2
The in-situ testing device is used for testing the lithium salt concentration of the battery, the onset temperature corresponds to the lithium salt concentration in the battery, and when the onset temperature deviates to the high temperature direction, the lithium salt concentration in the battery is correspondingly reduced, so that the lithium salt concentration change in the battery can be correspondingly obtained by calculating the variation condition of the onset temperature.
The onset temperature change value of the reference cell during the acceleration cycle is
△T s ＝T se -T si ＝(-15.3)-(-17.9)＝2.6
The onset temperature change value of the battery to be tested in the acceleration cycle process is
△T＝T e -T i ＝(-18.7)-(-20.1)＝1.4
Due to delta T (1.4)<△T s (2.6), it indicates that the battery under test is in the accelerated cycle periodThe amount of lithium salt consumed is lower than that of the reference battery, so the cycle performance of the battery to be tested is better than that of the reference battery.
In this embodiment, accelerated cycle testing is performed on the battery to be tested and the reference battery, so that it can be known that the cycle performance of the battery to be tested is better than that of the reference battery and is consistent with an actual cycle test result, as shown in fig. 1.
The accelerated cycle test only takes 7 days to obtain the evaluation result consistent with the actual cycle test, thereby greatly shortening the evaluation period of the cycle performance of the battery, effectively shortening the development period of the battery, saving the occupied time of test resources, obviously reducing the energy consumption and indirectly reducing the development cost of the battery.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many modifications and adaptations can be made without departing from the principle of the present invention, and such modifications and adaptations should also be considered as the scope of the present invention.
Claims (3)
1. A lithium ion battery cycle accelerated evaluation method is characterized by comprising the following steps:
accelerating circulation is carried out on the battery to be tested under a certain SOC, and the corresponding charging current and discharging current under the corresponding SOC in the circulation system and the actual circulation system are consistent;
the performance of the battery before and after the accelerated cycle test is characterized and analyzed to achieve the purpose of analyzing the cycle performance of the battery;
the method specifically comprises the following steps:
the first step is as follows: taking a battery to be tested and a reference battery, testing the lithium salt concentration of the battery and the reference battery by using an in-situ testing device, and obtaining the onset temperature T of the battery to be tested after data processing i Reference cell onset temperature T si ；
The second step: taking the battery to be tested and the reference battery to perform a circulation acceleration test by using charge and discharge equipment;
the third step: taking the battery to be tested and the reference battery, and testing the lithium salt concentration by using the in-situ testing device againAfter data processing, the onset temperature T of the battery to be measured is obtained e Onset temperature T of reference cell se ；
The fourth step: circularly accelerating evaluation and analysis of the battery to be tested;
in the fourth step, including the capacity fade analysis during the accelerated cycling,
the small current charge capacity of the reference cell before accelerated cycling is C sci After circulation is C sce The charge capacity retention ratio of the reference cell after accelerated cycling is P sc ＝C sce /C sci ；
The small current charging capacity of the battery to be tested before accelerated circulation is C ci After circulation is C ce The retention rate of the charging capacity of the battery to be tested after accelerated circulation is P c ＝C ce /C ci ；
The small-current discharge capacity of the reference cell before accelerated cycling is C sdi After circulation is C sde The discharge capacity retention rate of the reference cell after accelerated cycling is P sd ＝C sde /C sdi ；
The small-current discharge capacity of the battery to be tested before accelerated circulation is C di After circulation is C de If the retention rate of the discharge capacity of the battery to be tested after the pulse cycle is P d ＝C de /C di ；
When P is present c <P sc And P is d <P sd When the current battery is in the accelerated cycle, the capacity attenuation of the battery to be tested in the accelerated cycle period is higher than that of the reference battery, namely the cycle performance of the battery to be tested is inferior to that of the reference battery;
when P is present c >＝P sc And P is d >＝P sd Then, it indicates that the capacity fade of the cell under test during the accelerated cycling is lower than or equal to that of the reference cell, and the following further analysis is required;
after the capacity fade analysis, the lithium salt consumption during accelerated cycling was also included,
the in-situ testing device is utilized to test the lithium salt concentration of the battery, the onset temperature corresponds to the lithium salt concentration in the battery, and when the onset temperature deviates to the high-temperature direction, the lithium salt concentration in the battery is correspondingly reduced, so that the lithium salt concentration change in the battery can be correspondingly obtained by calculating the variation condition of the onset temperature;
the onset temperature variation of the reference cell during the acceleration cycle is Δ T s ＝T se -T si ，
The onset temperature change value of the battery to be tested in the accelerating circulation process is delta T = T e -T i ，
When Δ T>△T s When the amount of lithium salt consumed by the battery to be tested during the accelerated cycle is higher than that of the reference battery, the battery to be tested may jump in advance due to insufficient active lithium during the cycle,
when Δ T<＝△T s And then, the lithium salt consumed by the battery to be tested during the accelerated cycle is less than or equal to that of the reference battery, so that the cycle performance of the battery to be tested is better than that of the reference battery.
2. The lithium ion battery cycle accelerated evaluation method according to claim 1,
the reference cell is a fresh cell of the same type and same system of a cell which passes cycle verification and is not subjected to cycle test.
3. The lithium ion battery cycle accelerated evaluation method according to claim 1,
in the second step, the method specifically comprises the following steps:
step 1, setting a low-current charging and discharging process to obtain the charging capacity C of the battery to be tested under the low-current charging and discharging c0 And discharge capacity C d0 Reference cell charge capacity C at the same low current charge and discharge sc0 And discharge capacity C sd0 The small current is generally set to be 0.05C-0.5C, the charging and discharging cut-off voltage is consistent with the charging and discharging cut-off voltage of the battery in the circulating system to be evaluated, and the constant-voltage charging stage takes the current reduced to 0.02-0.05C as the cut-off condition;
step 2, charging the battery to a certain SOC with a small current, and standing for 10-30 minutes;
selecting a charging current Ic and a discharging current Id corresponding to the SOC of the battery to be tested in the actual circulation system, and performing charging and discharging circulation on the battery within a certain SOC range, wherein the SOC range is 5-20% of SOC, the circulation times are set to be 100-500 times, and the charging and discharging time is cut off to enable the charging and discharging capacity to be the same, namely Ic tc = Id td;
standing for 10-30 minutes after the charging and discharging are stopped respectively;
and step 4, continuously charging the battery to a cut-off voltage by using a small current, keeping the voltage constant until the current is reduced to 0.02-0.05C, continuously discharging, charging and discharging by using the small current, and acquiring the charging capacity C of the battery to be tested which is charged by using the small current after pulse circulation ce And discharge capacity C of small current discharge de Reference capacity C of the cell to be charged and discharged at a low current after pulse cycling sce And discharge capacity C sde 。
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