CN113176519A - Lithium ion battery service life acceleration method based on particle irradiation - Google Patents
Lithium ion battery service life acceleration method based on particle irradiation Download PDFInfo
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- CN113176519A CN113176519A CN202110412445.0A CN202110412445A CN113176519A CN 113176519 A CN113176519 A CN 113176519A CN 202110412445 A CN202110412445 A CN 202110412445A CN 113176519 A CN113176519 A CN 113176519A
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- 239000002245 particle Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000001133 acceleration Effects 0.000 title claims abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 23
- 238000007600 charging Methods 0.000 claims abstract description 31
- 238000007599 discharging Methods 0.000 claims abstract description 9
- 230000002238 attenuated effect Effects 0.000 claims abstract description 4
- 238000012360 testing method Methods 0.000 claims description 26
- 230000008569 process Effects 0.000 claims description 13
- 238000010281 constant-current constant-voltage charging Methods 0.000 claims description 8
- 238000011065 in-situ storage Methods 0.000 claims description 8
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 claims description 2
- 230000032683 aging Effects 0.000 abstract description 8
- 230000005251 gamma ray Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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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
-
- 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]
- G01R31/382—Arrangements for monitoring battery or accumulator variables, e.g. SoC
-
- 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
- G01R31/387—Determining ampere-hour charge capacity or SoC
Abstract
The invention discloses a lithium ion battery service life acceleration method based on particle irradiation, which comprises the following steps: s1: carrying out initial capacity calibration on the battery; s2: standing for 5-30 min; s3: charging the battery according to a specific system, and simultaneously performing pulse particle irradiation; s4: standing for 5-30 min; s5: discharging the battery according to a specific system, and simultaneously performing pulse particle irradiation; s6: and repeating the steps from S2 to S5 until the battery capacity is attenuated to the end of the service life. The invention can accelerate the capacity attenuation of the lithium ion battery, shorten the aging time of the battery, greatly improve the experimental efficiency and has important application significance.
Description
Technical Field
The invention relates to the technical field of chemical batteries, in particular to a lithium ion battery service life acceleration method based on particle irradiation.
Background
Due to the high energy and power density, the lithium ion battery is considered to be the most promising power source applied to the fields of electric automobiles, spaceflight and the like. However, such equipment generally requires a long service life, even as long as 10-15 years, and thus, a high requirement is imposed on the service life of the battery. In general, a battery aging test based on actual use conditions requires a long time. Therefore, how to quickly evaluate the lifetime of a lithium ion battery becomes a key to solving this problem. Establishing a method of accelerating aging of battery performance is considered as one of the ways in which battery life can be rapidly evaluated.
The service life accelerated evaluation conditions of the commonly used lithium ion battery mainly comprise charge and discharge rate, discharge depth, ambient temperature and the like. These conditions can accelerate the cell performance degradation to some extent, but still cannot meet the actual use requirements, and the too high intensity of the acceleration conditions can significantly change the degradation mechanism of the cell, seriously reducing the effectiveness of the acceleration method. There is therefore a pressing need to develop more efficient acceleration methods.
The irradiation of high-energy particles has very strong penetrability, and can interact with a battery, so that the physical, chemical and mechanical properties of key materials of the battery are changed, the electrochemical reaction process in the battery is further influenced, and the rapid attenuation of the battery is initiated. In addition, the particle irradiation is simple and convenient to implement, and the method is suitable for batteries with various compositions and structures.
Based on the method, the lithium ion battery service life acceleration method based on particle irradiation not only can be used as an acceleration condition independently, but also can be coupled with other acceleration conditions (such as charge and discharge multiplying power, discharge depth, ambient temperature, vibration and the like), so that the test efficiency is greatly improved, the battery service life attenuation is accelerated, the test time is shortened, the test cost is reduced, and the method has important application value.
Disclosure of Invention
In view of the above, the present invention provides a method for accelerating the lifetime of a lithium ion battery, in which particle irradiation is used as an acceleration factor, pulse irradiation is selected as a battery lifetime acceleration condition, and other acceleration conditions (one or more of charge and discharge rate, discharge depth, and ambient temperature) are coupled to perform an accelerated aging test on the battery, so as to further accelerate the aging of the battery under the existing research conditions.
In order to achieve the purpose, the invention adopts the following technical scheme:
a lithium ion battery life acceleration method based on particle irradiation comprises the following steps:
s1: carrying out initial capacity calibration on the battery;
s2: standing for 5-30 min;
s3: charging the battery according to a specific system, and simultaneously performing pulse particle irradiation;
s4: standing for 5-30 min;
s5: discharging the battery according to a specific system, and simultaneously performing pulse particle irradiation;
s6: and repeating the steps from S2 to S5 until the battery capacity is attenuated to the end of the service life.
Preferably, S1 includes:
s11: discharging the battery to cut-off voltage under constant current under a specific multiplying power condition;
s12: and (4) carrying out two charge-discharge cycle tests on the battery after the discharge is finished at a specific multiplying power, and calculating the average value of two discharge capacities to obtain the initial capacity of the battery.
Preferably, the specific magnification condition used in S11 and S12 is in the range of 0.3C to 1.0C.
Preferably, the specific charging regime in S3 is a constant current-constant voltage charging regime comprising two phases: in the first stage, with constant current IchCharging the battery until the battery voltage reaches a charge cut-off voltage Vch(ii) a In the second stage, the battery voltage is at VchKeeping constant, continuously reducing charging current, and stopping charging when charging current is reduced to charge cut-off current IendWhen so, the charging process ends.
Preferably, S3 includes:
s31: under the condition of certain environmental temperature and certain charging multiplying power, a constant-current-constant-voltage charging system is adopted to carry out charging test on the battery, and in-situ pulse irradiation is carried out on the battery in the charging process;
s32: when the battery is charged to the charge cutoff current, the charging is ended and the pulse irradiation is stopped.
Preferably, the specific discharge pattern in S5 is a constant current discharge pattern with a constant current IdischDischarging the battery when the discharge voltage drops to a discharge cut-off voltage VendWhen this happens, the discharge process ends.
Preferably, S5 includes:
s51: pulse irradiation is coupled with one or more acceleration conditions of ambient temperature, discharge rate and discharge depth, a constant current discharge system is adopted to perform discharge test on the battery under certain ambient temperature and under certain discharge rate and discharge depth conditions, and in-situ pulse irradiation is performed on the battery in the discharge process;
s52: when the battery is discharged to the discharge cutoff voltage, the discharge ends and the pulse irradiation is stopped.
Preferably, in S3 and S5, the particles in the pulsed particle irradiation include any one or more of electrons, protons, alpha particles, beta particles and gamma particles; s3, S5, the pulsed particle irradiation includes a particle irradiation stage and a rest stage, in which the particle irradiation time range: 10-60 s, standing time range: 10min to 60 min.
Preferably, in S3 and S5, the acceleration condition of the irradiation coupling of the particles in the charge and discharge test includes any one or more of ambient temperature, charge and discharge rate, and discharge depth, and the ambient temperature range is: 30-55 ℃, charge-discharge multiplying power range: 1.0-5.0C, depth of discharge: 30 to 100 percent.
Preferably, in S6, the life is terminated when the battery capacity is less than 80% of the initial capacity.
Compared with the prior art, the technical scheme provided by the invention provides a lithium ion battery service life acceleration method based on particle irradiation, namely pulse irradiation is used as a battery service life acceleration condition. A pulse is a signal that occurs for a short time in the entire signal period relative to a continuous signal, with no signal for most of the signal period. Compared with continuous irradiation, the special intermittent time of pulse irradiation can effectively relieve the polarization of the battery and the structural damage caused by rapid insertion and extraction of lithium ions, and the damage to the battery under the long-time irradiation condition and the change of an attenuation mechanism are avoided. The invention aims to accelerate the capacity attenuation of the lithium ion battery and shorten the aging time of the battery. The particle irradiation can accelerate the capacity attenuation of the full cell, and the particle irradiation not only can be used as an acceleration factor alone, but also can be coupled with other acceleration factors, thereby greatly improving the experimental efficiency and having important application significance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a flow chart of a lithium ion battery life acceleration method based on particle irradiation
FIG. 2 is a graph showing LiNi under non-accelerated test conditions0.8Co0.1Mn0.1O2(NCM 811)/graphite 18650 battery capacity retention rate as a function of cycle time plot;
FIG. 3 is a graph of the capacity retention versus cycle time for an NCM 811/graphite 18650 cell under accelerated and non-accelerated conditions of example 2;
FIG. 4 is a graph of the capacity retention rate of the NCM 811/graphite 18650 battery as a function of cycle time under different charge and discharge rate conditions under the electron pulse irradiation condition in example 2.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1 was carried out:
LiNi0.8Co0.1Mn0.1O2accelerated aging test of graphite 18650 battery under gamma-ray pulse condition
S1: calibrating the battery capacity;
s11: since the cell was in a half-state during storage, the cell was first discharged to a voltage of 2.5V at 1.0C (2.75A);
s12: performing two-time circulation tests, wherein the charge-discharge multiplying power is 1.0C, the charge-discharge voltage range is 2.5-4.2V, constant-current-constant-voltage charging is adopted, the charge cutoff current is 0.02C, constant-current discharging is adopted, and the average value of the two-time discharge capacity is the initial capacity;
s2: standing for 5 min;
s3: carrying out charging test on the battery, and simultaneously carrying out gamma-ray pulse irradiation on the battery;
s31: under the environment temperature of 30 ℃, a constant current-constant voltage charging system is adopted under the condition of 1.0C multiplying power, the battery is subjected to charging test, the battery in the charging process is subjected to in-situ gamma ray pulse irradiation, the primary pulse irradiation comprises the gamma ray irradiation for 30s, and the interval time is 30 min;
s32: when the battery is charged to the current of 0.02C at the constant voltage of 4.2V, the charging is finished, and the gamma-ray pulse irradiation is stopped;
s4: standing for 5 min;
s5: carrying out discharge test on the battery, and simultaneously carrying out gamma ray pulse irradiation on the battery;
s51: under the environment temperature of 30 ℃, under the condition of 1.0C multiplying power, a constant current discharge system is adopted, the discharge depth is 100 percent, the battery is subjected to discharge test, the battery in the discharge process is subjected to in-situ gamma ray pulse irradiation, the primary pulse irradiation comprises the gamma ray irradiation for 30s, and the interval time is 30 min;
s52: when the cell was discharged to 2.5V, the discharge was terminated and the pulse irradiation was stopped.
S6: repeating S2-S5 until the battery capacity decays to 80% below the initial capacity.
Example 2 was carried out:
LiNi0.8Co0.1Mn0.1O2accelerated aging test of graphite 18650 battery under different electron pulse irradiation conditions and different cycle rates
S1: calibrating the battery capacity;
s11: since the cell was in a half-state during storage, the cell was first discharged to a voltage of 2.5V at 1.0C (2.75A);
s12: performing two-time circulation tests, wherein the charge-discharge multiplying power is 1.0C, the charge-discharge voltage range is 2.5-4.2V, constant-current-constant-voltage charging is adopted, the charge cutoff current is 0.02C, constant-current discharging is adopted, and the average value of the two-time discharge capacity is the initial capacity;
s2: standing for 5 min;
s3: carrying out charging test on the battery, and simultaneously carrying out electronic pulse irradiation on the battery;
s31: under the environment temperature of 30 ℃, a constant current-constant voltage charging system is adopted under the multiplying power conditions of 1.0C, 1.2C, 1.5C and 1.8C respectively to carry out charging test on the battery, and the battery in the charging process is subjected to in-situ electron pulse irradiation, wherein the primary pulse irradiation comprises electron irradiation for 30s, and the interval time is 30 min;
s32: when the battery is charged to the current of 0.02C at the constant voltage of 4.2V, the charging is finished, and the electron pulse irradiation is stopped;
s4: standing for 5 min;
s5: carrying out discharge test on the battery, and simultaneously carrying out electronic pulse irradiation on the battery;
s51: under the environment temperature of 30 ℃, respectively adopting a constant current discharge system under the multiplying power conditions of 1.0C, 1.2C, 1.5C and 1.8C, carrying out discharge test on the battery, and carrying out in-situ electron pulse irradiation on the battery in the discharge process, wherein the primary pulse irradiation comprises electron irradiation for 30s, and the interval time is 30 min;
s52: when the battery is discharged to 2.5V, the discharge is finished, and the pulse irradiation is stopped;
s6: and repeating the steps from S2 to S5 until the capacity of the battery is attenuated to 80 percent of the initial capacity.
Table 1 time taken for the cell to age to end of life at different cycling rates without irradiation and with irradiation as in example 2
As is evident from table 1, the irradiated cells were able to reach end of life in a shorter time under the same rate conditions.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A lithium ion battery life acceleration method based on particle irradiation is characterized by comprising the following steps:
s1: carrying out initial capacity calibration on the battery;
s2: standing for 5-30 min;
s3: charging the battery according to a specific system, and simultaneously performing pulse particle irradiation;
s4: standing for 5-30 min;
s5: discharging the battery according to a specific system, and simultaneously performing pulse particle irradiation;
s6: and repeating the steps from S2 to S5 until the battery capacity is attenuated to the end of the service life.
2. The method for accelerating the service life of the lithium ion battery based on the particle irradiation as claimed in claim 1, wherein S1 includes:
s11: discharging the battery to cut-off voltage under constant current under a specific multiplying power condition;
s12: and (4) carrying out two charge-discharge cycle tests on the battery after the discharge is finished at a specific multiplying power, and calculating the average value of two discharge capacities to obtain the initial capacity of the battery.
3. The method for accelerating the service life of the lithium ion battery based on the particle irradiation as claimed in claim 2, wherein the specific multiplying power conditions adopted in S11 and S12 are in the range of 0.3C to 1.0C.
4. The method of claim 1, wherein the specific charging system at S3 is a constant current-constant voltage charging system, comprising the following two stages: in the first stage, with constant current IchCharging the battery until the battery voltage reaches a charge cut-off voltage Vch(ii) a In the second stage, the battery voltage is at VchKeeping constant, continuously reducing charging current, and stopping charging when charging current is reduced to charge cut-off current IendWhen so, the charging process ends.
5. The method for accelerating the service life of the lithium ion battery based on the particle irradiation as claimed in claim 4, wherein S3 includes:
s31: under the condition of certain environmental temperature and certain charging multiplying power, a constant-current-constant-voltage charging system is adopted to carry out charging test on the battery, and in-situ pulse irradiation is carried out on the battery in the charging process;
s32: when the battery is charged to the charge cutoff current, the charging is ended and the pulse irradiation is stopped.
6. The method of claim 1, wherein the specific discharge schedule of S5 is a constant current discharge schedule, and the constant current I is used as the constant currentdischDischarging the battery when the discharge voltage drops to a discharge cut-off voltage VendWhen this happens, the discharge process ends.
7. The method for accelerating the service life of the lithium ion battery under the particle irradiation condition according to claim 6, wherein S5 comprises:
s51: pulse irradiation is coupled with one or more acceleration conditions of ambient temperature, discharge rate and discharge depth, a constant current discharge system is adopted to perform discharge test on the battery under certain ambient temperature and under certain discharge rate and discharge depth conditions, and in-situ pulse irradiation is performed on the battery in the discharge process;
s52: when the battery is discharged to the discharge cutoff voltage, the discharge ends and the pulse irradiation is stopped.
8. The method for accelerating the service life of the lithium ion battery based on the particle irradiation as claimed in claim 1, wherein in S3 and S5, the particles in the pulsed particle irradiation include any one or more of electrons, protons, alpha particles, beta particles and gamma particles; s3, S5, the pulsed particle irradiation includes a particle irradiation stage and a rest stage, in which the particle irradiation time range: 10-60 s, standing time range: 10min to 60 min.
9. The method for accelerating the lifetime of a lithium ion battery based on particle irradiation as claimed in claim 5 or 7, wherein in S3 and S5, the acceleration conditions of particle irradiation coupling in the charge and discharge test include any one or more of ambient temperature, charge and discharge rate, and depth of discharge, and the ambient temperature range is: 30-55 ℃, charge-discharge multiplying power range: 1.0-5.0C, depth of discharge: 30 to 100 percent.
10. The method for accelerating lifetime of a lithium ion battery based on particle irradiation as claimed in claim 1, wherein in S6, the lifetime is terminated when the battery capacity is lower than 80% of the initial capacity.
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CN113884932A (en) * | 2021-10-28 | 2022-01-04 | 广东电网有限责任公司 | Method and device for evaluating service life of battery |
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