CN114527393A - System and method for analyzing gas production acquisition time sequence of thermal runaway reaction of lithium ion battery - Google Patents
System and method for analyzing gas production acquisition time sequence of thermal runaway reaction of lithium ion battery Download PDFInfo
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- CN114527393A CN114527393A CN202210183820.3A CN202210183820A CN114527393A CN 114527393 A CN114527393 A CN 114527393A CN 202210183820 A CN202210183820 A CN 202210183820A CN 114527393 A CN114527393 A CN 114527393A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims description 31
- 238000006243 chemical reaction Methods 0.000 title claims description 27
- 239000007789 gas Substances 0.000 claims abstract description 103
- 238000001514 detection method Methods 0.000 claims abstract description 20
- 239000012495 reaction gas Substances 0.000 claims abstract description 11
- 238000012300 Sequence Analysis Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000005070 sampling Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 14
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 claims description 3
- 238000004146 energy storage Methods 0.000 claims description 3
- 238000013459 approach Methods 0.000 claims description 2
- 230000009471 action Effects 0.000 abstract description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 description 4
- 238000013461 design Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011160 research Methods 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]
- G01R31/378—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC] specially adapted for the type of battery or accumulator
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/22—Devices for withdrawing samples in the gaseous state
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3504—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing gases, e.g. multi-gas analysis
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R1/00—Details of instruments or arrangements of the types included in groups G01R5/00 - G01R13/00 and G01R31/00
- G01R1/02—General constructional details
- G01R1/04—Housings; Supporting members; Arrangements of terminals
- G01R1/0408—Test fixtures or contact fields; Connectors or connecting adaptors; Test clips; Test sockets
- G01R1/0425—Test clips, e.g. for IC's
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N2021/3595—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using FTIR
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas chromatography
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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
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Abstract
The invention relates to a lithium ion battery thermal runaway reaction gas production acquisition time sequence analysis system which comprises a heater for heating a lithium ion power battery to generate thermal runaway, gas detection equipment connected with the lithium ion power battery through a flexible gas conduit for time sequence analysis, and a plurality of gas acquisition bags sequentially arranged on the flexible gas conduit, wherein each gas acquisition bag is provided with an electromagnetic valve controlled to be opened and closed through an electromagnetic valve controller. Compared with the prior art, the invention has the advantages of short action time, good safety, good synchronism, capability of realizing staged collection of the sub-air bags, good stability, good mobility and the like.
Description
Technical Field
The invention relates to the field of thermal runaway and thermal safety of pure electric vehicles and lithium ion power batteries, in particular to a system and a method for analyzing a thermal runaway reaction gas production acquisition time sequence of a lithium ion battery.
Background
The lithium ion power battery has been widely recognized and utilized in transportation and 3C electronic products due to the advantages of high specific energy, long cycle life and the like, however, with the continuously higher requirements of the market and users on endurance mileage, battery box weight volume and corresponding power consumption, the specific energy of the lithium ion power battery is continuously improved, and the risk of safety accidents caused by thermal runaway is greatly increased by connecting the batteries with high energy density into a group, so that the development requirements of the pure electric vehicle put higher requirements on the thermal safety mechanism research, detection, early warning and protection design of the lithium ion power battery pack.
At present, three methods for warning the thermal runaway of the lithium ion battery are mainly used, namely a method based on the change of a thermal runaway voltage signal; secondly, a method based on the surface temperature of the battery; and thirdly, a method based on gas released after the battery is broken.
For monitoring and alarming thermal runaway of the lithium ion power battery pack, a pressure release valve designed by the lithium ion power battery pack is mainly used at present, and a better method which can be popularized does not exist at present.
In addition, because the reaction mechanism of the thermal runaway process is very complex, the reaction gas production time sequence is not clear, and signals such as voltage, temperature, gas production after package breaking and the like have serious hysteresis, no reliable early warning method exists at present.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a system and a method for analyzing a thermal runaway reaction gas production acquisition time sequence of a lithium ion battery.
The purpose of the invention can be realized by the following technical scheme:
the system comprises a heater for heating the lithium ion power battery to generate thermal runaway, a gas detection device connected with the lithium ion power battery through a flexible gas conduit and used for performing time sequence analysis, and a plurality of gas collection bags sequentially arranged on the flexible gas conduit, wherein each gas collection bag is provided with an electromagnetic valve which is controlled to be opened and closed through an electromagnetic valve controller.
The gas collection bag is opened in sequence according to time sequence in the gas collection process to collect gas in each sampling period.
And a battery clamp is arranged outside the lithium ion power battery to enable the thermal runaway triggering and gas collecting process to approach the actual pre-tightening force of the power battery system or the energy storage battery system.
One end of the flexible gas conduit penetrates through the battery shell and is implanted into the lithium ion power battery, and the collection of the gas generated by the thermal runaway reaction is realized through the pressure difference between the inside and the outside of the battery.
The gas detection device adopts a GC/FTIR gas detection instrument.
The generated gas is CO and CO2、H2、C2H4、CH4、C2H6And C3H6。
The electromagnetic valve realizes that the control action duration of the opening and closing of the gas collection bag is millisecond grade, and is used for realizing high-frequency collection of gas produced in the thermal runaway reaction process.
The heater and the lithium ion power battery are clamped in the battery clamp together.
A method for analyzing a gas generation acquisition time sequence of a thermal runaway reaction of a lithium ion battery comprises the following steps:
1) starting a heater to heat the lithium ion power battery to trigger thermal runaway, starting an electromagnetic valve of a first gas collection bag in the 1 st sampling period of the thermal runaway reaction, and collecting reaction gas in the 1 st sampling period;
2) opening the electromagnetic valve of the second gas collection bag at the beginning of the 2 nd sampling period, and closing the electromagnetic valve of the first gas collection bag at the same time;
3) in each sampling period, repeating the step 2), opening the next gas acquisition bag and closing the previous gas acquisition bag until all sampling periods finish the acquisition according to the time sequence;
4) and respectively introducing the collected gas into gas detection equipment 5 to obtain gas components and corresponding percentages.
And after the gas production type and percentage of each time interval in the thermal runaway reaction process are obtained according to the time sequence, a lithium ion battery thermal runaway reaction database is formed and is used as a basis for the subsequent thermal runaway judgment of the lithium ion battery.
Compared with the prior art, the invention has the following advantages:
firstly, the action time is short: the electromagnetic valve is adopted to control the opening and closing action of the air bag, and the sampling frequency can reach millisecond level;
secondly, the safety is good: the collecting and analyzing device and other components are controlled by the control system without manual operation. The operating personnel are far away from the thermal runaway battery monomer, and casualties in the experimental process can be fully avoided;
thirdly, the synchronism is good: the control system carries out linkage control on the gas acquisition part and the thermal runaway heating triggering part, so that the gas acquisition system can be fully started at the moment of heating the battery, and gas generated by the reaction of the battery in the thermal runaway whole process can be effectively acquired;
step four, the gas bag can be collected in stages, and the gas generated in each reaction stage can be fully collected;
fifthly, good stability: through the design of early pressure relief of the implanted gas conduit and the action of the clamp, the stable collection of the thermal runaway gas production close to the practical engineering application working condition can be realized.
Sixthly, good mobility: besides the square-shell battery, the invention can meet the requirements of thermal runaway gas generation acquisition and analysis of batteries with various packaging modes, capacity and material systems.
Drawings
FIG. 1 is a block diagram of a control system according to the present invention, wherein T is a sampling period.
FIG. 2 is a schematic view showing the connection of the components of the apparatus of the present invention.
The notation in the figure is:
1. the device comprises a heater, 2, a lithium ion power battery, 3, a battery clamp, 4, a gas acquisition system, 5 and gas detection equipment.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Examples
As shown in fig. 2, the present invention provides a system and a method for analyzing a gas generation acquisition time sequence of a thermal runaway reaction of a lithium ion battery, wherein the system comprises the following components:
As shown in fig. 1, the reaction gas production acquisition process comprises the following steps:
1) starting a heater 1 to heat the lithium ion power battery 2 to trigger thermal runaway, and simultaneously starting an electromagnetic valve of a first gas collection bag;
2) after the 1 st sampling period, opening the electromagnetic valve of the second gas collection bag, and closing the electromagnetic valve of the first gas collection bag;
3) in each sampling period, repeating the step 2), opening the next gas acquisition bag and closing the previous gas acquisition bag until all the gas acquisition bags are completely acquired;
4) the collected gases are introduced into a gas detection device 5 such as GC/FTIR, and the gas components and percentages are analyzed.
The method and the system are based on the principle of 'rapid acquisition and off-line monitoring', different gas acquisition bags are controlled to be opened at different time intervals to acquire gas, and the detection of reaction time sequences at different time intervals can be realized.
The invention adopts the electromagnetic valve to realize the opening and closing of the gas collection bag, can compress the control action duration to millisecond level, realizes high-frequency collection of gas produced in the thermal runaway reaction process, and effectively makes up the defect of low detection precision of gas detection equipment.
The flexible gas conduit implantation is carried out on the lithium ion power battery 2, so that the collection of the gas generated by the thermal runaway reaction can be realized by means of the internal and external pressure difference of the battery.
The implantation of the flexible gas conduit can realize the thermal runaway of the battery and release the pressure in advance, thereby avoiding the severe reaction caused by the eruption of the battery from damaging the battery and influencing the gas collection and detection.
The collection of the reaction gas generated in the whole process of battery temperature rise and overheating thermal runaway can be realized by adopting the heater and the electromagnetic valve controller for linkage control.
The arrangement of the battery clamp 3 can lead the triggering and collecting processes to be close to the actual pretightening force of the power battery system or the energy storage battery system, and in addition, the limitation of the battery clamp is beneficial to the gas collecting system to stably collect CO and CO in the reaction process2、H2、C2H4、CH4、C2H6And C3H6And the like.
The principle of generation of various gases is as follows:
C3H4O3(EC)+2.5O2→3CO2+2H2O (1)
C3H4O3(EC)+O2→3CO+2H2O (2)
2CO2+2Li++2e-→Li2CO3+CO (3)
CMC-OH+Li→CMC-OLi+0.5H2 (4)
C3H6O3(DMC)+2Li++2e-+H2→Li2CO3+2CH4 (5)
C3H4O3(EC)+2Li→Li2CO3+C2H4 (6)
C3H6O3(PC)+2Li→Li2CO3+C3H6 (7)
according to the gas generation principle, the types and the percentages of generated gases are respectively collected according to time sequence in the thermal runaway process of the battery, and when the method is actually applied, the stages of the battery in the thermal runaway process can be accurately judged according to the types and the percentages of the gases collected at the current time period, so that data support is provided for subsequent battery monitoring.
In conclusion, the method can realize the reaction gas production acquisition and detection in the thermal runaway whole process, can be used for exploring the thermal runaway reaction mechanism and reaction time sequence of various batteries, and can provide guidance for the thermal runaway early warning, protection and fire extinguishing design of a battery system according to the conclusion obtained in the detection process.
The above description is only exemplary of the present invention, and is not intended to limit the scope of the present invention, which is within the spirit and principle of the present invention.
Claims (10)
1. The utility model provides a lithium ion battery thermal runaway reaction produces gas and gathers time sequence analysis system, its characterized in that, this system is including being used for heating lithium ion power battery (2) and triggering thermal runaway's heater (1), be connected gas detection equipment (5) that are used for carrying out the time sequence analysis through flexible gas conduit and lithium ion power battery (2) and set gradually a plurality of gas collection bags on flexible gas conduit, and every gas collection bag all is equipped with the solenoid valve of opening and close through solenoid valve controller control.
2. The system for analyzing the gas generation collection time sequence of the thermal runaway reaction of the lithium ion battery according to claim 1, wherein the gas collection bag is sequentially opened according to the time sequence in the gas collection process to collect the gas in each sampling period.
3. The system for analyzing the thermal runaway reaction gas generation acquisition time sequence of the lithium ion battery according to claim 1, wherein a battery clamp (3) is arranged outside the lithium ion power battery (2) to enable the thermal runaway triggering and gas acquisition process to approach the actual pre-tightening force of the power battery system or the energy storage battery system.
4. The system for collecting and analyzing the lithium ion battery thermal runaway reaction produced gas collection sequence according to claim 1, wherein one end of the flexible gas conduit penetrates through a battery shell and is implanted into the lithium ion power battery (2), and collection of the thermal runaway reaction produced gas is realized through the internal and external pressure difference of the battery.
5. The system for collecting and analyzing the gas generation timing sequence of the thermal runaway reaction of the lithium ion battery according to claim 1, wherein the gas detection device (5) adopts a GC/FTIR gas detection instrument.
6. The system according to claim 2, wherein the generated gas is CO or CO2、H2、C2H4、CH4、C2H6And C3H6。
7. The system according to claim 1, wherein the solenoid valve controls the opening and closing of the gas collection bag to be in the order of milliseconds, so as to achieve high-frequency collection of gas produced during the thermal runaway reaction.
8. The system for analyzing the gas generation acquisition time sequence of the thermal runaway reaction of the lithium ion battery according to claim 3, wherein the heater (1) and the lithium ion power battery (2) are clamped together in a battery clamp (3).
9. An acquisition time sequence analysis method of a lithium ion battery thermal runaway reaction gas generation acquisition time sequence analysis system according to any one of claims 1 to 8, comprising the steps of:
1) starting a heater (1) to heat a lithium ion power battery (2) to trigger thermal runaway, starting an electromagnetic valve of a first gas collection bag in the 1 st sampling period of the thermal runaway reaction, and collecting reaction gas in the 1 st sampling period;
2) opening the electromagnetic valve of the second gas collection bag at the beginning of the 2 nd sampling period, and closing the electromagnetic valve of the first gas collection bag at the same time;
3) in each sampling period, repeating the step 2), opening the next gas acquisition bag and closing the previous gas acquisition bag until all sampling periods finish the acquisition according to the time sequence;
4) and respectively introducing the collected gas into gas detection equipment 5 to obtain gas components and corresponding percentages.
10. The acquisition time sequence analysis method according to claim 9, wherein in the step 4), after the gas production type and percentage of each time interval in the thermal runaway reaction process are obtained according to the time sequence, a lithium ion battery thermal runaway reaction database is formed and is used as a basis for subsequent lithium ion battery thermal runaway judgment.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115598206A (en) * | 2022-10-14 | 2023-01-13 | 吉林大学（Cn） | Lithium ion power battery thermal runaway gas production dynamics testing arrangement |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115598206A (en) * | 2022-10-14 | 2023-01-13 | 吉林大学（Cn） | Lithium ion power battery thermal runaway gas production dynamics testing arrangement |
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