CN114545248A - Characterization method and detection device for thermal runaway characteristic of lithium ion battery - Google Patents

Characterization method and detection device for thermal runaway characteristic of lithium ion battery Download PDF

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CN114545248A
CN114545248A CN202110824441.3A CN202110824441A CN114545248A CN 114545248 A CN114545248 A CN 114545248A CN 202110824441 A CN202110824441 A CN 202110824441A CN 114545248 A CN114545248 A CN 114545248A
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thermal runaway
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battery
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张道振
韩笑
王勇
陈彬
饶绍建
杨明
胡江生
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Wanxiang A123 Systems Asia Co Ltd
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Abstract

The invention discloses a characterization method and a detection device for thermal runaway characteristics of a lithium ion battery, and the characterization method for the thermal runaway characteristics of the lithium ion battery comprises the steps of placing batteries with different SOC states in a closed device to trigger thermal runaway, monitoring the surface temperature of the batteries before and after the thermal runaway in the device, the environmental temperature and the pressure change, calculating the thermal runaway gas production rate and the gas production speed according to an ideal gas state equation, and quantitatively characterizing the gas production speed and the gas production rate under the thermal runaway condition. The utility model provides a lithium ion battery thermal runaway characteristic detection device includes cavity, anchor clamps and heating plate, the cavity outside is connected with intake pipe and outlet duct respectively, the center at the cavity is established to anchor clamps, the heating plate is established in anchor clamps, the top of heating plate is equipped with the spatial position of installation battery, detection device is favorable to the research of battery thermal runaway gas production volume, the calculation of gas production speed and thermal runaway characteristic.

Description

Characterization method and detection device for thermal runaway characteristic of lithium ion battery
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a characterization method and a detection device for thermal runaway characteristics of a lithium ion battery.
Background
The lithium ion battery is one of the core components of the electric automobile, and the safety performance of the lithium ion battery is crucial to directly influence the life and property safety of people. The safety of the national standard on the power battery for the electric automobile is generally verified by tests such as overcharge, short circuit, heating, needling and the like, the fire and explosion do not occur and are taken as qualitative judgment standards, and no requirements are made on thermal characteristics such as thermal runaway trigger temperature, thermal runaway maximum temperature, heat generation quantity and the like. The thermal runaway thermal characteristic is used as a physical quantity for directly reflecting the thermal state of the battery, is used as one of main indexes for evaluating the safety of the power battery, and provides a theoretical basis for the cause, occurrence and evolution rule of the thermal runaway behavior of the power battery. In recent years, many reports have been made on the study of thermal runaway behavior of power batteries using thermal characteristics as a measure, and particularly on the study and analysis of thermal runaway behavior of large-capacity power batteries. For the research on the thermal runaway characteristic of the battery, most researches in the industry at present provide a controllable and accurate thermal insulation environment through an acceleration calorimeter (ARC), simulate the thermal characteristic in the heat release process when the heat in the battery cannot be timely dissipated, not only can obtain the thermal characteristic in the charge and discharge process of the battery, but also can reflect the kinetic parameters of the heat release reaction under the thermal runaway condition, and quantitatively represent the safety performance of the battery by using three key parameters, namely the initial temperature of the self-generated heat of the battery, the thermal runaway initiation temperature and the maximum temperature of the thermal runaway.
For example, the invention discloses a lithium battery thermal runaway tool and a test method disclosed in Chinese patent literature, and the publication number is "CN 111929582A", and relates to the field of lithium batteries. According to the invention, the test battery can be more conveniently clamped through the arranged heating aluminum plate, the adjusting screw, the positive electrode and the negative electrode of the battery, the heating pipe hole, the temperature sensor, the control cabinet, the temperature display and the power supply control switch, the clamping and fixing height can be adjusted, the test of batteries with different thicknesses can be flexibly performed, the device has a simple structure, the manufacturing cost is low, and the market circulation is easy. But does not relate to the quantitative analysis of the gas production speed, the gas production quantity and the like of the battery under the thermal runaway condition.
Disclosure of Invention
The invention aims to solve the problem that the gas production speed, the gas production rate and the temperature of the battery under the thermal runaway condition are not quantitatively evaluated in the existing open standard, method and research. The characterization method comprises the steps of placing batteries with different SOC states in a closed device to trigger thermal runaway, monitoring the surface temperature of the batteries before and after the thermal runaway in the device, the environmental temperature and the pressure change, calculating the thermal runaway gas production rate and the gas production speed according to an ideal gas state equation, and quantitatively characterizing the gas production speed and the gas production rate under the thermal runaway condition, thereby being beneficial to the research of the thermal runaway characteristics of the batteries.
In order to achieve the purpose, the invention adopts the following technical scheme: a lithium ion battery thermal runaway characteristic characterization method is characterized by comprising the following steps:
s1, installing the 30% SOC battery in a detection device, wherein the volume of a cavity of the detection device is V;
s2, adjusting the gas environment inside the cavity according to the requirement, introducing appropriate gas to replace the gas environment in the cavity, charging the 30% SOC battery to 100% SOC at the speed of 1C, standing until the environment temperature is stable, and recording the environment temperature T 1Temperature T of upper and lower surfaces of battery2、T3And pressure P1；
S3, heating the battery by using a heating sheet with power P to trigger a thermal runaway condition, recording the ambient temperature, the temperature of the upper surface and the lower surface of the battery and the air pressure in real time, and stopping heating by using the heating sheet when the temperature and the air pressure change to exceed the specified threshold values;
s4, collecting the surface temperature and the air pressure of the battery in the S3 in real time until the temperature and the air pressure are stable, and recording the leakage time t of the electrolyte or the gas1Triggering out-of-control time t2Time of pressure peak t3Pressure P at steady pressure2And temperature T1', calculating gas production rate and gas production rate;
s5, detecting gas components;
according to actual requirements, the gas environment in the cavity is adjusted, gases with different components are introduced, the ambient temperature in the cavity of the detection device and the temperatures of the upper surface and the lower surface of the battery are detected by the temperature sensors, the air pressure is detected by the pressure sensors, the heating plate below the installation position of the battery can heat the battery with stable power so as to trigger a thermal runaway condition, and when the temperature and the air pressure change to exceed the specified threshold values, the heating plate stops heating. The quantity change of temperature and air pressure is collected in real time, and the electrolyte or gas leakage time t is obtained by recording the relation graph of heating triggering thermal runaway temperature, air pressure and time 1Triggering out-of-control time t2Time of pressure peak t3Pressure P at steady pressure2And temperature T1The method comprises the steps of obtaining various data, calculating gas production rate and gas production rate, namely quantitatively representing the gas production rate and the gas production rate under the thermal runaway condition, setting the surface pressure of a battery to be 5-10 psi, arranging a heating plate below a battery core, setting the volume of a cavity to be V, and detecting the gas components in the cavity through an external gas component detection device.
Preferably, the specific calculation process of the gas production rate and the gas production rate in step S4 is that the gas production rate is calculated according to an ideal gas state equation according to the following formula:
Figure BDA0003173155110000021
the gas production rate is approximately calculated as:
Figure BDA0003173155110000022
Δ n is the amount of gas generating substance and v is the gas generation rate. And substituting the data read out from each detected sum chart into the calculation to obtain a result.
Preferably, the gas environment, the gas pressure and the temperature in the detection device before the test are adjustable. The stability of the whole device is ensured.
Preferably, the detection device is provided with a current collecting terminal and a voltage collecting terminal respectively. The battery is connected with the external charging and discharging equipment of the detection device through the current and voltage acquisition terminal, so that the charging or discharging of the battery is realized.
Preferably, the thermal runaway condition further includes a needle stick or overcharge. The two conditions of incontrollable heat of touch can also realize the calculation of gas production rate and gas production speed.
The utility model provides a lithium ion battery thermal runaway characteristic detection device, is applicable to foretell lithium ion battery thermal runaway characteristic characterization method, including cavity, anchor clamps and heating plate, the cavity outside is connected with intake pipe and outlet duct respectively, be equipped with first electronic valve in the intake pipe, be equipped with the second electronic valve on the outlet duct, anchor clamps are established at the center of cavity, the heating plate is established in anchor clamps, the top of heating plate is equipped with the spatial position of installation battery, inside first temperature sensor and the pressure sensor of being equipped with of cavity, the spatial position top of installation battery is equipped with second temperature sensor, the spatial position below of installation battery is equipped with third temperature sensor. The first temperature sensor and the pressure sensor respectively detect the cavity environment temperature and the cavity environment pressure, the second temperature sensor and the third sensor respectively detect the upper surface temperature and the lower surface temperature of the battery, the device ensures the triggering and the detection of the thermal runaway characteristic, the batteries with different SOC states are placed in the sealing device to trigger the thermal runaway, and the surface temperature, the environment temperature and the pressure change of the battery before and after the thermal runaway are monitored.
Preferably, the outer side of the cavity is connected with a detection air pipe, and the detection air pipe is connected with a gas component detection device. The gas component detection device detects gas components in the cavity.
Therefore, the invention has the following beneficial effects:
1. the gas production speed and the gas production rate under the thermal runaway condition are quantitatively represented, and the research on the thermal runaway characteristic of the battery is facilitated;
2. real-time monitoring of the temperature and pressure states of thermal runaway and thermal runaway gas generation components in different modes under different conditions in a limited space are realized.
Drawings
Fig. 1 is a schematic diagram of a lithium ion battery thermal runaway characteristic detection device according to the invention;
FIG. 2 is a graph of temperature, gas pressure and time for a heat triggered thermal runaway in accordance with the present invention;
FIG. 3 is an enlarged partial view of a graph of heat triggered thermal runaway temperature, gas pressure and time in accordance with the present invention;
in the figure: 1. the device comprises a device 2, an air inlet pipe 21, a first electronic valve 3, an air outlet pipe 31, a second electronic valve 4, a pressure sensor 5, a battery 6, a clamp 7, a heating plate 8, a first temperature sensor 9, a second temperature sensor 10 and a third temperature sensor.
Detailed Description
Example 1
The embodiment provides a method for characterizing thermal runaway characteristics of a lithium ion battery, which comprises the following steps:
s1, installing the 30% SOC battery in a detection device, wherein the volume of a cavity of the detection device is V;
s2, replacing the atmosphere in the cavity with argon with the purity of 99.99%, charging the battery with 30% SOC to 100% SOC at the speed of 1C, and recording the ambient temperature T when the ambient temperature is stable after standing 1Temperature T of upper and lower surfaces of battery2、T3And pressure P1；
S3, heating the battery by using a heating sheet with power P to trigger a thermal runaway condition, recording the ambient temperature, the temperature of the upper surface and the lower surface of the battery and the air pressure in real time, and stopping heating by using the heating sheet when the temperature and the air pressure change to exceed the specified threshold values;
s4, collecting the surface temperature and the air pressure of the battery in the S3 in real time until the temperature and the air pressure are stable, and recording the leakage time t of the electrolyte or the gas1Touch and touchTime t out of control2Time of pressure peak t3Pressure P at steady pressure2And temperature T1', calculating gas production rate and gas production rate;
s5, detecting gas components;
the 30% SOC battery is specifically installed in a clamp of a detection device cavity, the purpose of passing argon with the purity of 99.99% is to discharge air in the detection device cavity, the air interference to the method is prevented, the ambient temperature in the detection device cavity and the temperatures of the upper surface and the lower surface of the battery are detected by a temperature sensor, the air pressure is detected by a pressure sensor, a heating sheet located below the installation position of the battery can heat the battery with stable power so as to trigger a thermal runaway condition, and when the temperature and the air pressure change and exceed a specified threshold value, the heating sheet stops heating. The quantity change of temperature and air pressure is collected in real time, and the electrolyte or gas leakage time t is obtained by recording the relation graph of heating triggering thermal runaway temperature, air pressure and time 1Triggering out-of-control time t2Pressure peak time t3Pressure P at the time of pressure stabilization2And temperature T1' data of each item and calculation of gas production rate and gas production rate. The air condition parameters in the lower cavity in a stable state before and after thermal runaway are shown in the following table:
initial state P1＝105.0kPa T1＝302.65K
Steady state P2＝186.2625kPa T1′＝330.95K
。
The specific calculation process of the gas production rate and the gas production rate in the step S4 is that the gas production rate is calculated according to the ideal gas state equation as follows:
Figure BDA0003173155110000041
converting the gas generation rate into 25 ℃ and under 101.33kPa, the gas generation rate is approximately calculated as:
Figure BDA0003173155110000042
wherein, t is derived from FIGS. 2 and 33-t2And (6) s, wherein deltan is the amount of the substance generating the gas, and v is the gas production rate, so that the gas production rate and the gas production rate of the gas are calculated.
The stability of whole device is guaranteed to gaseous environment, atmospheric pressure and adjustable assurance of temperature before experimental in the detection device, is equipped with electric current, voltage acquisition terminal on the detection device, and the battery passes through electric current, voltage acquisition terminal and is connected with the outside charging and discharging equipment of detection device, realizes charging or discharging of battery itself, and in addition, triggers thermal runaway condition and still includes acupuncture or overcharge. The two conditions of incontrollable heat of touch can also realize the calculation of gas production rate and gas production speed. And finally, detecting the gas components in the cavity through an external gas component detection device.
Example 2
This example has provided a lithium ion battery thermal runaway characteristic detection device, be applicable to foretell lithium ion battery thermal runaway characteristic characterization method, refer to fig. 1, including cavity 1, anchor clamps 6 and heating plate 7, the cavity 1 outside is connected with intake pipe 2 and outlet duct 3 respectively, be equipped with first electronic valve 21 on the intake pipe 2, be equipped with second electronic valve 31 on the outlet duct 3, anchor clamps 6 are established at the center of cavity 1, heating plate 7 is established in anchor clamps 6, the top of heating plate 7 is equipped with the spatial position of installation battery 5. A first temperature sensor 8 and a pressure sensor 4 are arranged in the cavity 1, a second temperature sensor 9 is arranged above the spatial position of the battery 5, and a third temperature sensor 10 is arranged below the spatial position of the battery. The outer side of the cavity 1 is connected with a detection air pipe, and the detection air pipe is connected with a gas component detection device.
After the battery is installed in the clamp 6, the first electronic valve 21 of the air inlet pipe 2 is opened, argon with the purity of 99.99% enters the cavity 1 of the detection device through the air inlet pipe, in order to exhaust air in the cavity 1 of the detection device, the first temperature sensor 8 and the pressure sensor 4 respectively detect the cavity environment temperature and the cavity environment pressure, the second temperature sensor 9 and the third sensor 10 respectively detect the upper surface temperature and the lower surface temperature of the battery 5, then the lithium battery is charged to 100% SOC at the speed of 1C, the cavity environment pressure and the temperature and the upper surface temperature and the lower surface temperature of the battery are detected and recorded after standing, after the heating piece is heated and the thermal runaway is triggered, the cavity 1 environment temperature and the air pressure and the upper surface temperature and the lower surface temperature of the battery are recorded, the temperature and air pressure data are collected in real time, and the electrolyte or gas leakage time t is obtained through a detection statistical chart 1Triggering out-of-control time t2Time of pressure peak t3Pressure P at steady pressure2And temperature T1', thereby calculating the gas production rate and the gas production rate. And finally, the gas component detection device is used for detecting the components of the gas, so that the quantitative research on the thermal runaway characteristic of the battery is facilitated.

Claims (7)

1. A characterization method for thermal runaway characteristics of a lithium ion battery is characterized by comprising the following steps:
s1, installing the 30% SOC battery in a detection device, wherein the volume of a cavity of the detection device is V;
s2, adjusting the gas environment inside the cavity according to the requirement, introducing appropriate gas to replace the gas environment in the cavity, charging the 30% SOC battery to 100% SOC at the speed of 1C, standing until the environment temperature is stable, and recording the environment temperature T1Temperature T of upper and lower surfaces of battery2、T3And pressure P1；
S3, heating the battery by using a heating sheet with power P to trigger a thermal runaway condition, recording the ambient temperature, the temperature of the upper surface and the lower surface of the battery and the air pressure in real time, and stopping heating by using the heating sheet when the temperature and the air pressure change to exceed the specified threshold values;
s4, collecting the surface temperature and the air pressure of the battery in the S3 in real time until the temperature and the air pressure are stable, and recording the leakage time t of the electrolyte or the gas1Triggering out-of-control time t2Time of pressure peak t 3Pressure P at steady pressure2And temperature T1', calculating gas production rate and gas production rate;
and S5, detecting the gas components.
2. The method for characterizing the thermal runaway characteristics of the lithium ion battery according to claim 1, wherein the specific calculation process of the gas production rate and the gas production rate in the step S4 is that the gas production rate is calculated according to an ideal gas state equation, and the formula is as follows:
Figure FDA0003173155100000011
the gas production rate is approximately calculated as:
Figure FDA0003173155100000012
Δ n is the amount of gas generating substance and v is the gas generation rate.
3. The method for characterizing the thermal runaway characteristics of the lithium ion battery according to claim 1, wherein a gas environment, a gas pressure and a temperature before a test in the detection device are adjustable.
4. The method for characterizing the thermal runaway characteristics of the lithium ion battery according to claim 1, wherein the detection device is provided with current and voltage acquisition terminals respectively.
5. The method for characterizing the thermal runaway of a lithium ion battery according to claim 1, wherein the trigger thermal runaway condition further comprises a needle stick or an overcharge.
6. A lithium ion battery thermal runaway characteristic detection device adopts the lithium ion battery thermal runaway characteristic characterization method of claims 1-5, and is characterized by comprising a cavity (1), a clamp (6) and a heating plate (7), wherein the outer side of the cavity (1) is respectively connected with an air inlet pipe (2) and an air outlet pipe (3), the air inlet pipe (2) is provided with a first electronic valve (21), the air outlet pipe (3) is provided with a second electronic valve (31), the clamp (5) is arranged at the center of the cavity (1), the heating plate (7) is arranged in the clamp (6), a space position for installing a battery (5) is arranged above the heating plate (7), a first temperature sensor (8) and a pressure sensor (4) are arranged inside the cavity (1), a second temperature sensor (9) is arranged above the space position for installing the battery (5), and a third temperature sensor (10) is arranged below the spatial position where the battery (5) is arranged.
7. The lithium ion battery thermal runaway characteristic detection device according to claim 6, wherein a detection gas pipe is connected to the outside of the cavity (1), and the detection gas pipe is connected to a gas component detection device.
CN202110824441.3A 2021-07-21 2021-07-21 Characterization method and detection device for thermal runaway characteristic of lithium ion battery Pending CN114545248A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115079015A (en) * 2022-08-22 2022-09-20 苏州时代华景新能源有限公司 Quality evaluation method and system for lithium battery
CN115963400A (en) * 2023-03-17 2023-04-14 中国华能集团清洁能源技术研究院有限公司 Quantitative calculation method and system for hydrogen after thermal runaway of lithium ion battery

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115079015A (en) * 2022-08-22 2022-09-20 苏州时代华景新能源有限公司 Quality evaluation method and system for lithium battery
CN115079015B (en) * 2022-08-22 2022-12-20 苏州时代华景新能源有限公司 Lithium battery quality evaluation method and system
CN115963400A (en) * 2023-03-17 2023-04-14 中国华能集团清洁能源技术研究院有限公司 Quantitative calculation method and system for hydrogen after thermal runaway of lithium ion battery
CN115963400B (en) * 2023-03-17 2023-05-16 中国华能集团清洁能源技术研究院有限公司 Quantitative calculation method and system for hydrogen after thermal runaway of lithium ion battery

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