CN212433028U - Gas production detection device for battery - Google Patents

Gas production detection device for battery Download PDF

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CN212433028U
CN212433028U CN202021083552.0U CN202021083552U CN212433028U CN 212433028 U CN212433028 U CN 212433028U CN 202021083552 U CN202021083552 U CN 202021083552U CN 212433028 U CN212433028 U CN 212433028U
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battery
gas
sample tube
connecting pipe
control valve
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钱大艳
张亮
吴琼
张秦岳
董瑱
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Zhuhai Cosmx Battery Co Ltd
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Zhuhai Cosmx Battery Co Ltd
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Abstract

A battery gassing detection device includes: an adiabatic acceleration calorimeter; a source of purge gas; a gas composition analyzer; the system comprises a sample tube and/or a battery gas production detection assembly, wherein the sample tube and/or the battery gas production detection assembly is arranged in a heat insulation cavity of the heat insulation acceleration calorimeter, the sample tube is provided with a sample tube gas inlet and a sample tube gas outlet, the sample tube gas inlet is communicated with a purge gas source, and the sample tube gas outlet is communicated with a gas inlet of a gas component analyzer; the battery gas production detection assembly comprises a battery gas inlet connecting pipe and a battery gas outlet connecting pipe, the battery gas inlet connecting pipe is used for communicating the purging gas source with a battery gas inlet, and the battery gas outlet connecting pipe is used for communicating the gas component analyzer with a battery gas outlet; the first air inlet pipeline control valve is used for controlling the on-off of the purging gas inlet pipeline; and the first gas outlet pipeline control valve is used for controlling the on-off of the sample gas production and discharge pipeline. The utility model discloses a detection device can carry out real-time online gas production to battery raw and other materials and electric core and detect.

Description

Gas production detection device for battery
Technical Field
The utility model belongs to the technical field of the battery detects, more specifically says, relates to an utilize adiabatic acceleration calorimeter (ARC) to carry out the device that detects to the inside gas production composition of battery material or battery.
Background
Lithium ion batteries have been widely used in consumer electronics, energy storage devices, and new energy vehicles due to their excellent performance. The lithium ion battery mainly comprises flammable electrode materials and electrolyte, and is very easy to cause self-heat release of the battery under abuse conditions, so that thermal runaway of the battery is caused, even explosion can occur, and the lithium ion battery is a root cause of frequent safety accidents of the lithium ion battery. Different gases can be generated in the thermal decomposition process of the battery raw material, and the research on the gas components generated in the self-heat release stage of the lithium ion battery, particularly the gas generation mechanism, is an effective means for improving the safety performance of the battery.
At present, the battery gas production test method in the industry needs to enable the battery to produce enough gas to carry out related tests, and the battery raw material gas production at different temperatures cannot be tested on line in real time. Some instrument manufacturers propose a TGA (Thermogravimetric Analysis, TGA for short) and GC-MS (gas chromatography-mass spectrometry) combination scheme to test the gas generated by the battery, but the temperature control precision of the TGA is poor, the defects of excessive purge gas and too fast temperature rise rate exist, and the condition that a finished product battery core cannot be tested exists. Therefore, a device capable of detecting the gas generated from the raw material of the battery or the gas generated from the battery cell in real time on line is needed, so as to facilitate the research on the gas generation mechanism of the battery in the self-heat release stage.
SUMMERY OF THE UTILITY MODEL
The utility model aims at providing a battery gas production detection device based on ARC can produce gas or the product gas of electricity core detects battery raw and other materials in real time on line.
In order to achieve the above object, the present invention adopts the following technical solutions:
a battery gassing detection device includes: an adiabatic acceleration calorimeter; a source of purge gas; a gas composition analyzer; the sample tube and/or the battery gas production detection assembly is arranged in a heat insulation cavity of the heat insulation acceleration calorimeter, wherein the sample tube is provided with a sample tube gas inlet and a sample tube gas outlet, the sample tube gas inlet is communicated with the purging gas source, and the sample tube gas outlet is communicated with a gas inlet of the gas component analyzer; the battery gas production detection assembly comprises a battery gas inlet connecting pipe and a battery gas outlet connecting pipe, the battery gas inlet connecting pipe is used for communicating the purging gas source with a battery gas inlet, and the battery gas outlet connecting pipe is used for communicating the gas component analyzer with a battery gas outlet; the first air inlet pipeline control valve is used for controlling the on-off of the purging gas inlet pipeline; and the first gas outlet pipeline control valve is used for controlling the on-off of the sample gas production and discharge pipeline.
Further, the gas component analyzer is a gas chromatography-mass spectrometer or a gas chromatography analyzer.
Furthermore, the battery gas production detection assembly further comprises a first purging branch pipe and a second purging branch pipe, the first purging branch pipe and the second purging branch pipe are both communicated with the purging gas source, the first purging branch pipe is connected to the gas outlet end of the battery gas inlet connecting pipe and provided with a first purging branch pipe control valve, and the second purging branch pipe is connected to the gas inlet end of the battery gas outlet connecting pipe and provided with a second purging branch pipe control valve; and a second air inlet pipeline control valve is arranged between the first scavenging branch pipe and the battery air inlet, and a second air outlet pipeline control valve is arranged between the second scavenging branch pipe and the battery air outlet.
Preferably, the battery air inlet connecting pipe and the battery air outlet connecting pipe are respectively provided with a flowmeter.
Preferably, a thermostat is arranged on the battery air outlet connecting pipe.
Further, the thermostat is a peltier thermostat.
Preferably, a filtering device is arranged at the air inlet of the battery and/or the air outlet of the battery.
Preferably, the battery gas production detection assembly further comprises a battery clamping plate pair for clamping the soft package battery.
According to the above technical scheme, the utility model discloses utilize ARC to carry out battery production test, ARC test is gone on under adiabatic state, the accuse temperature precision is high, it is accurate to heat up, and equipment can look for exothermic stage, thereby realize different stages, especially from the real-time online test of production of exothermic stage battery raw and other materials and electric core, ARC equipment's adiabatic cavity is except can realizing carrying out the analysis to specific material under isolated air and adiabatic environment simultaneously, can also avoid interference experiment results such as water in the air and carbon dioxide, form the test environment that does not interfere, it is more accurate and effective to make the testing result. In addition, benefit from ARC insulation chamber's multilayer explosion-proof structure, the utility model discloses especially, be fit for being used for having the gas production of certain dangerous sample and detect, the utility model discloses an ARC can be used jointly with gas composition analytical instruments such as GC, GC-MS, provides more test scheme, and application scope is wider.
Drawings
In order to illustrate the embodiments of the present invention more clearly, the drawings that are needed in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings can be obtained by those skilled in the art without inventive effort.
Fig. 1 is a schematic structural diagram of an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of a sample tube according to an embodiment of the present invention;
fig. 3 is a schematic diagram of a battery gas circuit when the embodiment of the utility model is used for detecting the soft package battery;
fig. 4 is a schematic diagram of the detection of the pouch battery according to the embodiment of the present invention;
fig. 5 is a schematic diagram of a battery gas circuit when the square aluminum-shell battery is detected by adopting the embodiment of the utility model;
fig. 6 is a schematic view illustrating a use of a battery clamping plate according to an embodiment of the present invention;
FIG. 7 is a temperature rise curve diagram of a sample to be tested when the embodiment of the present invention is used for testing;
FIG. 8 is a graph showing the results of gas components that have evolved from the initial heat release at 90 ℃ when measured by the embodiment of the present invention;
FIG. 9 is a graph showing the results of the gas components which strongly self-release heat and generate a large amount of gas at 120 ℃ when the embodiment of the present invention is used for detection.
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings, wherein for convenience of illustration, the drawings showing the structure of the device are not to scale and are partially enlarged, and the drawings are only examples, which should not limit the scope of the invention. It should be noted that the drawings are in simplified form and are not to precise scale, which is only used for the purpose of facilitating and clearly assisting in the description of the embodiments of the present invention.
As shown in fig. 1 and fig. 2, the battery gas production detection apparatus of this embodiment is used for performing real-time online detection on a lithium battery raw material or a battery core gas production process, and includes an adiabatic acceleration calorimeter 1, a gas component analyzer 2, and a purge gas source 3, where a sample tube 1-1 is disposed in the adiabatic acceleration calorimeter 1, a sample to be detected is placed in the sample tube 1-1, and the gas component analyzer 2 may be a gas chromatography-mass spectrometry (GC-MS) or a Mass Spectrometry (MS) or a Gas Chromatography (GC). The sample tube 1-1 is provided with a sample tube gas inlet 1-1a and a sample tube gas outlet 1-1b, wherein the sample tube gas inlet 1-1a is communicated with a purge gas source 3 through a connecting pipeline, and the sample tube gas outlet 1-1b is communicated with a gas inlet of a gas component analyzer 2 through a connecting pipeline. A first air inlet pipeline control valve A is arranged at the position of the air inlet 1-1a of the sample tube or on a connecting pipeline connected with the air inlet 1-1a of the sample tube and is used for controlling the on-off of a purging gas inlet pipeline (a pipeline between a purging gas source and the air inlet of the sample tube); a first gas outlet pipeline control valve B is arranged at the gas outlet 1-1B of the sample tube or on a connecting pipeline connected with the gas outlet 1-1B of the sample tube and is used for controlling the on-off of a gas outlet pipeline (a pipeline between the gas outlet of the sample tube and a gas component analyzer) of the sample. The connecting pipeline can be a high-temperature-resistant metal pipeline, such as a stainless steel pipe, a copper pipe, an aluminum pipe and the like. Argon was used as the purge gas in this example. The purging gas enters the sample tube 1-1 from the gas source 3 of the purging gas through the connecting pipeline from the gas inlet 1-1a of the sample tube, and the gas generated by the sample to be detected enters the gas component analyzer 2 for analysis through the gas outlet 1-1b of the sample tube. The sample tube may be spherical, tubular or square in shape. The setting mode of air inlet and gas outlet on the sample cell includes: and the air path design modes of air inlet and air outlet at the same side, air inlet at one side, air outlet at the bottom end, air outlet at the top end, air outlet at the middle air inlet top end and the like are adopted.
The utility model discloses a detection device can detect by the raw and other materials of lithium cell, and the raw and other materials of lithium cell include but not limited to anodal powder, negative pole powder, gluing agent, conductive agent, electrolyte, lithium salt, esters etc.. When the lithium battery raw material is detected, a sample to be detected is placed into the sample tube 1-1, then the air inlet pipeline control valve A is opened, argon is used for purging the sample tube 1-1 for a period of time, such as 10 minutes, so as to remove air in the sample tube 1-1, and then the first air inlet pipeline control valve A is closed. The sample tube is located in a heat insulation cavity of the heat insulation acceleration calorimeter 1, the heat insulation acceleration calorimeter 1 is started for testing, when the temperature in the heat insulation cavity rises to the temperature required by testing, the first air inlet pipeline control valve A and the air outlet pipeline control valve B are opened, argon enters the sample tube through the first air inlet pipeline control valve A for blowing, the first air inlet pipeline control valve A is closed after blowing is completed, and gas generated by a sample to be tested in the sample tube 1-1 enters the gas component analyzer 2 from the sample tube gas outlet 1-1B through the first air outlet pipeline control valve B, so that gas components can be analyzed.
The utility model discloses a detection device also can test laminate polymer battery (3C consumer battery, soft packet of power battery, soft packet of abnormal shape battery) or square aluminum hull battery, as shown in fig. 3 for carry out gas composition to the battery and examine time measuring, the utility model discloses a detection device still includes the gas detection subassembly is produced to the battery, and this gas detection subassembly is produced to the battery includes the battery gas inlet connection pipe 4 and the battery gas outlet connection pipe 5 of being connected with the battery, and the battery gas inlet connection pipe 4 links to each other with the gaseous air supply that sweeps, and the battery gas outlet connection pipe 5 links to each other with the gas inlet of gaseous composition analysis appearance. An air inlet pipeline control valve (a first air inlet pipeline control valve A and a second air inlet pipeline control valve E) is arranged on the battery air inlet connecting pipe 4 and used for controlling the on-off of a purging gas inlet pipeline between a battery air inlet and a purging gas source, and an air outlet pipeline control valve (a first air outlet pipeline control valve B and a second air outlet pipeline control valve F) is arranged on the battery air outlet connecting pipe 5 and used for controlling the on-off of a sample gas production and discharge pipeline between a battery air outlet and a gas composition analyzer. The battery inlet connecting pipe 4 and the battery outlet connecting pipe 5 are high temperature resistant pipes, such as stainless steel pipes, copper pipes, aluminum pipes, polymer pipes (PEEK, PE, PP, PA), and the like. Preferably, the present embodiment further includes a first branch purge gas pipe 6 and a second branch purge gas pipe 7, both the first branch purge gas pipe 6 and the second branch purge gas pipe 7 are communicated with a purge gas source, the first branch purge gas pipe 6 is connected to the gas outlet end of the battery gas inlet connecting pipe 4 (i.e. the end of the battery gas inlet connecting pipe 4 connected to the battery gas inlet), and is provided with a first branch purge gas pipe control valve C, the second branch purge gas pipe 7 is connected to the gas inlet end of the battery gas outlet connecting pipe 5 (i.e. the end of the battery gas outlet connecting pipe 5 connected to the battery gas outlet), and is provided with a second branch purge gas pipe control valve D; the second inlet pipe control valve E is located between the first purge gas branch pipe 6 and the battery inlet, and the second outlet pipe control valve F is located between the second purge gas branch pipe 7 and the battery outlet. More preferably, a filtering device 8 is disposed at the air inlet and the air outlet of the battery, and the filtering material of the filtering device 8 may be an inorganic material or an organic material.
As a preferred embodiment of the utility model, this embodiment all is provided with flowmeter 11 at battery connecting pipe 4 and battery connecting pipe 5 of giving vent to anger, and flowmeter 11 has timing function and data derivation function, can realize detecting gas volume ration. The flowmeter can adopt 316 stainless steel flowmeter, and EPDM is used as sealing material. Furthermore, a thermostat 12 can be disposed on the battery outlet connection pipe 5 to control the temperature of the gas fed to the gas component analyzer 2, and the thermostat 12 of the present embodiment is a peltier thermostat of 12706 ceramic semiconductor, and has a working voltage of 5V and a control temperature of 25 ± 1 ℃.
Referring to fig. 3 and 4, when testing the soft package battery, first closing the second air inlet pipeline control valve E, opening the first air inlet pipeline control valve a and the first scavenging branch pipe control valve C, and introducing argon gas from the first scavenging branch pipe 6 to purge the battery air inlet connecting pipe 4, for example, purging for 5 minutes, so as to remove air in the battery air inlet connecting pipe 4 and eliminate air interference; the same operation is performed on the battery gas outlet connecting pipe 5 (the purging operations of the two pipelines can be performed simultaneously), the second gas outlet pipeline control valve F is closed, the first gas outlet pipeline control valve B and the second purging branch pipe control valve D are opened, argon gas is introduced from the second purging branch pipe 7 to purge the battery gas outlet connecting pipe 5, and air in the battery gas outlet connecting pipe 5 is removed. After air is removed, the first air inlet pipeline control valve A and the first scavenging branch pipe control valve C are in a closed state, the second air inlet pipeline control valve E is in an open state, the second scavenging branch pipe control valve D is in a closed state, and the first air outlet pipeline control valve B and the second air outlet pipeline control valve F are in an open state. Open adiabatic acceleration calorimeter 1 and test, when the temperature in the adiabatic cavity risees to the required temperature of test, open first air inlet pipeline control valve A, argon gas sweeps in getting into the battery from battery air inlet connecting pipe 4, closes first air inlet pipeline control valve A after sweeping, and the gas that produces in the battery is given vent to anger from battery connecting pipe 5 and is got into gas composition analysis appearance 2 to can carry out the analysis to gas composition.
Because laminate polymer battery can cause certain bulging at the gas production in-process that releases heat certainly, in order to guarantee good detection effect, as shown in fig. 5, the utility model discloses a detection device still includes battery splint to 9, and laminate polymer battery 100 places between two battery splint 9, by the centre gripping of battery splint 9, accessible threaded fastener 10 links together between the battery splint 9.
The detection process for the square aluminum-shell battery is similar, as shown in fig. 6, the second air inlet pipeline control valve E and the second air outlet pipeline control valve F are closed, the first air inlet pipeline control valve a, the first purging branch pipe control valve C, the first air outlet pipeline control valve B and the second purging branch pipe control valve D are opened, argon is introduced from the first purging branch pipe 6 to purge the battery air inlet connecting pipe 4, and argon is introduced from the second purging branch pipe 7 to purge the battery air outlet connecting pipe 5. After air is removed, the first air inlet pipeline control valve A and the first scavenging branch pipe control valve C are in a closed state, the second air inlet pipeline control valve E is in an open state, the second scavenging branch pipe control valve D is in a closed state, and the first air outlet pipeline control valve B and the second air outlet pipeline control valve F are in an open state. Open adiabatic acceleration calorimeter 1 and test, when the temperature in the adiabatic cavity risees to the required temperature of test, open first air inlet pipeline control valve A, argon gas sweeps in getting into the battery from battery air inlet connecting pipe 4, closes first air inlet pipeline control valve A after sweeping, and the gas that produces in the battery is given vent to anger from battery connecting pipe 5 and is got into gas composition analysis appearance 2 to can carry out the analysis to gas composition.
The detection device of the embodiment is adopted to detect the lithium ion soft package battery of the lithium cobaltate system, and the detection conditions are as follows: setting the cut-off temperature of ARC at 170 ℃, scanning at 5 ℃ in each step to determine whether self-heat release exists, wherein the slope sensitivity is 0.02 ℃/min, and the waiting time is 15 minutes; a heating-waiting-searching cyclic pattern is used. Setting the temperature of a sample inlet of a GC at 250 ℃, the split ratio of 30:1, the split flow of 30ml/min, the temperature raising program of a column incubator at 60 ℃ for 3.5min, then raising the temperature to 180 ℃ at 20 ℃/min, and using Agilent G3591 series packed columns with the size of 30m multiplied by 0.53mm multiplied by 20 mu m; the carrier gas was 99.999% high purity Ar. When the detection is started, the time for setting the flowmeter is consistent with the time of the ARC system, meanwhile, the thermostat is started, gas which is already gas-produced when the gas is just started to release heat at 90 ℃ and gas which is violently released and produces a large amount of gas at 120 ℃ are respectively collected according to actual experiment requirements, and the collected gas is tested by using a GC. The parameter settings of ARC and GC or GC-MS can be modified accordingly according to actual requirements to achieve optimal testing effect.
Referring to fig. 7, 8 and 9, it can be seen from the detection results that the proportion of carbon dioxide generated in the initial heat release phase of the cell is only 16%, and when the cell enters the severe heat release phase, the proportion of carbon dioxide generated is as high as 90%, so that the data can be used for optimizing the cell orientation performance.
In addition, the matching of the electrolyte and the anode material can be directionally improved by combining the measurement data (shown in the following table) of the flowmeter and analyzing the gas production rate at different stages, so that the battery performance is purposefully improved, and the customer requirements in different fields are met.
Figure BDA0002537400060000071
The utility model discloses a detection device can carry out real-time online gas production to battery raw and other materials and electric core and detect, has especially realized the gas production from exothermic stage and has detected, with ARC and GC or GC-MS or MS test scheme that allies oneself with, can carry out accurate analysis to specific material under specific adiabatic environment, the gas composition result that reachs is more accurate and effective, more can match the kind that battery material produced gas in different stages to more accurate research and development is fit for the material.
The above embodiments are only used to illustrate the technical solutions of the present invention and not to limit the same, although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that the present invention can still be modified or replaced with equivalents, and any modification or equivalent replacement without departing from the spirit and scope of the present invention should be covered by the scope of the present invention.

Claims (8)

1. A battery gas production detection device is characterized by comprising:
an adiabatic acceleration calorimeter;
a source of purge gas;
a gas composition analyzer;
the sample tube and/or the battery gas production detection assembly is arranged in a heat insulation cavity of the heat insulation acceleration calorimeter, wherein the sample tube is provided with a sample tube gas inlet and a sample tube gas outlet, the sample tube gas inlet is communicated with the purging gas source, and the sample tube gas outlet is communicated with a gas inlet of the gas component analyzer; the battery gas production detection assembly comprises a battery gas inlet connecting pipe and a battery gas outlet connecting pipe, the battery gas inlet connecting pipe is used for communicating the purging gas source with a battery gas inlet, and the battery gas outlet connecting pipe is used for communicating the gas component analyzer with a battery gas outlet;
the first air inlet pipeline control valve is used for controlling the on-off of the purging gas inlet pipeline;
and the first gas outlet pipeline control valve is used for controlling the on-off of the sample gas production and discharge pipeline.
2. The battery gassing detection device of claim 1 wherein: the gas component analyzer is a gas chromatography-mass spectrometer or a gas chromatography analyzer.
3. The battery gassing detection device of claim 1 wherein: the battery gas production detection assembly further comprises a first purging branch pipe and a second purging branch pipe, the first purging branch pipe and the second purging branch pipe are both communicated with the purging gas source, the first purging branch pipe is connected to the gas outlet end of the battery gas inlet connecting pipe and provided with a first purging branch pipe control valve, and the second purging branch pipe is connected to the gas inlet end of the battery gas outlet connecting pipe and provided with a second purging branch pipe control valve; and a second air inlet pipeline control valve is arranged between the first scavenging branch pipe and the battery air inlet, and a second air outlet pipeline control valve is arranged between the second scavenging branch pipe and the battery air outlet.
4. The battery gassing detection device of claim 1 wherein: and flowmeters are respectively arranged on the battery air inlet connecting pipe and the battery air outlet connecting pipe.
5. The battery gassing detection device of claim 1 wherein: and a thermostat is arranged on the battery air outlet connecting pipe.
6. The battery gassing detection device of claim 5 wherein: the thermostat is a Peltier thermostat.
7. The battery gassing detection device of claim 1 wherein: and a filtering device is arranged at the air inlet of the battery and/or the air outlet of the battery.
8. The battery gassing detection device of claim 1 wherein: the battery gas production detection assembly further comprises a battery clamping plate pair used for clamping the soft package battery.
CN202021083552.0U 2020-06-12 2020-06-12 Gas production detection device for battery Active CN212433028U (en)

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