JP6730056B2 - Method and apparatus for analyzing generated gas of power storage device - Google Patents

Description

The present invention relates to a method and an apparatus for analyzing generated gas of an electricity storage device, which collects and analyzes gas generated from the electricity storage device.

In recent years, lithium ion batteries and the like have been widely used as power storage devices. Lithium-ion batteries have high versatility because of their high energy density and good performance balance. However, there is still a problem regarding safety such that the electrolytic solution inside is decomposed and vaporized due to abrupt heat generation, and a harmful gas is generated. Therefore, an analyzer that analyzes the gas generated during the safety evaluation test of the lithium-ion battery and evaluates its safety has been proposed (for example, Patent Document 1). In this analyzer, as shown in FIG. 6, a power storage device 11 is set in a test container 19 that serves as a sealed pressure resistant booth, and a safety evaluation test for short-circuiting the power storage device 11 is performed. The total amount of gas generated during this test is collected in the gas bag 71 communicating with the buffer tank 67 through the pipe 65, and the gas accumulated in the gas bag 71 is analyzed. According to this test apparatus, the entire amount of gas generated from the electricity storage device 11 is collected during the safety evaluation test, and the collected gas is collectively provided for analysis after the test.

JP, 2011-3513, A

However, according to the above method, although it is possible to analyze the total amount of generated gas and gas components generated from the start to the end of the test, changes in the gas amount during the test and changes in each gas component However, there is a problem in that it is not possible to grasp the changes over time.

Therefore, an object of the present invention is to provide a method for analyzing generated gas of an electricity storage device, which is capable of analyzing a temporal change of gas generated from the electricity storage device during the test while performing a safety evaluation test of the electricity storage device.

The present invention provides the following generated gas analysis method for an electricity storage device.
A method for analyzing generated gas of an electricity storage device, which collects and analyzes gas generated from the electricity storage device, the method comprising:
A test container in which the power storage device having a housing is housed inside the container together with the housing, and the inside of the container is filled with an inert gas; a plurality of sample containers held at an internal pressure lower than that of the test container; A gas including a plurality of communication flow paths for communicating a test container and a plurality of the sample containers, and a flow path opening/closing valve provided between the test container and the sample container of the plurality of communication flow paths, respectively. Using a collector, after closing the flow passage opening/closing valve and starting a safety evaluation test of the electricity storage device, the flow passage opening/closing valves provided in the plurality of communication passages are provided for each of the communication passages. Opening and closing operations at different timings sequentially, and sucking and collecting the internal gas of the test container at the timing when the flow path opening and closing valve opens and closes in the sample container communicating with the opened and closed flow path opening and closing valve. When,
A step of analyzing the internal gas collected in each of the plurality of sample containers at different timings, for each sample container;
And a method for analyzing generated gas of an electricity storage device .

According to the present invention, it is possible to analyze the change with time of the generated gas during the safety evaluation test of the electricity storage device.

It is a typical block diagram which is a 1st structural example of the generated gas analyzer of an electrical storage device. It is a typical block diagram of the analyzer of a 2nd structural example. It is a graph which shows the mode of time change of battery surface temperature, atmosphere temperature, and voltage which the data logger of the analyzer of the 1st example of composition recorded. 7 is a graph showing changes in voltage, current, battery temperature, and ambient temperature recorded by the data logger of the analyzer of the second configuration example with respect to the charging depth. It is a graph which shows the result of having analyzed a part of gas generated during a test continuously with the analyzer. It is a typical block diagram which shows the conventional analyzer. It is a graph which shows the mode of the time change of voltage, nail penetration depth, battery surface temperature, and atmospheric temperature by the conventional analyzer.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
<First configuration example>
FIG. 1 is a schematic configuration diagram of an evolved gas analyzer 100 for an electricity storage device. The generated gas analyzer for the electricity storage device (hereinafter abbreviated as “analyzer”) 100 collects gas generated from the electricity storage device 11 during a safety evaluation test of the electricity storage device 11, and analyzes the collected gas. To do. The electricity storage device 11 used here is, for example, a lithium ion battery, but may be another type of battery.

The analyzer 100 includes a gas collector 13 for collecting gas generated from the electricity storage device 11, an analyzer 15 for analyzing the gas collected by the gas collector 13, and a data logger 45 described later. Equipped with.

The gas collector 13 includes a test container 19 and one or more gas collection lines 21 connected to the test container 19. The test container 19 houses the electricity storage device 11 in the container interior 17, and the container interior 17 is filled with an inert gas. In this state, the safety evaluation test of the electricity storage device 11 is performed. Further, the gas collection line 21 in the illustrated example has a configuration having a total of four lines, but is not limited to this, and an arbitrary number of gas collection lines can be arranged.

The gas collection line 21 has a communication channel 23 extending from the housing of the test container 19 or the power storage device 11. In this communication flow path 23, an upstream flow path opening/closing valve 27, a sample container 29, and a downstream flow path opening/closing valve 31 are arranged in order from the test container 19 side.

The upstream channel opening/closing valve 27 is, for example, an electromagnetic valve that is opened/closed by a drive signal, and limits the flow of gas into the sample container 29. The sample container 29 is a gas collection container, is connected to a vacuum pump or the like (not shown), and is maintained at an internal pressure lower than that of the test container 19. The downstream flow passage opening/closing valve 31 is closed when the gas is collected in the sample container 29, and is opened when the collected gas collected in the sample container 29 is sent to the analyzer 15.

The tip of the communication channel 23 on the side of the test container 19 may be arranged inside the housing of the electricity storage device 11 as in the illustrated example, or may be opened inside the test container 19 near the outside of the electricity storage device 11.

The test container 19 is provided with a nail insertion portion 33 for performing a nail penetration test which is one of safety evaluation tests. The nail insertion portion 33 has a nail portion 33a at the tip thereof that pierces the electricity storage device 11, and the nail portion 33a is supported so as to be vertically movable. The vertical movement of the nail portion 33a may be manual, or may be operation by a drive mechanism such as a motor.

Further, a temperature sensor 35 that detects the temperature of the electricity storage device 11 is arranged on the surface of the electricity storage device 11 housed in the test container 19. Inside the test container 19, a temperature sensor 37 that detects the ambient temperature of the electricity storage device 11 is arranged. A thermocouple, a thermistor, or the like can be used as the temperature sensors 35 and 37.

To the electrode terminals 41A and 41B of the electricity storage device 11, a current/voltage detector 43 that detects the current and voltage of the electricity storage device 11 is connected. The temperature sensors 35 and 37 and the current/voltage detector 43 are connected to the data logger 45. The data logger 45 records changes over time in the output signals of the connected temperature sensors 35 and 37 and the current/voltage detector 43. The above-mentioned respective parts are integrally controlled by a gas collection drive part (not shown).

Next, a method of analyzing the generated gas using the analyzer 100 having the above configuration will be described.
First, the power storage device 11 to be tested is set in the test container 19. The temperature sensor 35 is attached to the surface of the electricity storage device 11, and the probe of the current/voltage detector 43 is attached to the electrode terminals 41A and 41B of the electricity storage device 11. Then, the inside of the test container 19 accommodating the electricity storage device 11 is filled with an inert gas such as helium gas or nitrogen gas from an inert gas supply unit (not shown).

On the other hand, in the gas collection line 21, both the upstream flow passage opening/closing valve 27 and the downstream flow passage opening/closing valve 31 are closed, and the internal pressure of the sample container 29 is reduced by a vacuum pump (not shown). At this time, the internal pressure of the sample container 29 is made lower than the internal pressure of the test container 19.

After completing the above-described preparation process, the nail piercing portion 33 is driven to pierce the electricity storage device 11 with the nail portion 33a, and the safety evaluation test is started.

After the safety evaluation test is started, gas is generated from the inside of the housing of the electricity storage device 11. The generated gas is sequentially collected by the plurality of gas collection lines 21 at different timings. This gas collection method will be specifically described below.

The safety evaluation test is started in a state where both the upstream side flow passage opening/closing valve 27 and the downstream side flow passage opening/closing valve 31 are closed. After the test is started, the upstream side flow passage opening/closing valves 27 provided in the plurality of communication flow passages 23 are sequentially opened at different timings. Then, the internal pressure in the test container 19 or the housing of the electricity storage device 11 is sucked through the communication channel 23 due to the internal pressure of the sample container 29. The sucked gas is taken into the sample container 29. Then, for each gas collection line 21, the upstream side flow passage opening/closing valve 27 is closed when the internal pressure of the sample container 29 reaches the atmospheric pressure or after a predetermined time.

As a result, the sample container 29 of each gas collection line 21 collects the gas sucked from the test container 19 side at the timing of opening and closing the upstream flow passage opening/closing valve 27 for each gas collection line 21. .. That is, the gas sucked from the inside of the housing of the test container 19 or the power storage device 11 is collected in each sample container 29 at different timings with time.

Next, the gas collected in each sample container 29 is sequentially analyzed by the analyzer 15 for each sample container 29. For example, the sample containers 29 of the plurality of gas collection lines 21 are set on the analyzer 15 in the order of earlier opening/closing operation of the upstream side flow path opening/closing valve 27 on the time axis, Analyze the collected gas.

In the step of analyzing the collected gas by the analyzer 15, analysis based on at least one of GC-MS method, GC method, IC method, ICP-AES method, ICP-MS method, absorptiometry method, and IR method is performed. It is a process.

The GC-MS (Gas Chromatograph Mass Spectrometry) method is an analysis method using a gas chromatograph-mass spectrometer. According to this method, a chromatogram represented by the detection time on the horizontal axis and the detection intensity on the vertical axis is measured, and the gas species is identified from the mass spectrum measured for each component separated based on this. The GC (Gas Chromatograph) method is an analysis using the above chromatogram.

In the IC (Immunochromatography) method, a solution sample is passed through an ion exchange resin to separate the contained ionic species, and the electrical conductivity is measured. It is a measuring method for quantitatively determining the content of ionic species in a sample from the relational line between the electric conductivity and the content of ions prepared in advance with a standard solution.

The ICP-AES (Inductively Coupled Plasma Atomic Emission Spectroscopy) method is an emission spectroscopic analysis method using a high frequency inductively coupled plasma (ICP) as a light source. The sample solution is atomized and introduced into Ar plasma, and the light emitted when the excited element returns to the ground state is dispersed, and the element is qualitatively determined from the wavelength and quantitatively determined from the intensity.

An optimum method is selected from the above-described analysis methods according to the type of the power storage device 11, the evaluation item, and the evaluation purpose.

Further, the safety evaluation test of the electricity storage device 11 is not limited to the nail penetration test described above, and may be, for example, an overcharge test, a heating test, an external short circuit test, an overdischarge test, a crush test, a charge/discharge test, a storage test, or the like. It may be either.

Explaining each test concretely, the overcharge test is a test for evaluating durability against a voltage equal to or higher than the charging voltage, for example, UN 38.3.4.7, IEC62660-2 6.3.2, UL2580 8, UL2271 7.2, SAE. 2464 4.5.2, QC/T743-2006 6.2.12.2, 6.3.8.2, KMVSS 48.6.2, SBA S1101:2011 8.2.5 and the like.

In the heating test, a single cell of the electricity storage device is subjected to a heating test with a heater, and the temperature of the cell surface and the temperature of the gas ejected are measured. For example, the temperature of the battery is raised at a constant rate, and after reaching a predetermined temperature, the temperature is sufficiently maintained for a long time, and it is confirmed that smoking, ignition and rupture do not occur. Regarding the test temperature, for example, the UL standard [Underwriters Laboratories Inc., UL1642 (lithium battery)] is 150° C., and the lithium secondary battery safety evaluation standard guideline (Battery Industry Association) is 130° C.

The external short-circuit test is a test in which the electrodes of the battery are short-circuited with a small resistance, and examples thereof include tests of the following standards. UN 38.3.4.5, IEC62660-2 6.3.1, UL2580 9, UL2271 7, SAE 2464 4.5.1, QC/T743-2006 6.2.12.3, 6.3.8.3, KMVSS 48.6.5, SBA S1101:2011 8.2.1

In the crush test, for example, according to the safety standard defined in IEC62133, even if a flat plate is applied with a load of up to 13 kN, it does not ignite.

Storage tests are specified in ISO 12405-1, IEC 62660-1, JIS C 8711, QC/T 743, etc.

The charge/discharge test is a test for evaluating deterioration of a battery by repeatedly performing charging and discharging, and the over-discharge test is a test for evaluating deterioration of the battery when left in a discharged state.

According to the analyzer 100 of this configuration, while performing the safety evaluation test of the electricity storage device 11, the gas generated from the electricity storage device 11 during the test is sequentially collected in the plurality of sample containers 29 at different timings with time. it can. Since the collected gas is stored in each sample container 29, the collected gas can be analyzed at each collection timing by examining the gas in each of the plurality of sample containers 29. Therefore, it is possible to grasp the amount of gas generated over time, the components of the generated gas, etc. during the safety evaluation test, and to quantitatively analyze the generated gas over time.

<Second configuration example>
Next, a second configuration example of the generated gas analyzer of the electricity storage device will be described.
FIG. 2 is a schematic configuration diagram of the analysis device 200 of the second configuration example. In the following description, the same parts and members as those of the analyzer 100 of the first configuration example described above will be assigned the same reference numerals, and the description thereof will be omitted or simplified.

The analysis apparatus 200 of this configuration has a test container 19 in which the electricity storage device 11 is housed, an analyzer 15, and a communication passage 51 that serves as a gas discharge passage that connects the inside of the housing of the electricity storage device 11 to the analyzer 15. And an inert gas supply unit 53, a gas bag 55, and a data logger 45.

The inert gas supply unit 53 supplies an inert gas into the housing of the electricity storage device 11 and functions as a gas discharge drive unit. The gas bag 55 collects the gas discharged from the electricity storage device 11 by supplying the inert gas.

A branch channel 57 is provided that branches from the communication channel 51 through which the exhaust gas flows toward the gas bag 55.

The data logger 45 includes a temperature sensor 35 provided on the surface of the electricity storage device 11, a temperature sensor 37 arranged in the test container 19 to detect an ambient temperature, and a current/voltage detector 43 connected to the electrode terminals 41A and 41B. Various output signals from are input.

Next, a method of analyzing generated gas using the analyzer 200 having the above configuration will be described.
First, the power storage device 11 to be tested is set in the test container 19, the temperature sensor 35 is arranged on the surface of the power storage device 11, and the probe of the current/voltage detection unit 43 is connected to the electrode terminals 41A and 41B.

After completing the above preparation steps, the safety evaluation test of the electricity storage device 11 is started. The safety evaluation test of the electricity storage device 11 may be any of a nail penetration test, an overcharge test, a heating test, an external short circuit test, an overdischarge test, a crush test, a charge/discharge test, and a storage test, as described above.

After this safety evaluation test is started, gas is generated from the electricity storage device 11. The generated gas is pushed out into the communication channel 51 by supplying the He gas into the housing of the electricity storage device 11 by the inert gas supply unit 53 at a specific timing. The extruded gas is collected in the gas bag 55, and a part of the gas is sent to the analyzer 15 for analysis.

In the analysis step by the analyzer 15 in this case, analysis based on the GC-MS method or the IR method is performed.

By supplying air from the inert gas supply unit 53 intermittently or continuously after the start of the safety evaluation test, the generated gas can be sequentially sent to the analyzer 15 at different timings with time. Thereby, the analyzer 15 can analyze the gas blown from the power storage device 11 at different timings with time at different timings. Therefore, it is possible to grasp the amount of gas generated over time, the components of the generated gas, etc. during the safety evaluation test, and to quantitatively analyze the generated gas over time.

The air supply timing of the inert gas supply unit 53 can be arbitrarily changed, and analysis can be performed at desired time intervals. Further, when air is continuously supplied from the inert gas supply unit 53, it is possible to perform a time-dependent analysis at each repeating cycle time of the analysis process of the analyzer 15.

Next, the analysis results obtained by the analysis apparatus 100 having the first configuration example and the analysis apparatus 200 having the second configuration example, and the analysis results obtained by collectively analyzing the gases that have continuously been collected during the safety evaluation test as a comparative example. And explain.

<Analysis result by the analyzer 100 of the first configuration example>
Using the analyzer 100 shown in FIG. 1, a nail penetration test was performed as a safety evaluation test on the 3 Ah lithium ion battery which is the electricity storage device 11. During the test, the surface temperature of the lithium ion battery and the ambient temperature of the test container 19 were detected by the temperature sensors 35 and 37 and recorded in the data logger 45. The battery voltage was also recorded in the data logger 45 by the current/voltage detector 43. Then, the gas generated from the lithium-ion battery is supplied to the upstream side channel opening/closing of each time zone during four time zones during the test (before nail penetration, 3 seconds after nail penetration, 6 seconds after nail penetration, and 6 minutes after nail penetration). With the opening time of the valve 27 being 3 seconds), a plurality of sample containers 29 were intermittently collected with time, and the gas generation amount and the generated gas component of the collected gas were analyzed.

FIG. 3 is a graph showing the changes over time in the battery surface temperature, the ambient temperature and the voltage recorded by the data logger. Around 1.22 minutes after the start of the test, the nail portion 33a of the nail piercing portion 33 began to pierce the lithium-ion battery, a short circuit occurred, and the voltage started to largely drop. At the same time, the surface temperature of the lithium ion battery started to rise. The voltage that drastically dropped once returned to around 4V when about 1.4 minutes passed, and continued to be maintained at around 4V after that. The maximum surface temperature of the lithium-ion battery rose to around 55°C.

The gas generated from the lithium-ion battery was aged for 4 time periods during the test (before nail penetration, 3 seconds after nail penetration, 6 seconds after nail penetration, 6 minutes after nail penetration, and 3 seconds after valve opening time for 3 seconds). Table 1 shows the results of analysis by intermittently collecting and collecting. It was found that the main components of the generated gas were hydrogen, carbon dioxide, carbon monoxide, methane, ethane and ethylene. The concentration of each gas was high 3 seconds after nail pricking and decreased to half or less 6 seconds after nail pricking, which was not much different from the concentration 6 minutes after nail pricking. From this result, it was found that a large amount of gas was generated within 3 seconds immediately after nail penetration.

<Analysis result by the analyzer 200 of the second configuration example>
Using the analyzer 200 shown in FIG. 2, the gas generated during the safety evaluation test was collected in a gas bag, and part of the gas was sent directly to the analyzer for analysis. An overcharge test was performed using a 5 Ah prismatic lithium ion battery as the electricity storage device 11. During the test, the surface temperature of the lithium ion battery and the ambient temperature of the test container 19 were detected by the temperature sensors 35 and 37 and recorded in the data logger 45. Further, the battery voltage and the energized current were detected by the current/voltage detector 43 and recorded in the data logger 45. The gas generated from the lithium ion battery during the test was collected in the gas bag by sending He gas from the inert gas supply unit 53 into the housing of the lithium ion battery and pushing the generated gas out of the housing. Moreover, a part of the generated gas pushed out was sent to the mass spectrometer which is the analyzer 15, and was continuously analyzed during the test.

The graph of FIG. 4 shows how the voltage, current, battery temperature, and ambient temperature recorded by the data logger 45 change with respect to the charging depth. The scales of voltage and current on the vertical axis of the graph are shown by common values. As shown in FIG. 4, charging was started from the discharge state (charge depth: SOC 0%). A temperature rise of the lithium ion battery started to be observed from around 150% SOC, and a smoke was observed from the lithium ion battery with a rapid temperature rise around 350% SOC.

Table 2 shows the analysis results of the generated gas collected in the gas bag 55 from the start to the end of the safety evaluation test. It was found that the main constituents of the gas generated during the test were CO ₂ and H ₂ , CO, ethane, and diethyl carbonate (DEC), except for He as the atmospheric gas. The amounts of generated gas were 0.69L, 0.66L, 0.15L, 0.12L and 0.11L, respectively.

The results of continuous analysis of part of the gas generated during the test with an analyzer are shown in FIG. It was found that CO ₂ was abruptly generated near the SOC of 150%, and that CO, methane, and ethane were also increased in the amount around this. By using the quantitative analysis result of the generated gas collected in the gas bag 55, the generated amount per measurement interval (220 msec) can be calculated, and the generated amount of CO ₂ was almost 0 up to SOC 130%. However, it was found that the amount of 20 to 25 μL was generated per measurement interval after SOC 170%.

<Structure of Analytical Device of Comparative Example>
FIG. 6 is a reference diagram showing a schematic configuration of an analyzer as a comparative example.
The analyzer 300 of the comparative example includes a frame 63 in which the nail piercing part 33 having the nail part 33 a is attached to the elevating frame 61, a test container 19 in which the electricity storage device 11 is housed, and a pipe 65 in the test container 19. And a gas bag 71 connected to the buffer tank 67 through a pipe 69. An inert gas can be supplied to the test container 19 through a pipe 73.

This analyzer 300 accumulates all the gas generated from the electricity storage device 11 in the test container 19 during the safety evaluation test, which is a nail penetration test, and after the test, the gas in the test container 19 is piped from the test container 19 to the pipe 65. Through to the gas bag 71 communicating with the buffer tank 67. Then, the gas containing the gas generated from the electricity storage device 11 stored in the gas bag 71 is analyzed using an analyzer (not shown).

<Analysis result by analyzer of comparative example>
Using the analyzer 300 having the above structure, a nail penetration test was carried out on a 5 Ah lithium-ion battery. During the test, the surface temperature of the lithium ion battery and the ambient temperature of the test container 19 were measured with a thermocouple and recorded in a data logger. The battery voltage was also recorded on the data logger. All the gas generated during the test was collected in the gas bag 71, and the collected gas was analyzed (gas generation amount and generated gas component).

FIG. 7 is a graph showing changes over time in voltage, nail penetration depth, battery surface temperature, and ambient temperature recorded by a data logger. In addition, the scales of the nail penetration depth and the temperature on the vertical axis of the graph are shown by common values. According to this recording result, it is considered that the nail started to pierce the lithium ion battery in the vicinity of about 0.13 minutes, and at the same time, the battery voltage started to drop and the battery temperature and the temperature inside the container were observed to rise. The voltage became zero when about 0.3 minutes had passed.

As a result of analyzing the gas collected in the gas bag 71 with an analyzer, it was found that the main components of the collected gas were H ₂ , CO, CO ₂ , CH ₄ , and C ₂ H ₄ . Further, the amount each of _{H 2: 0.10L, CO: 1.3L} , CO 2: 4.0L, CH 4: 0.28L, C 2 H 4: it is 1.1 L, and the gas generating The total volume was found to be about 8L. However, it is unclear about changes over time in each gas component and gas generation amount.

The present invention is not limited to the above-described embodiments, and the configurations of the embodiments may be combined with each other, or may be modified and applied by those skilled in the art based on the description of the specification and well-known techniques. The invention is planned and is included in the scope of protection required.

As described above, the following items are disclosed in this specification.
(1) A method for analyzing generated gas of an electric storage device, which collects and analyzes gas generated from the electric storage device,
A test container containing the electricity storage device inside the container, the inside of the container being filled with an inert gas, a plurality of sample containers held at an internal pressure lower than that of the test container, the test container and the plurality of sample containers Using a gas collector provided with a plurality of communication channels for communicating with each other, and a channel opening/closing valve respectively provided between the test container and the sample container of the plurality of communication channels, After starting the safety evaluation test of the electricity storage device by closing the passage opening/closing valve, the passage opening/closing valves provided in the plurality of the communication passages are sequentially opened/closed at different timings for each of the communication passages, A step of sucking and collecting the internal gas of the test container at the timing when the flow path opening/closing valve is opened/closed, in the sample container communicating with the flow path opening/closing valve that has been opened/closed;
A step of analyzing the internal gas collected in each of the plurality of sample containers at different timings, for each sample container;
And a method for analyzing generated gas of an electricity storage device.
According to the method for analyzing the generated gas of the electricity storage device, the gas inside the test container is sucked at different timings with time to be collected in the sample container, and the gas collected in these sample containers is analyzed by the analyzer. Analyze each sample container according to. As a result, it becomes possible to analyze the change with time of the generated gas.

(2) The step of analyzing the internal gas is a step of analyzing based on at least one of GC-MS method, GC method, IC method, ICP-AES method, ICP-MS method, absorptiometry method, and IR method. (1) The method for analyzing generated gas of an electricity storage device according to (1).
According to the method of analyzing the generated gas of the electricity storage device, various analysis methods are selectively carried out, so that the desired analysis of the generated gas becomes possible.

(3) A method for analyzing generated gas of an electricity storage device, which collects and analyzes gas generated from the electricity storage device,
A test container that accommodates the power storage device inside a container, an inert gas supply unit that supplies an inert gas into the housing of the power storage device, and a gas discharge channel that discharges the internal gas in the housing of the power storage device. Using a gas collector comprising, after starting the safety evaluation test of the electricity storage device, a step of supplying an inert gas from the inert gas supply unit into the housing of the electricity storage device at a specific timing,
A step of analyzing the internal gas discharged from the inside of the housing of the electricity storage device at each of the specific timings at the supply timing of the inert gas;
And a method for analyzing generated gas of an electricity storage device.
According to the method for analyzing the generated gas of the electricity storage device, the internal gas in the housing of the electricity storage device is pushed out at different timings with time and analyzed by the analyzer. As a result, it becomes possible to analyze the change with time of the generated gas.

(4) The method of analyzing the generated gas of the electricity storage device according to (3), wherein the step of analyzing the internal gas is a step of analyzing based on a GC-MS method or an IR method.
According to the method of analyzing the generated gas of the electricity storage device, various analysis methods are selectively carried out, so that the desired analysis of the generated gas becomes possible.

(5) The safety evaluation test is at least one of a nail penetration test, an overcharge test, a heating test, an external short circuit test, an overdischarge test, a crush test, a charge/discharge test, and a storage test (1) to ( 4) A method for analyzing generated gas of any one of the electric storage devices.
According to the method of analyzing the generated gas of the electricity storage device, it is possible to analyze the change with time of the gas generated in various safety evaluation tests.

(6) The method for analyzing the generated gas of the electricity storage device according to any one of (1) to (5), wherein the step of analyzing the internal gas is a step of determining at least one of a generated gas amount and a gas component.
According to the method for analyzing the evolved gas of the electricity storage device, the change in the amount of the evolved gas over time and the change in the gas component over time are required.

(7) A generated gas analyzer for an electricity storage device, which collects and analyzes gas generated from the electricity storage device,
A test container in which the electricity storage device is housed inside a container and the inside of the container is filled with an inert gas,
A plurality of sample containers held at a lower internal pressure than the test container,
A plurality of communication channels for communicating the test container and the plurality of sample containers,
A flow path opening/closing valve respectively provided between the test container and the sample container of the plurality of communication flow paths,
The flow passage opening/closing valves of the plurality of communication passages are sequentially opened/closed at different timings for each of the communication passages, and the flow passage opening/closing valves are connected to the sample container communicating with the opened/closed flow passage opening/closing valves. A gas collection drive unit that sucks and collects the internal gas of the test container at a timing when the opening and closing operation is performed,
The internal gas collected at a different timing in each of the plurality of sample containers, an analyzer for analyzing each sample container,
A generated gas analyzer for an electricity storage device, comprising:

(8) A generated gas analyzer for an electric storage device, which collects and analyzes gas generated from the electric storage device,
A test container for housing the electricity storage device inside the container,
An inert gas supply unit that supplies an inert gas into the housing of the electricity storage device,
A gas exhaust flow path through which the internal gas in the housing of the electricity storage device is exhausted;
A gas discharge driving unit configured to supply an inert gas from the inert gas supply unit into the housing of the electricity storage device at a specific timing, and discharge the internal gas to the gas discharge flow path,
The internal gas discharged at the specific timing to the gas discharge channel, an analyzer for analyzing each specific timing,
An apparatus for analyzing generated gas of an electricity storage device, comprising:

11 Electric Storage Device 13 Gas Collector 15 Analyzer 17 Inside Container 19 Test Container 21 Gas Collection Line 23 Communication Channel 27 Upstream Channel Open/Close Valve (Channel Open/Close Valve)
29 Sample container 31 Downstream flow path opening/closing valve 33 Nail insertion part 33a Nail part 35, 37 Temperature sensor 41A, 41B Electrode terminal 43 Current voltage detection part 45 Data logger 51 Communication flow path (gas discharge flow path)
53 Inert gas supply unit (gas discharge drive unit)
55 gas bag 57 branched flow channels 100, 200 analyzer (gas generator for storage device)

Claims (4)

A method for analyzing generated gas of an electricity storage device, which collects and analyzes gas generated from the electricity storage device, the method comprising:
A test container in which the power storage device having a housing is housed inside the container together with the housing, and the inside of the container is filled with an inert gas; a plurality of sample containers held at an internal pressure lower than that of the test container; A gas including a plurality of communication flow paths for communicating a test container and a plurality of the sample containers, and a flow path opening/closing valve provided between the test container and the sample container of the plurality of communication flow paths, respectively. Using a collector, after closing the flow passage opening/closing valve and starting a safety evaluation test of the electricity storage device, the flow passage opening/closing valves provided in the plurality of communication passages are provided for each of the communication passages. Opening and closing operations at different timings sequentially, and sucking and collecting the internal gas of the test container at the timing when the flow path opening and closing valve opens and closes in the sample container communicating with the opened and closed flow path opening and closing valve. When,
A step of analyzing the internal gas collected in each of the plurality of sample containers at different timings, for each sample container;
And a method for analyzing generated gas of an electricity storage device. The step of analyzing the internal gas is a step of analyzing based on at least one of a GC-MS method, a GC method, an IC method, an ICP-AES method, an ICP-MS method, an absorptiometric method, and an IR method. 2. The method for analyzing generated gas of the electricity storage device according to 1. The safety evaluation tests, the nail penetration test, overcharge test, heating test, the external short circuit test, the over-discharge test, crush test, a charge and discharge test, according to claim 1 or 2 is at least one test of storage test Method for analyzing generated gas of power storage device. Process, the amount of generated gas, generated gas analysis method of the electric storage device according to any one of claims 1 to 3 is a step of obtaining at least one gas component of analyzing the internal gas.