JP6504026B2 - Gas analysis system - Google Patents

Description

  The present invention relates to a gas analysis system including a gas analysis cell in which a pair of electrodes including a positive electrode and a negative electrode and a diaphragm disposed between the pair of electrodes are provided.

  In various batteries (secondary batteries) such as lithium ion batteries, a gas is generated from the positive electrode and the negative electrode at the time of discharge or charge, and the gas degrades the electrode or electrolyte, or reduces the efficiency of discharge or charge May. Therefore, in the research or development of a battery, the relationship between the change in voltage between the positive electrode and the negative electrode and the component or amount of gas generated from the positive electrode and the negative electrode with the change may be analyzed.

  In such a case, use the positive electrode and the negative electrode formed of the same material as that used in the actual battery, and place the positive electrode and the negative electrode in the gas analysis cell to perform discharge or charge. Thus, the gas generated in the gas analysis cell is analyzed by an analyzer such as a gas chromatograph (see, for example, Non-Patent Document 1 below).

"Electrochemical Test Cell ECC-DEMS User Manual", EL-CELL, [online], February 11, 2015, [October 28, 2015 search], Internet <URL: http: // el-cell. com / wp-content / uploads / manuals / ECC_DEMS_manual.pdf>

  In the conventional gas analysis cell as described above, when the syringe is inserted into the cell body, the gas generated in the cell body is sucked into the syringe, and the gas is injected into the analyzer using the syringe. It had been. Therefore, it is not possible to easily observe changes in the components contained in the gas generated in the cell body, and in order to conduct such a detailed analysis, it was necessary to process a vast amount of data. In addition to the above, there have been cases where the amount of sample has to be obtained in the conventional analysis method because the amount of gas generated is very small.

  The present invention has been made in view of the above-described circumstances, and an object of the present invention is to provide a gas analysis system capable of performing analysis on gas generated from a positive electrode and a negative electrode in more detail.

(1) A gas analysis system according to the present invention includes a cell for gas analysis, a gas analysis unit, and a display control unit. The gas analysis cell is internally provided with a pair of electrodes including a positive electrode and a negative electrode, and a diaphragm disposed between the pair of electrodes. The gas analysis unit is supplied with the gas generated in the gas analysis cell, detects the gas with a detector, and analyzes components contained in the gas. The display control unit displays a change over time of a component contained in the gas analyzed by the gas analysis unit.

  According to such a configuration, it is possible to easily observe changes over time of components contained in the gas to be analyzed by the gas analysis unit. This makes it possible to intuitively understand at which timing the composition change of the gas generated from the positive electrode and the negative electrode is generated, so that the analysis on the gas generated from the positive electrode and the negative electrode can be performed in more detail.

(2) The gas analysis system may further include a component determination unit that determines the component of the gas generated in the gas analysis cell based on the detection signal from the detector. In this case, the display control unit may display the change over time of the component contained in the gas analyzed by the gas analysis unit using the determination result by the component determination unit.

  According to such a configuration, the component of the gas generated in the gas analysis cell is automatically determined, and the change with time of the component contained in the gas analyzed by the gas analysis unit using the determination result Can be displayed automatically.

(3) The display control unit may display a change with time of a ratio of each component contained in the gas analyzed by the gas analysis unit.

  According to such a configuration, since changes in the composition ratio of the gas generated from the positive electrode and the negative electrode can be observed in association with time, analysis on the gas generated from the positive electrode and the negative electrode can be performed in more detail. .

(4) Even if the display control unit causes the voltage, current, or capacitance between the pair of electrodes to be displayed in association with the change with time of the component contained in the gas, Good.

  According to such a configuration, not only changes in composition (chemical characteristics) of the gas generated from the positive electrode and the negative electrode, but also changes in voltage, current or electric capacity (electrical characteristics) between the positive electrode and the negative electrode correspond to time. Since it can be attached and observed, analysis on the gas generated from the positive electrode and the negative electrode can be performed in more detail.

(5) The display control unit causes the amount of gas generated in the gas analysis cell or the change in detection intensity to occur over time in association with the change over time of the component contained in the gas. May be

  According to such a configuration, not only the composition change of the gas generated from the positive electrode and the negative electrode, but also the amount or detected intensity of the generated gas can be observed in association with time, the gas generated from the positive electrode and the negative electrode The analysis on can be done in more detail.

(6) The gas analysis system does not include the first supply state in which the gas generated in the gas analysis cell is supplied to the gas analysis unit together with the carrier gas, or the gas generated in the gas analysis cell is not included. The apparatus may further include a supply switching unit that switches the carrier gas to any one of the second supply states for supplying the gas analysis unit.

  According to such a configuration, continuous analysis can be performed by directly supplying the gas generated in the gas analysis cell to the gas analysis unit together with the carrier gas in the first supply state. Therefore, external air is less likely to be mixed in the gas flow path, as compared to a configuration in which the gas generated in the gas analysis cell is injected into the gas analysis unit using a syringe. Since this can prevent air contamination from affecting the analysis results, continuous analysis can be performed more accurately.

  In addition, since the gas generated in the gas analysis cell can be supplied to the gas analysis unit and analyzed at intervals during the switching of the supply switching unit, quantitative analysis of the gas generated in each interval can be accurately performed. It can be carried out.

  Furthermore, if the gas analysis cell is attached to the supply switching unit in the second supply state, piping can be connected while the gas analysis cell is not in communication with the gas analysis unit. As a result, there is no need to pass through the pipe communicating with the gas analysis unit and connect it to the gas analysis cell, which facilitates the mounting operation.

(7) In the first supply state, the carrier gas is supplied to the gas analysis unit via the gas analysis cell, and in the second supply state, the gas analysis unit is not performed via the gas analysis cell. Carrier gas may be supplied.

  According to such a configuration, in the first supply state, the gas generated in the gas analysis cell is directly supplied from the inside of the gas analysis cell to the gas analysis unit. Therefore, analysis can be performed more accurately with a simple configuration.

(8) The gas analysis system may further include a buffer unit for containing the gas generated in the gas analysis cell. In this case, in the first supply state, the carrier gas is supplied to the gas analysis unit through the buffer unit, and in the second supply state, the carrier gas is supplied to the gas analysis unit without the buffer unit. The gas generated in the gas analysis cell may be accommodated in the buffer unit.

  According to such a configuration, when the gas generated in the gas analysis cell is accommodated in the buffer unit in the second supply state, and then switched from the second supply state to the first supply state, the gas is accommodated in the buffer unit. Can be supplied to the gas analysis unit together with the carrier gas. Therefore, if it is possible to store more gas in the buffer unit than in the gas analysis cell, more gas can be supplied from the buffer unit to the gas analysis unit. The detection sensitivity in the above can be improved, and analysis can be performed with higher accuracy.

  According to the present invention, it is possible to intuitively understand at which timing the composition change of the gas generated from the positive electrode and the negative electrode is generated. Therefore, the analysis on the gas generated from the positive electrode and the negative electrode is performed in more detail Can.

It is a channel figure showing an example of composition of a gas analysis system concerning a 1st embodiment of the present invention. It is a channel figure showing an example of composition of a gas analysis system concerning a 1st embodiment of the present invention. It is a block diagram showing an example of an electric configuration of a gas analysis system. It is a figure showing an example of a display mode of an analysis result by a display control part. It is a figure showing a modification of a display mode of an analysis result by a display control part. It is a channel figure showing an example of composition of a gas analysis system concerning a 2nd embodiment of the present invention. It is a channel figure showing an example of composition of a gas analysis system concerning a 2nd embodiment of the present invention.

1. First Embodiment of Gas Analysis System FIGS. 1A and 1B are flow diagrams showing an example of the configuration of a gas analysis system according to a first embodiment of the present invention. The gas analysis system includes a gas analysis cell 1 and a gas analysis unit 100 that analyzes the gas generated in the gas analysis cell 1.

  The gas analysis cell 1 is for analyzing a gas generated from a lithium ion battery which is an example of a secondary battery. In the gas analysis cell 1, the same structure as that of the lithium ion battery is reproduced inside, so that the same gas as that of the lithium ion battery can be generated, and the gas can be analyzed by the gas analysis unit 100.

  The gas analysis cell 1 is internally provided with a positive electrode 7, a negative electrode 8, a separator (diaphragm) 9, and the like. The positive electrode 7 is formed of, for example, a lithium alloy. The negative electrode 8 is made of, for example, carbon. The separator 9 is a porous thin film made of, for example, polypropylene. However, the diaphragm disposed between the pair of electrodes 7 and 8 is not limited to the separator 9.

  The gas analysis cell 1 is filled with, for example, an electrolytic solution made of an organic solvent, and the positive electrode 7, the negative electrode 8, and the separator 9 are immersed in the electrolytic solution. At the time of charging, lithium ions are generated from the positive electrode 7, and the lithium ions pass through the separator 9 and move to the negative electrode 8 side. On the other hand, at the time of discharge, lithium ions on the negative electrode 8 side pass through the separator 9 and move to the positive electrode 7 side. When a gas is generated from each of the electrodes 7 and 8 or the separator 9 in a state in which the pair of electrodes 7 and 8 are energized, the gas is collected in the gas analysis cell 1.

  The carrier gas is supplied from the gas supply flow path 217 into the gas analysis cell 1, and the carrier gas is discharged from the gas analysis cell 1 through the gas discharge flow path 218. Thereby, the carrier gas supplied into the gas analysis cell 1 through the gas supply flow path 217 is discharged from the gas discharge flow path 218 together with the gas generated in the gas analysis cell 1. .

  This gas analysis system is for performing continuous analysis using the gas analysis cell 1, and the gas collected in the gas analysis cell 1 is led to the gas analysis unit 100. That is, the gas in the gas analysis cell 1 discharged from the gas discharge flow path 218 is an analysis target by the gas analysis unit 100.

  The gas analysis unit 100 includes a flow controller 101, a sample introduction unit 102, a column 103, a detector 104, and the like. For example, helium is used as the carrier gas. The flow rate of the carrier gas supplied from the gas supply unit (not shown) is controlled by the flow controller 101. The carrier gas supplied from the flow controller 101 to the gas analysis cell 1 is introduced to the sample introduction unit 102 together with the gas generated in the gas analysis cell 1, and introduced from the sample introduction unit 102 to the column 103.

  The components contained in the gas introduced into the column 103 are separated in the process of passing through the column 103, and the separated components are detected by the detector 104. As the detector 104, for example, a barrier discharge ionization detector (BID) or a pulse discharge ionization detector (PDD) is used. As a result, analysis can be performed more accurately by using a barrier discharge ionization detector or a pulse discharge ionization detector with high detection sensitivity.

  In particular, the gas generated from the positive electrode 7 and the negative electrode 8 used in a battery contains hydrogen, oxygen, nitrogen, carbon monoxide, carbon dioxide, methane or the like, and a barrier discharge ionization detector or pulse discharge Although the ionization detector has high detection sensitivity to these gases, it can not detect helium. Therefore, if helium is used as the carrier gas and the gas generated in the gas analysis cell 1 is detected by the barrier discharge ionization detector or the pulse discharge ionization detector, the gas analysis can be performed without being affected by the components of the carrier gas. A wide variety of gases generated in the cell 1 can be analyzed with high accuracy. However, the detector 104 is not limited to these, and may be another detector such as, for example, a thermal conductivity detector (TCD) or a flame ionization detector (FID). The thermal conductivity detector is insensitive to all components of hydrogen, oxygen, nitrogen, carbon monoxide, carbon dioxide and methane, and the hydrogen flame ionization detector is sensitive to methane, but hydrogen, Insensitive to oxygen, nitrogen, carbon monoxide and carbon dioxide, barrier discharge ionization detectors and pulse discharge ionization sensitive to all components of hydrogen, oxygen, nitrogen, carbon monoxide, carbon dioxide and methane The detector is more appropriate as the detector 104 in this embodiment.

  In the example of FIGS. 1A and 1B, the gas analysis cell 1 is connected between the flow controller 101 and the sample introduction unit 102 via a six-way valve 105 as a supply switching unit. Specifically, among the six ports 151 to 156 provided in the six-way valve 105, the flow controller 101 is connected to the first port 151, and the sample introduction unit 102 is connected to the second port 152. In addition, in the gas analysis cell 1, the gas supply flow channel 217 is connected to the third port 153, and the gas discharge flow channel 218 is connected to the fourth port 154. The fifth port 155 is connected to a flow controller 106 different from the flow controller 101 of the gas analysis unit 100, and the sixth port 156 is an exhaust port. The flow controller 106 supplies the same carrier gas (for example, helium) as the flow controller 101.

  In the state of FIG. 1A, the first port 151 and the second port 152 communicate with each other. Accordingly, the carrier gas supplied from the flow controller 101 is sent to the sample introduction unit 102 without passing through the gas analysis cell 1, and is supplied from the sample introduction unit 102 to the column 103. In this state, the gas generated in the gas analysis cell 1 is not introduced into the column 103, and only the carrier gas is supplied to the column 103.

  In the state of FIG. 1A, the third port 153 and the fifth port 155 communicate with each other, and the fourth port 154 and the sixth port 156 communicate with each other. Therefore, the carrier gas supplied from the flow controller 106 is supplied into the gas analysis cell 1 through the fifth port 155 and the third port 153, and together with the gas generated in the gas analysis cell 1, the fourth port It is discharged to the outside through the 154 and the sixth port 156.

  When the six-way valve 105 is rotated from this state to the state shown in FIG. 1B, the first port 151 and the third port 153 communicate with each other, and the second port 152 and the fourth port 154 communicate with each other. In the state of FIG. 1B, the carrier gas from the flow controller 101 is supplied into the gas analysis cell 1 and introduced into the column 103 from the sample introduction unit 102 together with the gas generated in the gas analysis cell 1. Further, the fifth port 155 and the sixth port 156 communicate with each other, and the carrier gas from the flow controller 106 is discharged to the outside as it is.

  The state shown in FIG. 1B is a first supply state in which the carrier gas is supplied to the gas analysis unit 100 via the gas analysis cell 1. On the other hand, the state shown in FIG. 1A is a second supply state in which the carrier gas is supplied to the gas analysis unit 100 without the intervention of the gas analysis cell 1. By rotating the six-way valve 105 at a predetermined interval of, for example, 5 to 40 minutes, the first supply state and the second supply state are alternately switched.

  In the present embodiment, in the first supply state (see FIG. 1B) in which the gas generated in the gas analysis cell 1 is supplied to the gas analysis unit 100 together with the carrier gas by the six-way valve 105 or in the gas analysis cell 1. It is possible to switch to one of the second supply states (see FIG. 1A) in which the carrier gas that does not contain the generated gas is supplied to the gas analysis unit 100. In the first supply state, continuous analysis can be performed by directly supplying the gas generated in the gas analysis cell 1 to the gas analysis unit 100 together with the carrier gas. Therefore, external air is less likely to be mixed in the gas flow path, as compared with a configuration in which the gas generated in the gas analysis cell 1 is injected into the gas analysis unit 100 using a syringe. Since this can prevent air contamination from affecting the analysis results, continuous analysis can be performed more accurately.

  In addition, since the gas generated in the gas analysis cell 1 can be supplied to the gas analysis unit 100 and analyzed at intervals during switching of the six-way valve 105, quantitative analysis of the gas generated in each interval is performed. It can be done correctly.

  Furthermore, if the gas analysis cell 1 is attached to the six-way valve 105 in the second supply state shown in FIG. 1A, piping can be connected in a state where the gas analysis cell 1 does not communicate with the gas analysis unit 100. As a result, there is no need to pass through the pipe communicating with the gas analysis unit 100 and connect it to the gas analysis cell 1, so the mounting operation becomes easy.

  In particular, in the present embodiment, the gas generated in the gas analysis cell 1 is directly supplied from the inside of the gas analysis cell 1 to the gas analysis unit 100 in the first supply state shown in FIG. 1B. Therefore, analysis can be performed more accurately with a simple configuration. However, the supply switching unit is not limited to the six-way valve 105, and may be configured by another valve.

  The gas analysis cell 1 and the hexagonal valve 105 can also be temperature-controlled to a relatively high temperature of, for example, room temperature to 90 ° C., more preferably about 80 ° C. This allows for a rigorous durability check. The regulated temperature is set to an appropriate value according to the boiling point of the electrolytic solution in the gas analysis cell 1.

2. Electrical Configuration of Gas Analysis System FIG. 2 is a block diagram showing an example of the electrical configuration of the gas analysis system. In the present embodiment, the operation of the gas analysis system is controlled by the control unit 10 including, for example, a CPU (Central Processing Unit). The charging state of the positive electrode 7 and the negative electrode 8 is controlled by the charging / discharging device 20 at a constant current or a constant voltage, and the output voltage at that time is input to the control unit 10. In addition, the gas analysis system is provided with a display unit 30 configured of, for example, a liquid crystal display, and the display unit 30 displays an analysis result and the like.

  The control unit 10 functions as an analysis control unit 11, a display control unit 12, and a component determination unit 13 when the CPU executes a program. The analysis control unit 11 performs continuous analysis by controlling the operations of the flow controllers 101 and 106, the hexagonal valve 105, and the like in the manner described with reference to FIGS. 1A and 1B. Specifically, in each of the charge and discharge alternately performed by the charge / discharge device 20, the six-way valve 105 is rotated at the above-described predetermined interval to allow the gas analysis unit 100 to be performed via the gas analysis cell 1. The first supply state in which the carrier gas is supplied and the second supply state in which the carrier gas is supplied to the gas analysis unit 100 without the gas analysis cell 1 are alternately switched.

  The display control unit 12 controls the display on the display unit 30 based on input signals from the charge and discharge device 20 and the detector 104. The component determination unit 13 determines the component of the gas generated in the gas analysis cell 1 based on the detection signal from the detector 104. The display control unit 12 controls the display on the display unit 30 using the determination result of the component determination unit 13. Specifically, in addition to data of electrical characteristics obtained based on an input signal from charge / discharge device 20, detection of each component such as hydrogen, oxygen, nitrogen, carbon monoxide, carbon dioxide or methane in detector 104 Data of chemical characteristics such as intensity (signal intensity or concentration) are displayed on the display unit 30 by the control of the display control unit 12. Such display of the analysis result by the display control unit 12 may be performed in real time as time passes, or may be performed after the end of analysis.

3. Display Mode of Analysis Result FIG. 3 is a view showing an example of a display mode of the analysis result by the display control unit 12. In this example, the horizontal axis is time, the first axis of the vertical axis is the voltage between the positive electrode 7 and the negative electrode 8, and the second axis of the vertical axis is the signal of the gas generated in the gas analysis cell 1 in each interval. It is strength.

  In the present embodiment, for each of the charge and discharge performed alternately, each charge period and each discharge period, such as a first charge period, a first discharge period, a second charge period, a second discharge period, and so on. Is specified in association with the horizontal axis (time). Thereby, the change of the value of the vertical axis in each charge period and each discharge period is displayed in an easy-to-understand manner.

  With respect to the first axis of the vertical axis, the change over time of the voltage between the positive electrode 7 and the negative electrode 8 is displayed by a smooth line graph G1. As shown in FIG. 3, the voltage between the positive electrode 7 and the negative electrode 8 gradually increases during the charge period, and the voltage between the positive electrode 7 and the negative electrode 8 gradually decreases during the discharge period. During analysis, charge and discharge of a plurality of cycles are repeated based on a charge and discharge program set in advance, with one continuous charge period and one discharge period as one cycle (charge and discharge period).

  As for the second axis of the vertical axis, the total value of the signal intensity of each component generated in the gas analysis cell 1 in each interval is displayed by a smooth line graph G2 by being connected by a line. Further, the ratio of the signal strength of each component to the total value of the signal strength in each interval is displayed by the band graph G3. That is, the band graph G3 for each interval is displayed by expressing the ratio of the signal strength of each component in the bar graph having the total value of the signal strength as the length. The components to be displayed on the display unit 30 may be arbitrarily selected.

  As described above, in the present embodiment, the band graph G3 displayed on the display unit 30 under the control of the display control unit 12 displays the change over time of the component contained in the gas generated in the gas analysis cell 1 Be done. Therefore, it is possible to easily observe the change over time of the components contained in the gas analyzed by the gas analysis unit 100. This makes it possible to intuitively understand at which timing the composition change of the gas generated from the positive electrode 7 and the negative electrode 8 is generated. Therefore, analysis on the gas generated from the positive electrode 7 and the negative electrode 8 is performed in more detail. be able to. However, it is also possible to display the change with time progress of the component contained in the gas generated in the cell 1 for gas analysis not only in the band graph G3 but in other aspects, such as a line graph. For example, the color of the graph may be changed according to the type of gas component, or the graph may be displayed only for a specific component.

  In particular, in the present embodiment, not only the types of the respective components contained in the gas analyzed by the gas analysis unit 100 but also the change with the passage of time of the ratio can be displayed by the band graph G3. Thereby, changes in the composition ratio of the gas generated from the positive electrode 7 and the negative electrode 8 can be observed in association with time, so that analysis on the gas generated from the positive electrode 7 and the negative electrode 8 can be performed in more detail.

  Further, in the present embodiment, the change over time of the voltage between the pair of electrodes 7 and 8 is made in the gas analysis cell 1 by the line graph G1 displayed on the display unit 30 under the control of the display control unit 12. Is displayed in association with the change with time (band graph G3) of the component contained in the gas generated at time t2. Thus, not only changes in the composition (chemical characteristics) of the gas generated from the positive electrode 7 and the negative electrode 8 but also changes in the voltage (electrical characteristics) between the positive electrode 7 and the negative electrode 8 can be observed in association with time. Since it can be performed, analysis on the gas generated from the positive electrode 7 and the negative electrode 8 can be performed in more detail.

  However, the above electrical characteristics are not limited to the voltage between the positive electrode 7 and the negative electrode 8, but may be the current or the electric capacity between these electrodes 7 and 8. That is, the display unit 30 is not limited to the change with the passage of time of the voltage between the pair of electrodes 7 and 8 but the change with the passage of time of the current or the electric capacitance between the pair of electrodes 7 and 8 It may be displayed in association with the change over time of the component contained in the gas generated in the analysis cell 1.

  Furthermore, in the present embodiment, the change over time of the detection intensity of the gas generated in the gas analysis cell 1 by the line graph G2 displayed on the display unit 30 under the control of the display control unit 12 is for gas analysis. It is displayed in association with the change over time (band graph G3) of the components contained in the gas generated in the cell 1. As a result, not only the composition change of the gas generated from the positive electrode 7 and the negative electrode 8 but also the detected intensity of the generated gas can be observed in association with the time, so analysis on the gas generated from the positive electrode 7 and the negative electrode 8 It can be done in more detail.

  However, not the detected intensity of the gas generated in the gas analysis cell 1, but the change with time of the amount of gas calculated from the detected intensity is a component contained in the gas generated in the gas analysis cell 1 May be displayed in association with changes over time.

  In the example of FIG. 3, when transitioning from the charging period to the discharging period, and when transitioning from the discharging period to the charging period, the voltage between the positive electrode 7 and the negative electrode 8 changes rapidly and is relatively high. It can be seen that the gas generated in the gas analysis cell 1 is detected by the intensity.

  In the example of FIG. 3, the horizontal axis represents time, but the horizontal axis is limited to an accurate time if it can be configured to display changes in chemical characteristics or electrical characteristics over time. Alternatively, it may be another parameter that represents the passage of time, such as the number of charge / discharge cycles. As described above, when the number of charge / discharge cycles is taken as the horizontal axis, the total amount of gas generated in the gas analysis cell 1 in each cycle may be displayed on the second axis. Also, either one of the first axis or the second axis may be omitted. Furthermore, the graphs displayed on the display unit 30 are not limited to the line graphs G1 and G2, the band graph G3, and the like, and other various graphs can be used.

  FIG. 4 is a view showing a modification of the display mode of the analysis result by the display control unit 12. In this example, the horizontal axis is the number of charge / discharge cycles, and the vertical axis is the signal intensity of the gas generated in the gas analysis cell 1 in each cycle. On the vertical axis, the total value of the signal intensity of each component generated in the gas analysis cell 1 in each cycle is displayed by a smooth line graph G4 by being connected by a line. In addition, the ratio of the signal strength of each component to the total value of the signal strength in each cycle is displayed by the band graph G5. That is, the band graph G5 for each cycle is displayed by expressing the ratio of the signal strength of each component in the bar graph in which the total value of the signal strength is the length. The components to be displayed on the display unit 30 may be arbitrarily selected. As described above, various modes can be adopted as the display mode of the analysis result by the display control unit 12.

4. Second Embodiment of Gas Analysis System FIGS. 5A and 5B are flow charts showing an example of the configuration of a gas analysis system according to a second embodiment of the present invention. This gas analysis system is for performing continuous analysis using the gas analysis cell 1 as in the first embodiment, and the gas analysis cell 1 and the gas analysis cell 1 of the gas analysis cell 1 And a gas analysis unit 100 that analyzes the gas generated inside. Since the configuration of the gas analysis unit 100 is the same as that of the first embodiment, the same reference numerals are given to the same components as those in the first embodiment, and detailed description will be omitted.

  In this gas analysis system, the gas collected in the gas analysis cell 1 is guided to the gas analysis unit 100 as in the first embodiment. That is, the gas in the gas analysis cell 1 discharged from the gas discharge flow path 218 is an analysis target by the gas analysis unit 100.

  In the example of FIGS. 5A and 5B, the gas analysis cell 1 and the buffer unit 107 are connected between the flow controller 101 and the sample introduction unit 102 via the six-way valve 105 as a supply switching unit. The buffer section 107 is a so-called sample tube, and is a hollow member having a buffer area larger than the internal volume of the gas analysis cell 1 inside.

  The flow controller 106 is connected to the first port 151 among the six ports 151 to 156 provided in the six-way valve 105, and the gas analysis cell 1 is interposed between the flow controller 106 and the first port 151. It is done. That is, the gas supply flow path 217 of the gas analysis cell 1 is connected to the flow controller 106, and the gas discharge flow path 218 is connected to the first port 151. Further, the second port 152 and the fifth port 155 are connected, and the buffer unit 107 is interposed between the second port 152 and the fifth port 155. The sixth port 156 is connected to the flow controller 101, and the fourth port 154 is connected to the sample introduction unit 102. The third port 153 is an exhaust port. The flow controller 106 supplies the same carrier gas (for example, helium) as the flow controller 101.

  In the state of FIG. 5A, the fourth port 154 and the sixth port 156 communicate with each other. Therefore, the carrier gas supplied from the flow controller 101 is sent to the sample introduction unit 102 without passing through the buffer unit 107, and is supplied from the sample introduction unit 102 to the column 103. In this state, the gas generated in the gas analysis cell 1 is not introduced into the column 103, and only the carrier gas is supplied to the column 103.

  Further, in the state of FIG. 5A, the first port 151 and the second port 152 communicate with each other, and the third port 153 and the fifth port 155 communicate with each other. Therefore, the carrier gas supplied from the flow controller 106 is supplied into the gas analysis cell 1, and together with the gas generated in the gas analysis cell 1, the buffer unit 107 is provided via the first port 151 and the second port 152. After passing through the fifth port 155 and the third port 153, it is discharged to the outside. Thereby, the gas generated in the gas analysis cell 1 is accommodated in the buffer unit 107.

  When the six-way valve 105 is rotated from this state to the state shown in FIG. 5B, the second port 152 and the fourth port 154 communicate with each other, and the fifth port 155 and the sixth port 156 communicate with each other. In the state of FIG. 5B, the carrier gas from the flow controller 101 is supplied into the buffer unit 107 and introduced into the column 103 from the sample introduction unit 102 together with the gas in the buffer unit 107. Further, the first port 151 and the third port 153 communicate with each other, and the carrier gas from the flow controller 106 is discharged to the outside as it is through the gas analysis cell 1.

  The state illustrated in FIG. 5B is a first supply state in which the carrier gas is supplied to the gas analysis unit 100 via the buffer unit 107. On the other hand, the state shown in FIG. 5A is a second supply state in which the carrier gas is supplied to the gas analysis unit 100 without the buffer unit 107. By rotating the six-way valve 105 at a predetermined interval of, for example, 5 to 40 minutes, the first supply state and the second supply state are alternately switched.

  In the present embodiment, the first supply state (see FIG. 5B) in which the gas generated in the gas analysis cell 1 and stored in the buffer unit 107 by the six-way valve 105 is supplied to the gas analysis unit 100 together with the carrier gas, or It is possible to switch to one of the second supply states (see FIG. 5A) in which the carrier gas not containing the gas generated in the gas analysis cell 1 is supplied to the gas analysis unit 100. In the first supply state, continuous analysis can be performed by directly supplying the gas generated in the gas analysis cell 1 and contained in the buffer unit 107 to the gas analysis unit 100 together with the carrier gas. Therefore, external air is less likely to be mixed in the gas flow path, as compared with a configuration in which the gas generated in the gas analysis cell 1 is injected into the gas analysis unit 100 using a syringe. Since this can prevent air contamination from affecting the analysis results, continuous analysis can be performed more accurately.

  In addition, since the gas generated in the gas analysis cell 1 and contained in the buffer unit 107 can be supplied to the gas analysis unit 100 for analysis at each interval while the six-way valve 105 is switched, Quantitative analysis of the gas generated by

  In particular, in the present embodiment, in the second supply state shown in FIG. 5A, if the gas generated in the gas analysis cell 1 is accommodated in the buffer unit 107 and then switched to the first supply state shown in FIG. The gas contained in the unit 107 can be supplied to the gas analysis unit 100 together with the carrier gas. Therefore, as in the present embodiment, in the configuration in which more gas can be accommodated in the buffer area in the buffer unit 107 than in the gas analysis cell 1, more gas can be supplied from the buffer unit 107. Since the gas analysis unit 100 can be supplied, the detection sensitivity in the gas analysis unit 100 is improved, and analysis can be performed with higher accuracy.

  Note that the temperature of the gas analysis cell 1, the hexagonal valve 105, and the buffer unit 107 can be adjusted to a relatively high temperature of, for example, room temperature to 90 ° C., more preferably about 80 ° C. This allows for a rigorous durability check. The regulated temperature is set to an appropriate value according to the boiling point of the electrolytic solution in the gas analysis cell 1. Further, the buffer unit 107 is provided with, for example, a filter (not shown) that does not pass high-boiling substances, whereby the contamination of the column 103 is prevented.

  In any of the first embodiment and the second embodiment, the valve 215 is connected to the gas supply flow channel 217 of the gas analysis cell 1, and the valve 216 is connected to the gas discharge flow channel 218. The valve 215 constitutes a supply side valve for opening and closing the gas supply flow channels 217 and 227, and the valve 216 constitutes a discharge side valve for opening and closing the gas discharge flow channel 218. For example, two-way valves can be used as the valves 215 and 216.

  As a result, when the gas analysis cell 1 is manufactured, the gas analysis cell 1 is assembled in an environment without air (replaced with a specific gas such as argon or helium), and the supply side valve (valve 215) When the side valve (valve 216) is closed, air does not enter the gas analysis cell 1 and the internal components do not deteriorate. Then, after the gas supply flow path 217 and the gas discharge flow path 218 of the gas analysis cell 1 were connected to the six-way valve 105, the supply side valve (valve 215) and the discharge side valve (valve 216) were opened. By switching to the state, the installation work can be easily performed while preventing the mixing of air.

DESCRIPTION OF SYMBOLS 1 gas analysis cell 7 positive electrode 8 negative electrode 9 separator 10 control unit 11 analysis control unit 12 display control unit 20 charge / discharge device 30 display unit 100 gas analysis unit 101 flow controller 102 sample introduction unit 103 column 104 detector 105 six-way valve 106 flow Controller 107 Buffer section 215, 216 Valve 217 Gas supply flow path 218 Gas discharge flow path G1 Line graph G2 Line graph G3 Band graph

Claims (7)

A gas analysis cell having therein a pair of electrodes comprising a positive electrode and a negative electrode, and a diaphragm disposed between the pair of electrodes;
A gas analysis unit which is supplied with a gas generated in the gas analysis cell and detects the gas with a detector to analyze components contained in the gas;
A display control unit configured to display a change over time of a component contained in the gas to be analyzed by the gas analysis unit ;
The said display control part displays the change accompanying the time progress of the ratio of each component contained in the said gas analyzed by the said gas analysis part . A gas analysis cell having therein a pair of electrodes comprising a positive electrode and a negative electrode, and a diaphragm disposed between the pair of electrodes;
A gas analysis unit which is supplied with a gas generated in the gas analysis cell and detects the gas with a detector to analyze components contained in the gas;
A display control unit for displaying a change over time of a component contained in the gas analyzed by the gas analysis unit;
The first supply state in which the gas generated in the gas analysis cell is supplied to the gas analysis unit together with the carrier gas, or the carrier gas not containing the gas generated in the gas analysis cell is supplied to the gas analysis unit A supply switching unit which switches to any of the second supply states
And an analysis control unit configured to switch to the first supply state or the second supply state by controlling the supply switching unit. In the first supply state, a carrier gas is supplied to the gas analysis unit via the gas analysis cell,
The gas analysis system according to claim 2 , wherein in the second supply state, a carrier gas is supplied to the gas analysis unit without passing through the gas analysis cell. It further comprises a buffer unit for containing the gas generated in the gas analysis cell,
In the first supply state, a carrier gas is supplied to the gas analysis unit via the buffer unit,
In the second supply state, the carrier gas is supplied to the gas analysis unit without passing through the buffer unit, and the gas generated in the gas analysis cell is accommodated in the buffer unit. gas analysis system according to 2. The system further includes a component determination unit that determines the component of the gas generated in the gas analysis cell based on the detection signal from the detector.
The display controller, using the determination result by the component determining device, according to claim 1-4, characterized in that to display the change with time of the components contained in the gas to be analyzed by the gas analyzer The gas analysis system according to any one of the preceding claims. The display control unit is characterized by displaying a change over time of voltage, current or capacitance between the pair of electrodes in association with a change over time of a component contained in the gas. The gas analysis system according to any one of claims 1 to 5 . The display control unit is characterized in that the amount of gas generated in the gas analysis cell or the change with time of detection intensity is displayed in association with the change with time of the component contained in the gas. The gas analysis system according to any one of claims 1 to 6 .

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