Electrochemical measurement device

• US 10,018,586 B2
• Filed: 01/14/2014
• Issued: 07/10/2018
• Est. Priority Date: 01/23/2013
• Status: Active Grant

• Current Assignee: Hitachi High-Tech Company Limited (Hitachi, Ltd.)
• Original Assignee: Hitachi High-Technologies Corporation (Hitachi, Ltd.)
• Inventors: Matsuoka, Shinya, Oguchi, So, Tokiwa, Yukie, Sakurai, Toshinari, Niiyama, Yasushi, Iizumi, Noriko
• Primary Examiner(s): Ball, J. Christopher
• Application Number:
  US14/760,032
• Publication Number:
  US 20150355140A1
• Time in Patent Office: 1,638 Days
• CPC Class Codes: G01N 27/4163 checking the operation of, or calibrating, the measuring apparatus G01N27/3274, G01N27/4175 and G01N33/0006 take precedence

Abstract

A flow cell for electrochemical measurement which introduces a sample solution, applies a voltage between a working electrode and a counter electrode to analyze the sample solution electrochemically, discharges the sample solution, and performs the electrochemical measurement continuously. The flow cell includes a unit which measures a value of a current flowing between electrodes at the time of applying a voltage, a unit which records the measured current value, a unit which compares the recorded current value with a current value set separately as a determination standard, and a unit which determines whether the current value measured at a cycle of a determination target and the recorded current value is normal by the comparison.

Claims

1. An electrochemical measurement device comprising:

a flow cell for electrochemical measurement of a sample solution, the flow cell including a flow channel, a working electrode and a counter electrode; and

a control device connected to the flow cell and

configured to control the flow cell to perform the electrochemical measurement by repeatedly performing a cycle, including a conditioning step including applying a first voltage between the working electrode and the counter electrode, an electrochemical measurement step including applying a second voltage between the working electrode and the counter electrode to analyze the sample solution in the flow cell, and a cleaning step including applying a third voltage between the working electrode and the counter electrode, as a plurality of cycles,

wherein the control device is further configured to;

measure, in the conditioning step, the electrochemical measurement step, or the cleaning step of a determination target cycle of the plurality of cycles, a current value of a current flowing between the working electrode and the counter electrode at the time of applying the first voltage, the second voltage, or the third voltage thereto;

record the measured current value;

compare the measured current value with a determination standard based on a current value obtained from the plurality of cycles which precede the determination target cycle including one of the plurality of cycles that occurred immediately before the determination target cycle; and

determine whether the measured current value is abnormal based on a result of the comparison; and

when the measured current value is abnormal, output an abnormality notification of the measured current value.

2. The electrochemical measurement device according to claim 1, wherein

the determination standard is a standard value based on the current value of a current flowing between the working electrode and the counter electrode at the time of applying the first voltage in the conditioning step, the second voltage in the electrochemical step, or the third voltage in the cleaning step of the plurality of cycles which precede the determination target cycle.

3. The electrochemical measurement device according to claim 1, wherein the control device is further configured to:

calculate the determination standard for each of the cycles.

4. The electrochemical measurement device according to claim 1, further comprising:

a display unit which displays the abnormality notification.

5. The electrochemical measurement device according to claim 1, wherein the control device is further configured to:

store current values measured in the conditioning step or the cleaning step associated with each of the cycles in time series after starting the electrochemical measurement in the flow cell, and

when the current values measured in the cycles are continuously increasing or decreasing a predetermined number of times or more as compared with the determination standard, output an alarm.

6. The electrochemical measurement device according to claim 5, wherein the control device is further configured to:

determine an electrode state of the working electrode and the counter electrode based on the current values measured in the cycles increasing or decreasing continuously, a number of times of use of the electrochemical flow cell, or a combination thereof.

7. The electrochemical measurement device according to claim 6, wherein the control device is further configured to:

output an exchange time for the electrochemical flow cell based on the electrode state.

8. An electrochemical measurement system, comprising:

an electrochemical measurement device;

a display device which is located remote from the electrochemical measurement device;

a control device which is located remote from the electrochemical measurement device and which is connected to the electrochemical measurement device and the display device,

wherein the electrochemical measurement device includes a flow cell for electrochemical measurement of a sample solution, the flow cell including a flow channel, a working electrode and a counter electrode,

wherein the control device is configured to control the flow cell to perform the electrochemical measurement by repeatedly performing a cycle, including a conditioning step including applying a first voltage between the working electrode and the counter electrode, an electrochemical measurement step including applying a second voltage between the working electrode and the counter electrode to analyze the sample solution in the flow cell, and a cleaning step including applying a third voltage between the working electrode and the counter electrode, as a plurality of cycles,

wherein the control device is further configured to;

measure, in the conditioning step, the electrochemical measurement step, or the cleaning step of a determination target cycle of the plurality of cycles, a current value of a current flowing between the working electrode and the counter electrode at the time of applying the first voltage, the second voltage, or the third voltage thereto;

record the measured current value;

compare the measured current value with a determination standard based on a current value obtained from the plurality of cycles which precede the determination target cycle including one of the plurality of cycles that occurred immediately before the determination target cycle; and

determine whether the measured current value is abnormal based on a result of the comparison; and

when the measured current value is abnormal, output an abnormality notification of the measured current value to the display device.

9. A method of detecting an abnormality in an electrochemical measurement device having a flow cell for electrochemical measurement of a sample solution, the flow cell including a flow channel, a working electrode and a counter electrode, the method comprising:

controlling the flow cell to perform the electrochemical measurement by repeatedly performing a cycle, including a conditioning step including applying a first voltage between the working electrode and the counter electrode, an electrochemical measurement step including applying a second voltage between the working electrode and the counter electrode to analyze the sample solution in the flow cell, and a cleaning step including applying a third voltage between the working electrode and the counter electrode, as a plurality of cycles;

measuring, in the conditioning step, the electrochemical measurement step, or the cleaning step of a determination target cycle of the plurality of cycles, a current value of a current flowing between the working electrode and the counter electrode at the time of applying the first voltage, the second voltage, or the third voltage thereto;

comparing the measured current value with a determination standard based on a current value obtained from the plurality of cycles which precede the determination target cycle including one of the plurality of cycles that occurred immediately before the determination target cycle;

determining whether the measured current value is abnormal based on a result of the comparison; and

when the measured current value is abnormal, outputting an abnormality notification of the measured current value.