KR100974564B1 - Reference electrode with automatic calibration function and electrochemical potential calibration device using the same - Google Patents

Abstract

The present invention relates to a reference electrode having an automatic calibration function having a function of maintaining a measurement accuracy of a reference electrode used in electrochemical measurement for a long time, and an electrochemical potential calibration device using the same. A reference electrode including an electrode separation membrane formed at the inside, an electrode outer body filled with an electrode electrolyte solution therein, and two or more inner electrodes formed on the electrode outer body and immersed in the electrode electrolyte solution and electrically separated from each other; And a reference potential corrector configured to measure an electrical conductivity of the electrode electrolyte solution by applying an alternating voltage to the internal electrode, and output a correction signal for a reference potential change of the reference electrode. By measuring the concentration of the internal electrolyte, Appropriately correct the change, there is an effect that it is possible to maintain the function of the long-term reference electrode through it.

Electrochemistry, Reference Electrode, Internal Electrode, Automatic Calibration, Electrolyte, Electrical Conductivity

Description

Reference Electrode With Self-Calibrated Function And Automatic Electrochemical Potential Correction Apparatus Using The Same}

The present invention relates to a reference electrode and an automatic electrochemical potential calibration device using the same, and more particularly, to a reference electrode having an automatic calibration function used for measuring chemical and electrochemical reactions, and an electrochemical potential automatic calibration device using the same.

Electrochemical methods have been widely used since the late 19th century to measure and control chemical and electrochemical reactions in liquid media such as aqueous solutions, organic solutions, and hot molten salts. In particular, since the end of the 20th century, research and development in the fields of secondary lithium battery, fuel cell, and solar cell have been expanded, and the demand for electrochemical methods is rapidly increasing.

In the electrochemical method, the use of a reference electrode is essential to accurately measure and control the potential of the working electrode. In general, the reference electrode is manufactured by using a reaction that is clearly seen in the potential region where the redox reaction is narrow.

Representative electrode reactions used as reference electrodes so far include the following reactions (Bard, A.J. & L.R. Faulkner, Electrochemical Methods: Fundamentals and Applications.New York: John Wiley & Sons, 2nd Edition, 2000).

2H ⁺ + 2e ^- H ₂ (Pt); Standard hydrogen electrode (SHE) (E = 0.000V)

AgCl + e Ag + Cl ^-; Silver Chloride Electrode (E = 0.225V saturated)

Hg ₂ ^{2 +} + 2e 2Hg, Hg ₂ ^{2 +} + 2 Cl ^- Hg ₂ Cl ₂ ; Saturated calomel electrode (SCE) (E = + 0.242V saturated)

Cu ^{2 ++} 2e Cu; Copper-copper (II) sulfate electrode (E = -0.318V)

In the above electrode reaction, the reaction between the hydrogen ion and the hydrogen gas, which is the first electrode reaction, is a standard reaction (E = 0.0 V), but since the hydrogen gas must be handled, it is rarely used in actual situations.

1 is a cross-sectional view showing the structure of a conventional reference electrode conventionally used.

Referring to FIG. 1, in the conventional reference electrode, one internal electrode 20 is formed on an electrode outer body in which an electrolyte separation membrane 11 is formed at one end, and the electrolyte 30 is partially locked so that a part of the internal electrode 20 is submerged. It is configured to be filled in the electrode outer body.

In general, the reference electrode most used in research or industrial fields is the internal electrode 20 is a silver / silver chloride electrode or a caramel electrode. In this electrode reaction, since the activity of chlorine ion in the electrolyte 30 is constant, the concentration of chlorine ion (Cl ⁻ ) in the electrode must be kept constant during the measurement.

In Korean Patent 10-0477448-0000 (2005.03.09), a nano-flow control microvalve was installed in an electrode system using a shape memory alloy thin film to minimize KCl (Cl ⁻ ) consumption. In addition, the Republic of Korea Patent 10-0329393-0000 (2002.03.07) and 10-0483628-0000 (2005.04.07) and the like to improve the electrode durability by suppressing the leakage of KCl, the internal solution of the electrode using a polymer material. Korean Patent No. 10-0612270-0000 (2006.08.07) also configured a polymer electrolyte to maintain a constant KCl concentration, and configured an electrode system to be used in a high temperature and high pressure aqueous solution environment.

In U.S. Patent 4,822,456 (1989.04.18), a junction is made using a permeable membrane inside the reference electrode to prevent electrode contamination, and an electrode is installed inside and outside the junction to change relative voltage between internal and external electrodes. The device was designed to detect the contamination of the electrolyte inside the reference electrode by measuring it.

In addition, international PCT patents, WO 89/07758 (1989.08.24), PCT / US 89/00628 (1989.02.15), Korean patent 10-0152426-0000 (1998.06.26) and Korean patent 10-0411715-0000 (2003.12 .05), 10-0439645-0000 (Jun. 30, 2004) developed a technique for electrode miniaturization by incorporating thin film processing technology to apply the reference electrode to the semiconductor field.

Thus far, technical improvements in the field of reference electrodes have been developed in order to prevent leakage of the internal solution of electrodes and to develop new materials in the manufacture of electrodes or to make them suitable for the unique environment in which the electrodes are used, and to develop technologies for miniaturization of electrodes. It has been going on. However, no attempt has been made to correct the potential of the reference electrode by detecting the concentration of the electrolyte which directly affects the electrode reaction of the reference electrode.

The present invention has been made to solve the above-described problems of the prior art, by continuously detecting the change in the concentration of the solution inside the electrode generated during the use of the reference electrode using an electrical conductivity meter to provide a function for maintaining the accuracy of the reference electrode for a long time An object of the present invention is to provide a reference electrode having an automatic calibration function and an electrochemical potential calibration device using the same.

The reference electrode having an automatic calibration function according to the first aspect of the present invention for solving the above problems is formed on the electrode outer body, the electrode outer body is filled with an electrode electrolyte solution therein, and the electrode electrolyte solution is filled in one end; It is formed to be submerged in the electrode electrolyte solution, and includes two or more internal electrodes electrically separated.

In addition, the reference electrode having an automatic calibration function according to a second aspect of the present invention for solving the above problems is formed in the electrode outer membrane, the electrode outer body, the electrode outer body is filled with an electrode electrolyte solution at one end; At least one inner electrode installed and immersed in the electrode electrolyte solution, and installed at the electrode outer body and immersed in the electrode electrolyte solution, the at least one conductivity measuring cell measuring the electrical conductivity of the electrode electrolyte solution. do.

In addition, the electrochemical potential self-correction apparatus using a reference electrode having an automatic calibration function according to the first aspect of the present invention for solving the above problems, the electrolyte separator is formed at one end, the electrode electrolyte solution is filled therein An electrical conductivity of the electrode electrolyte solution by applying an alternating current voltage to the reference electrode and the reference electrode including two or more internal electrodes formed on the outer body and the electrode outer body and submerged in the electrode electrolyte solution and electrically separated from each other; And a reference potential corrector for outputting a correction signal regarding a reference potential change of the reference electrode.

In addition, the electrochemical potential automatic correction apparatus using a reference electrode having an automatic calibration function according to the second aspect of the present invention for solving the above problems is an electrode in which an electrolyte separator is formed at one end, the electrode electrolyte solution is filled therein One or more internal electrodes installed on the outer body, the electrode outer body and immersed in the electrode electrolyte solution and formed on the electrode outer body and immersed in the electrode electrolyte solution, to measure the electrical conductivity of the electrode electrolyte solution And a reference potential calibrator for outputting a correction signal regarding a reference potential change of the reference electrode according to the electrical conductivity measured by the conductivity measurement cell.

The reference electrode having the automatic calibration function and the electrochemical potential automatic calibration device using the same according to the present invention configured as described above can calculate the concentration of the internal electrolyte such as chlorine ion by measuring the electrical conductivity of the internal electrolyte of the reference electrode. Even if the concentration of the electrolyte solution inside the electrode changes due to exposure to the test environment, the potential change of the reference electrode can be properly compensated. This has the effect of maintaining the function of the reference electrode for a long time.

Hereinafter, with reference to the accompanying drawings will be described specific details and embodiments of the present invention.

2 is a diagram illustrating a first embodiment of a reference electrode having an automatic calibration function according to the present invention.

2, a first embodiment of a reference electrode having an automatic calibration function according to the present invention includes an electrode outer body 100, two or more inner electrodes 210 and 220 installed in the electrode outer body 100, and The electrode electrolyte solution 400 is filled in the electrode outer body.

2 illustrates a case where two internal electrodes are provided.

An electrolyte separator 110 is formed at the end of the electrode outer body 100 to prevent the electrode electrolyte solution 400 and the solution outside the reference electrode from being mixed.

On the opposite end of the electrode outer body 100, a fixing part 120 in which an internal electrode is inserted and fixed is formed. The fixing part 120 fixes two internal electrodes spaced apart from each other by a predetermined interval.

The number of internal electrodes may be two or more.

The two or more internal electrodes are formed to be electrically separated from each other when the electrode electrolyte solution 400 is not present.

The internal electrodes 210 and 220 are formed of a material including at least one of a metal, a conductive nonmetal, a metal chloride, a metal oxide, and a metal sulfide.

Here, the metal and conductive nonmetal materials are silver (Ag), mercury (Hg), copper (Cu), platinum (Pt), gold (Au), nickel (Ni), titanium (Ti), zirconium (Zr), molybdenum (Mo), tungsten (W), glassy carbon, graphite.

The internal electrode is preferably one of silver (Ag), mercury (Hg), copper (Cu), platinum (Pt), gold (Au), titanium (Ti), zirconium (Zr), and glassy carbon. It is comprised from the material containing the above, More preferably, it is comprised from the metal material containing one or more of silver (Ag), mercury (Hg), and platinum (Pt).

The internal electrode has a structure including at least one of rod, wire, tube, mesh, plate, thin layer, and fiber. Preferably, the internal electrode is formed in a structure including one or more of a rod, a wire, a tube, and a thin layer.

The interval between two or more internally separated internal electrodes is in the range of 0.01 mm or more and 200 mm or less, preferably 0.1 mm or more and 50 mm or less, more preferably 0.2 mm or more and 10 mm or less.

As the deviation from the above-mentioned preferred value, the size of the reference electrode is not suitable for measurement and use, many measurement errors occur and it becomes difficult to miniaturize the reference electrode.

In addition, if the distance between the internal electrodes is too close, there is a high possibility that the internal electrodes are connected to each other and electrically shorted (short), and if the distance between the internal electrodes is too far, a voltage drop due to an unexpected other reaction occurs, the error in the conductivity measurement There is a lot of potential to occur.

The electrode electrolyte solution 400 is a medium for generating an electrode reaction of the reference electrode.

The concentration range of the electrode electrolyte solution 400 is from 10 ^-6 M to saturation concentration, preferably from 10 ^-5 M to saturation concentration, more preferably from 10 ^-4 M to 1 M concentration.

As the deviation from the preferable numerical value shown above increases the conductivity measurement error, the accuracy of calculating the concentration of the electrolyte (for example, KCl) from the electrical conductivity decreases. In other words, the potential value (voltage value) is proportional to the logarithmic value of the activity (concentration) of the electrolyte, so if the concentration is too low, there is a high possibility of error, and if it is too high, a difference in concentration from the measurement environment occurs. As a result, a decrease in concentration of the electrolyte due to diffusion occurs.

The electrode electrolyte includes one or more of chloride, sulfide, and bromide, and preferably, one or more of potassium chloride (KCl) and sodium chloride (NaCl).

The cell factor of the reference electrode including the internal electrode (geometric factor: distance between electrodes / electrode area) has a range of 10 ⁻⁸ to 10 ⁸ m ⁻¹ , preferably 10 ⁻⁶ to 10 ⁶ m ⁻¹ Has

The reference electrode may further include a temperature sensor (T in FIG. 6) for measuring the temperature of the electrode electrolyte solution 400. Since the temperature of the electrode electrolyte solution is substantially the same as the temperature of the solution in which the reference electrode is placed, the temperature sensor may be separately provided outside the reference electrode.

The reference electrode having an automatic calibration function configured as described above applies a voltage to the two internal electrodes 210 and 220 to measure the electrical conductivity of the electrode electrolyte solution 400, and the measured electrical conductivity and electrode electrolyte solution. Knowing the temperature of, it is possible to calculate how much the reference potential change of the reference electrode has occurred. By using the calculated value, more accurate potential measurement between the reference electrode and the indicator electrode is possible. A more detailed description will be described later.

3 is a diagram illustrating a second embodiment of a reference electrode having an automatic calibration function according to the present invention.

Referring to FIG. 3, a second embodiment of a reference electrode having an automatic calibration function according to the present invention includes an electrode outer body 100, at least one inner electrode 200 installed at the electrode outer body 100, and the electrode. An electrode electrolyte solution 400 is filled in the external body and a conductivity measuring cell 300 for measuring the electrical conductivity of the electrode electrolyte solution.

The electrode outer body 100, the inner electrode 200, and the electrode electrolyte solution 400 are substantially the same as in the first embodiment, and thus description thereof is omitted.

The conductivity measuring cell 300 is installed in the electrode outer body 100 and is immersed in the electrode electrolyte solution 400.

For example, the conductivity measuring cell 300 may be configured as a four-probe conductivity cell having four electrodes, and the electrical conductivity of the electrode electrolyte solution may be measured by a direct current measurement method.

4 to 6 are diagrams illustrating a first embodiment of an electrochemical potential correcting apparatus using a reference electrode having an automatic calibration function according to the present invention.

First of all, the basic theory is that, in general research and industry, the reference electrode is a silver / silver chloride electrode or a calomel electrode. The reference electrode has a potential that changes as a reference to the concentration of KCl, the electrolyte inside the electrode. For example, the silver / silver chloride electrode reaction can be confirmed by the following reaction equation and its Nernst equation. The silver / silver chloride reference electrode is characterized by chemical activity (a _Cl ), which is the effective concentration of chlorine ion in the electrolyte inside the electrode. Is determined.

^{AgCl + e ↔ Ag + + Cl} -; E ° = 0.222 V _SHE

E _{Ag / AgCl} = E ° _{Ag / AgCl} -0.059 log (a _Cl )

Here, E is the reference potential of the reference electrode in consideration of the influence of chlorine ions, E ° is the standard potential of the reference electrode.

In addition, the electrical conductivity of potassium chloride (KCl) used as the electrolyte inside the electrode at room temperature is proportional to the concentration of potassium chloride as shown in FIG. In addition, it is shown in FIG. 8 that this proportional relationship is maintained even under the same temperature condition even if the temperature is changed.

Therefore, if the temperature and electrical conductivity of the internal electrolyte of the reference electrode can be known, the concentration of the electrolyte inside the electrode can be easily calculated, and further, the potential reference indicated by the reference electrode can be predicted.

Since the matters related to the reference electrode are substantially the same as the first embodiment of the reference electrode of FIG. 1 described above, description thereof will be omitted.

The reference electrode refers to an electrode which is a reference when measuring or applying a voltage for electrochemical measurement, and the indicator electrode is collectively referred to as an indicator electrode. For example, if the pH is measured, the PH electrode is the indicator electrode, and if it detects ions, the ion sensing electrode is the indicator electrode.

In general, when the voltage of the indicator electrode 600 is measured at 1V, it means that it is 1V compared to the reference electrode (0V). Therefore, the indicator electrode 600 is changed according to the measurement target, but the reference electrode is not changed.

In FIG. 4 to FIG. 6, a portion indicated by a dotted line EC is an electrochemical potential automatic calibration apparatus using a reference electrode having an automatic calibration function according to the present invention.

4 to 6 are diagrams illustrating the state in which the indicator electrode 600 and the electrostatic potential / current measuring instrument 700 are connected to each other.

4 to 6, the first embodiment of the electrochemical potential automatic correction apparatus using a reference electrode having an automatic calibration function according to the present invention is formed with an electrolyte separator at one end, the electrode electrolyte solution 400 therein The electrode outer body 100 and the electrode outer body 100 to be filled and the reference electrode including two or more internal electrodes formed to be submerged in the electrode electrolyte solution and electrically separated, and the AC voltage to the inner electrode And a reference potential calibrator 500 for measuring an electrical conductivity of the electrode electrolyte solution by outputting the same, and outputting a correction signal regarding a reference potential change of the reference electrode.

The reference potential calibrator 500 measures an electrical conductivity of the electrode electrolyte solution by applying a voltage to two internal electrodes, calculates the concentration of the electrode electrolyte accordingly, and provides an information signal for a correction value to correct the reference potential accordingly. Send it out.

At this time, the reference potential calibrator 500 simply measures the electrical conductivity and transmits information thereof, and the electrostatic potential / current measuring instrument 700 may be configured to calculate the concentration of the electrode electrolyte and to correct the reference potential accordingly. It may be.

In addition, the reference potential calibrator 500 may measure the electrical conductivity of the electrode electrolyte by an AC measuring method or a DC measuring method.

In the case of the AC measuring method, the measurement frequency range used for the measurement of the electrical conductivity is, for example, 0.1 Hz or more and 1000 KHz or less, preferably 0.1 Hz or more and 100 KHz or less, and more preferably 0.1 Hz or more and 10 KHz.

As the AC frequency deviates from the above-described range during conductivity measurement, a large error occurs in the conductivity measurement, which makes it difficult to accurately correct the reference electrode. If the measurement frequency is too fast, the capacitor component of the electrode / electrolyte interface is reflected in the conductivity measurement value. If the frequency is too slow, the resistance of the film formed on the surface of the electrode intervenes to give an error in the electrolyte conductivity measurement.

In the case of direct current measurement, the current range is preferably 10 ⁻¹ A cm ⁻² or less.

Deviating from the numerical values presented above, the size of the electric conductivity measuring cell and the power capacity of the measuring system are increased, so that the system is not optimized and may cause difficulty in accurate conductivity measurement.

In this case, when the temperature of the electrode electrolyte is required for more accurate calculation, a temperature sensor T for measuring the temperature of the electrode electrolyte may be further provided in the reference electrode as shown in FIG. 6.

4 is a relay connection state when calibrating the reference electrode.

When the potential of the reference electrode is to be corrected, the switch S1 is turned off and the switch S2 is turned on so that the reference potential calibrator 500 measures the electrical conductivity of the electrode electrolyte solution 400 using the internal electrode of the reference electrode. The correction signal in consideration of the electrical conductivity or the electrical conductivity is transmitted to the electrostatic potential / current measuring device 700 which is an external device.

5 is a relay connection when measuring with an electrochemical device.

When the reference electrode is not calibrated, that is, when measured by an electrochemical device, for example, the electrostatic potential / current measuring device 700 as an example, the switch S1 is turned on and the switch S2 is turned off.

One of the internal electrodes of the reference electrode and the indicator electrode 600 are connected to the electrostatic potential / current measuring device 700, and a general operation is performed.

Therefore, before or after the general measurement as shown in FIG. 5, the connection as shown in FIG. The final potential / current value is determined.

According to a second embodiment of an electrochemical potential correcting apparatus using a reference electrode having an automatic calibration function according to the present invention, an electrolyte separator is formed at one end, and an electrode outer body in which an electrode electrolyte solution is filled therein, the electrode outer body. One or more internal electrodes installed on the electrode electrolyte solution and submerged in the electrode electrolyte solution and installed on the electrode outer body and submerged in the electrode electrolyte solution, the reference comprising a conductivity measuring cell for measuring the electrical conductivity of the electrode electrolyte solution And a reference potential corrector for outputting a correction signal relating to a change in the reference potential of the reference electrode according to the electrical conductivity measured by the electrode and the conductivity measuring cell.

That is, the second embodiment of the electrochemical potential correcting apparatus using the reference electrode having an automatic calibration function according to the present invention uses a reference electrode of the type shown in FIG. 3 in comparison with the first embodiment. The difference is that the rest of the configuration is substantially the same as in the first embodiment, and thus the description is omitted.

7 is a graph of electrical conductivity change according to KCl concentration at room temperature, and FIG. 8 is a graph of electrical conductivity change according to temperature change of an aqueous solution having various KCl concentrations.

The present invention is described in detail by way of example in the case of using potassium chloride (KCL) as an electrode electrolyte.

The conductivity change when potassium chloride (KCl), which is widely used as the electrolyte inside the reference electrode, is diluted in distilled water is shown in FIG. 7. When 0.1 M KCl is used as the internal electrolyte of the reference electrode used for a long time in the heat exchanger cooling water, even if the concentration of the electrode electrolyte decreases, the conductivity of the reference electrode and the electrochemical potential correction device according to the present invention is measured. Since the concentration change can be predicted, the potential change of the reference electrode can be detected.

 In other words, the measured electrical conductivity has a linear proportionality with the KCl concentration. In this case, the measured electrical conductivity is generally measured by applying an AC voltage.

Knowing the electrical conductivity, KCl concentration can be determined (KCl concentration ≒ a _Cl ) and E _{Ag / AgCl} , which is the reference potential of the reference electrode, can be known using Equation 1.

As described above, the reference electrode having the automatic calibration function according to the present invention and the electrochemical potential automatic calibration apparatus using the same have been described with reference to the illustrated drawings, but the present invention is not limited to the embodiments and drawings disclosed herein. The technology can be applied within the scope of protection.

1 is a cross-sectional view showing a structure of a conventional reference electrode commonly used;

2 is a view showing a first embodiment of a reference electrode having an automatic calibration function according to the present invention;

3 is a view showing a second embodiment of a reference electrode having an automatic calibration function according to the present invention;

4 to 6 is a view showing an embodiment in which the electrochemical potential automatic correction device according to the present invention is connected to the indicator electrode and the electrochemical measuring device,

7 is a graph of electrical conductivity change according to KCl concentration at room temperature,

8 is a graph of electrical conductivity change according to temperature change of an aqueous solution having various KCl concentrations.

<Explanation of symbols on main parts of the drawings>

100: electrode outer body 110: electrolyte separator

200, 210, 220: internal electrode 300: conductivity measuring cell

400: electrode electrolyte solution 500: reference potential calibrator

600: indicator electrode 700: electrochemical measuring device

Claims (24)

An electrode outer body in which an electrolyte separator is formed at one end and an electrode electrolyte solution is filled therein; A reference electrode having an automatic calibration function installed on the electrode outer body and submerged in the electrode electrolyte solution and including two or more internal electrodes electrically separated from each other. An electrode outer body in which an electrolyte separator is formed at one end and an electrode electrolyte solution is filled therein; One or more internal electrodes installed on the electrode outer body and submerged in the electrode electrolyte solution; The reference electrode having an automatic calibration function is installed on the electrode outer body and is immersed in the electrode electrolyte solution, including at least one conductivity measuring cell for measuring the electrical conductivity of the electrode electrolyte solution. The method according to claim 1 or 2, The reference electrode having the automatic calibration function further comprises a temperature sensor for measuring the temperature of the electrolyte. The method according to claim 1 or 2, The internal electrode is a reference electrode having an automatic calibration function, characterized in that formed of a material containing at least one of metal, conductive nonmetal, metal chloride, metal oxide and metal sulfide. The method according to claim 1 or 2, The internal electrode may be formed in at least one of rod, wire, tube, mesh, plate, thin layer, and fiber. Reference electrode with calibration function. The method according to claim 1 or 2, The reference electrode having an automatic calibration function, characterized in that the number of the internal electrode is two or more than five. The method according to claim 1 or 2, The distance between the internal electrode is a reference electrode having an automatic calibration function, characterized in that 0.01mm or more and 200mm or less. The method according to claim 1 or 2, The concentration range of the electrode electrolyte solution is a reference electrode having an automatic calibration function, characterized in that between ^10-6 M saturation concentration. A reference electrode including an electrode separator formed at one end, an electrode outer body filled with an electrode electrolyte solution therein, and two or more inner electrodes formed on the electrode outer body and immersed in the electrode electrolyte solution and electrically separated from each other. ; And A reference potential corrector for applying an AC voltage to the internal electrode to measure an electrical conductivity of the electrode electrolyte solution and outputting a correction signal regarding a change in the reference potential of the reference electrode; Electrochemical potential automatic calibration device using a reference electrode having an automatic calibration function comprising a. An electrolyte separator is formed at one end, an electrode outer body filled with an electrode electrolyte solution therein, at least one inner electrode formed on the electrode outer body and immersed in the electrode electrolyte solution, and installed at the electrode outer body. A reference electrode formed to be immersed in an electrolyte solution, the reference electrode including a conductivity measurement cell for measuring electrical conductivity of the electrode electrolyte solution; And A reference potential corrector for outputting a correction signal relating to a change in the reference potential of the reference electrode according to the electrical conductivity measured by the conductivity measuring cell; Electrochemical potential automatic calibration device using a reference electrode having an automatic calibration function comprising a. The method according to claim 9 or 10, Wherein the internal electrode is formed of a material including at least one of a metal, a conductive nonmetal, a metal chloride, a metal oxide, and a metal sulfide. The method of claim 11, The metal and conductive nonmetal materials include silver (Ag), mercury (Hg), copper (Cu), platinum (Pt), gold (Au), nickel (Ni), titanium (Ti), zirconium (Zr), and molybdenum (Mo). ), Tungsten (W), glassy carbon (Glassy Carbon), graphite (Graphite) electrochemical potential automatic calibration device using a reference electrode having an automatic calibration function, characterized in that it comprises at least one. The method according to claim 9 or 10, The internal electrode may be formed in at least one of rod, wire, tube, mesh, plate, thin layer, and fiber. Electrochemical potential automatic calibration device using a reference electrode having a calibration function. The method according to claim 9 or 10, Electrochemical potential automatic calibration device using a reference electrode having an automatic calibration function, characterized in that the number of the internal electrode is two or more than five. The method according to claim 9 or 10, Electrochemical potential automatic calibration device using a reference electrode having an automatic calibration function, characterized in that the distance between the internal electrode is 0.01mm or more and 200mm or less. The method according to claim 9 or 10, Electrochemical potential automatic calibration device using a reference electrode having an automatic calibration function, characterized in that the concentration range of the electrode electrolyte solution is between 10 ^-6 M to saturation concentration. The method according to claim 9 or 10, The electrode electrolyte is an electrochemical potential automatic calibration device using a reference electrode having an automatic calibration function, characterized in that it comprises at least one of chloride, sulfide, bromide. The method according to claim 9 or 10, The electrode electrolyte is an electrochemical potential calibration device using a reference electrode having an automatic calibration function, characterized in that it comprises at least one of potassium chloride (KCl) and sodium chloride (NaCl). The method according to claim 9 or 10, The cell distance coefficient of the reference electrode (geometric factor: electrode distance / electrode area) is an electrochemical potential calibration device using a reference electrode having an automatic calibration function, characterized in that the range of 10 ^-8 ~ 10 ⁸ m ^-1 . The method according to claim 9 or 10, The current range used for measuring the electrical conductivity is 10 ^-1 A cm ^-2 or less in the case of the direct current method electrochemical potential automatic calibration device using a reference electrode having an automatic calibration function. The method according to claim 9 or 10, The measurement frequency range used for measuring the electrical conductivity is an electrochemical potential calibration device using a reference electrode having an automatic calibration function, characterized in that the AC method is 0.1 Hz or more and 1000 KHz or less. The method according to claim 9 or 10, The measurement frequency range used for the measurement of the electrical conductivity is an electrochemical potential calibration device using a reference electrode having an automatic calibration function, characterized in that 0.1 to 100 KHz in the AC system. The method according to claim 9 or 10, The measurement frequency range used for measuring the electrical conductivity is an electrochemical potential correction device using a reference electrode having an automatic calibration function, characterized in that the AC method is 0.1 Hz or more 10 KHz or less. The method according to claim 9 or 10, The electrochemical potential automatic calibration device using the reference electrode having the automatic calibration function further comprises a temperature sensor for measuring the temperature of the electrolyte electrochemical potential automatic calibration device using the reference electrode having an automatic calibration function.

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