CN113267548B

CN113267548B - Method for producing an electrode system for an electrochemical test system

Info

Publication number: CN113267548B
Application number: CN202110711496.3A
Authority: CN
Inventors: 李党国; 王家浩; 邵天敏
Original assignee: Tsinghua University
Current assignee: Tsinghua University
Priority date: 2021-06-25
Filing date: 2021-06-25
Publication date: 2022-03-29
Anticipated expiration: 2041-06-25
Also published as: CN113267548A

Abstract

A method of manufacturing an electrode system of an electrochemical testing system for performing an electrochemical test on a sample is provided. The electrode system comprises a working electrode, a reference electrode and a counter electrode. The manufacturing method of the working electrode comprises the following steps: welding a sample at one end of an electrode rod; placing an electrode rod and a sample into the sleeve for the working electrode, and enabling the sample to be positioned at one end of the sleeve for the working electrode; sealing one end of the sleeve for the working electrode where the sample is located by using high-temperature cement; sealing one end of the sleeve for the working electrode, where the non-sample is located, by using a sealant, and enabling the electrode rod to penetrate through the sealant; and after the sleeve for the working electrode is sealed by high-temperature cement and sealant, placing the working electrode in an environment of 10-40 ℃ for 8-12 hours, and then placing the working electrode in an environment of 150-300 ℃ for 2-5 hours to obtain the packaged working electrode.

Description

Method for producing an electrode system for an electrochemical test system

Technical Field

The present application relates to electrochemical test devices, and more particularly, to a method of manufacturing an electrode system for an electrochemical test system.

Background

In a marine environment, hot corrosion of hot end parts of an aircraft engine is one of the main causes of engine failure, so that the research on the hot corrosion problem of the high-temperature hot end parts of the aircraft engine is of great significance. The hot end component of the aircraft engine is mainly made of high-temperature alloy and high-temperature coating, and the corrosion resistance of the hot end component is closely related to the electrochemical property of an oxide layer on the surface of the hot end component. The change rule of the capacitance of the oxide layer along with the potential is obtained by measuring a Mott-Schottky curve, the defect type and the density of the oxide layer can be analyzed, and the energy band structure and the semiconductor property of the oxide layer are further obtained. The test of the Mott-Schottky curve is based on an impedance test of applying a high-frequency alternating current signal, the sensitivity is extremely high, and electromagnetic interference from the outside and a heating element in a furnace can greatly influence the sensitivity.

The existing high-temperature electrochemical device mostly ignores the electromagnetic shielding problem, and although the device can carry out tests such as potentiodynamic scanning and the like, the accurate and stable impedance test is difficult to carry out.

The traditional high-temperature working electrode is manufactured by mechanically connecting a sample and a lead and sealing the sample and the lead in a corundum sleeve by using high-temperature cement. Electrodes made in this way have many problems, for example, high temperature oxidation of the contact points can lead to inaccurate measurement results, and the sample is loosened due to insufficient adhesion of high temperature cement to the sample and the electrode casing. In addition, the sample can be subjected to solid salt corrosion along with the temperature rise process of the molten salt, the subsequent molten salt corrosion performance test can be influenced, a working electrode needs to be directly inserted into the molten salt from the normal temperature in order to solve the problem, and a common corundum sleeve of the electrode is easy to explode and cause danger when the electrode is rapidly cooled and heated.

The electrode rod of the traditional high-temperature reference electrode is made of silver, the manufacturing process is complex, and the stability of the electrode rod is poor after the electrode rod is used for multiple times. The use temperature of the electrochemical test cannot exceed 960 ℃ due to the limitation of the melting point of silver, and a new high-temperature reference electrode is required to replace the electrochemical test at higher temperature.

Disclosure of Invention

To ameliorate or solve at least one of the problems mentioned in the background, the present application provides a method of manufacturing an electrode system of an electrochemical testing system.

The electrode system of the electrochemical test system is used for carrying out electrochemical test on a sample, the electrode system comprises a working electrode, a reference electrode and a counter electrode,

the manufacturing method of the working electrode comprises the following steps:

providing an electrode rod, a sleeve for a working electrode, high-temperature cement and sealant;

welding the sample to one end of the electrode rod;

placing the electrode rod and the sample into the sleeve for the working electrode, so that the sample is positioned at one end of the sleeve for the working electrode;

sealing one end of the working electrode casing where the sample is located with the high temperature cement;

sealing one end, not provided with the sample, of the sleeve for the working electrode by using the sealant, and enabling the electrode rod to penetrate through the sealant; and

after the sleeve for the working electrode is sealed by the high-temperature cement and the sealant, the working electrode is placed for 8-12 hours at the temperature of 10-40 ℃, and then the working electrode is placed for 2-5 hours at the temperature of 150-300 ℃ to obtain the packaged working electrode.

In at least one embodiment, the electrode shaft is an iron-chromium-aluminum wire and the sleeve for the working electrode is made of mullite.

In at least one embodiment, the test face of the sample partially protrudes from the high temperature cement or the end face of the sample is flush with the high temperature cement.

In at least one embodiment, before the high temperature cement encapsulates the sample, the sample is ground so that the surface and corners of the sample protruding the high temperature cement are smooth, or the test surface of the sample flush with the high temperature cement and the corners of the test surface are smooth.

In at least one embodiment, in a state where the working electrode is completely encapsulated, a surface of the sample protruding the high temperature cement is ground, or a surface of the sample flush with the high temperature cement is ground.

In at least one embodiment, the sample is sanded using, in order, 800 # silicon carbide sandpaper, 2000 # silicon carbide sandpaper, 4000 # silicon carbide sandpaper, 7000 # silicon carbide sandpaper.

In at least one embodiment, after the sample is welded with the electrode rod and before the electrode sleeve for working is placed, the sealing glue is used for wrapping the electrode rod and the welding point of the electrode rod and the sample.

In at least one embodiment, the reference electrode is fabricated by a method comprising:

providing a platinum wire for a reference electrode, a sleeve for the reference electrode, high-temperature cement and a sealant;

placing the platinum wire for the reference electrode into the inside of the sleeve for the reference electrode;

sealing one end of the reference electrode casing with the high temperature cement;

sealing the other end of the sleeve for the reference electrode by the sealant, and enabling the platinum wire for the reference electrode to penetrate through the sealant; and

after the sleeve for the reference electrode is sealed by the high-temperature cement and the sealant, the reference electrode is placed for 8-12 hours at the temperature of 10-40 ℃, and then the reference electrode is placed for 2-5 hours at the temperature of 150-300 ℃, so that the packaged reference electrode is obtained.

In at least one embodiment, the platinum wire for the reference electrode partially protrudes from the high temperature cement, and the material of the casing for the reference electrode is mullite.

In at least one embodiment, the method of manufacturing the counter electrode includes:

providing a platinum wire for a counter electrode, a platinum sheet, a sleeve for the counter electrode, high-temperature cement and sealant;

welding the platinum wire for the counter electrode to the platinum sheet;

placing the platinum wire and the platinum sheet for the counter electrode into the sleeve for the counter electrode, so that the platinum sheet is positioned at one end of the sleeve for the counter electrode;

sealing one end of the sleeve for the counter electrode where the platinum sheet is located with the high-temperature cement;

sealing the other end of the sleeve for the counter electrode by the sealant, and enabling the platinum wire for the counter electrode to penetrate through the sealant; and

after the sleeve for the counter electrode is sealed by the high-temperature cement and the sealant, the counter electrode is placed for 8-12 hours at the temperature of 10-40 ℃, and then the counter electrode is placed for 2-5 hours at the temperature of 150-300 ℃ to obtain the packaged counter electrode.

In at least one embodiment, the material of the sleeve for the counter electrode is mullite, and the platinum sheet partially protrudes from the high-temperature cement.

In the prior art, the viscosity of high-temperature cement to an electrode rod is not enough, so that a sample on the electrode rod is easy to loosen. In this application, the non-sample end of the sleeve pipe for the working electrode far away from the molten salt is sealed through the sealant, and the electrode rod penetrates through the sealant. The solidified sealant is firmer than high-temperature cement, and has better fixing effect on the electrode rod, thereby preventing the sample from loosening better.

Drawings

Fig. 1 shows a schematic structural diagram of an electrochemical testing system for molten salt corrosion experiments according to an embodiment of the present application.

Fig. 2 shows a schematic structural diagram of a working electrode in an electrode system of an electrochemical testing system for molten salt corrosion experiments according to an embodiment of the present application.

Fig. 3 shows a bottom view of fig. 2.

Fig. 4 shows a schematic structural diagram of a reference electrode in an electrode system of an electrochemical testing system for molten salt corrosion experiments according to an embodiment of the present application.

Fig. 5 shows a schematic structural diagram of a counter electrode in an electrode system of an electrochemical testing system for molten salt corrosion experiments according to an embodiment of the present application.

Fig. 6 shows a schematic structural diagram of a bulk furnace plug and a furnace plug sleeve of an electrochemical testing system for molten salt corrosion experiments according to an embodiment of the present application.

Fig. 7 shows a schematic structural diagram of an experimental crucible and a gasket of an electrochemical testing system for molten salt corrosion experiments according to an embodiment of the present application.

Fig. 8 shows a schematic structural diagram of a comparative crucible of an electrochemical testing system for molten salt corrosion experiments according to an embodiment of the present application.

Description of the reference numerals

1, a reaction furnace body; 2, a shell; 3 a heating element; 4, a temperature control system; 5, a gasket; 6 crucible for experiment; 7, a protective cylinder; 8, shielding cylinder; 9, a furnace plug of the body; 10 a working electrode; 11 a reference electrode; 12 pairs of electrodes; 13 crucible for comparison; 14 electrode rods; 15 sample; 16 contact points; 17 a sleeve for a working electrode; 18 high temperature cement; 19 sealing glue; 20, testing surface; 21 platinum wire for reference electrode; 22 a sleeve for a reference electrode; 23 pairs of electrodes using platinum wire; 24 platinum sheets; 25 pairs of electrode sleeves; 26 furnace plug electrode holes; 27 furnace plug sleeve; 28 control crucible cover; 29 crucible body for comparison; 30 crucible cover for experiment; 31 crucible electrode hole for experiment; 32 crucible body for experiment.

Detailed Description

Exemplary embodiments of the present application are described below with reference to the accompanying drawings. It should be understood that the detailed description is only intended to teach one skilled in the art how to practice the present application, and is not intended to be exhaustive or to limit the scope of the application.

The application provides a system capable of carrying out molten salt corrosion experiments on metal and high-temperature-resistant coatings and carrying out electrochemical tests on corrosion layers. The system can be used for researching the corrosion electrochemical behavior of the metal and the coating in a high-temperature molten salt medium, and further reasonably explaining the high-temperature hot corrosion mechanism of the metal and the coating. It is understood that the metals described in this application include pure metals as well as alloys.

As shown in fig. 1 and 6, the electrochemical test system for molten salt corrosion experiments in the present application may include a reaction furnace body 1, a body furnace plug 9, a heating module, a crucible module, an electrode system, and an electromagnetic shielding module.

The wall of the reactor body 1 may be made of a heat insulating material such as ceramic fiber. The reaction furnace body 1 may include a side furnace door (not shown) for taking and placing a crucible (described later).

The reaction furnace body 1 may include a top opening, and the body furnace stopper 9 may be sealingly inserted into the top opening of the reaction furnace body 1. The bulk furnace plug 9 may include a furnace plug electrode hole 26 through which an electrode system (described later) may extend into the reactor body 1. For smooth disassembly and assembly, the diameter of the furnace plug electrode hole 26 may be larger than the diameter of the electrode in the electrode system.

In order to maintain the sealing property, a high temperature resistant glass cloth (not shown in the figure) can be used to block the gap between the furnace plug 9 and the reaction furnace body 1, and the gap between the electrode hole 26 of the furnace plug and the electrode. The molten salt experiment can be often accompanied with the production of acid toxic gases such as chlorine, sulfur dioxide, etc., alkaline liquids such as sodium bicarbonate solution can be regularly dripped on the high-temperature resistant glass fiber cloth to react with acid toxic gases such as chlorine, sulfur dioxide, etc., so as to prevent the toxic gases from leaking.

Heating module

As shown in fig. 1, the heating module may include a heating element 3, a temperature control system 4. The heating module can provide an experimental environment with the temperature of 600-1200 ℃ or even higher for the furnace chamber of the reaction furnace body 1.

The heating element 3 can be arranged in the furnace chamber of the reaction furnace body, and the heating element 3 includes but is not limited to a silicon carbide rod, a silicon molybdenum rod, a high temperature resistance wire and the like.

The temperature control system 4 can be an intelligent temperature control system of the existing reaction furnace, and realizes accurate control on the temperature in the furnace. For example, the temperature control system 4 can realize accurate temperature control with an error of not more than 5 ℃ within a range of 600-1200 ℃.

Crucible module

As shown in fig. 1, 7 and 8, the crucible module may include an experimental crucible 6, a shield cylinder 7 and a control crucible 13.

The crucible 6 may include a crucible body 32 and a crucible cover 30. The experimental crucible cover 30 can be covered on the experimental crucible body 32 to prevent the pollution of the crucible. The experimental crucible cover 30 is provided with an experimental crucible electrode hole 31, and the position of the experimental crucible electrode hole 31 can correspond to the position of the furnace plug electrode hole 26, so that an electrode in an electrode system can smoothly pass through each electrode hole.

The molten salt in the experimental crucible 6 can be flexibly selected according to the experimental environment, and the molten salt is ensured to be co-molten into a liquid state at the experimental temperature. For example, in one embodiment of the present application, a molten salt corrosion experiment may be performed using 70g of sodium chloride, 70g of potassium chloride, and 30g of sodium sulfate as molten salts under a temperature condition of 1000 ℃.

The experimental crucible 6 may correspond to the open top of the reactor body 1, and a protective tube 7 may be fitted around the outer periphery of the experimental crucible 6. The protective cylinder 7 can isolate the reaction system in the experimental crucible 6, and prevent the corrosive gas (such as chlorine, sulfur trioxide and sulfur dioxide) generated in the molten salt experiment in the experimental crucible 6 from overflowing to a certain extent.

Meanwhile, a shielding cylinder 8 (described later) may be fitted around the outer circumferential side of the shield cylinder 7. It can be understood that the diameter of the experimental crucible electrode hole 31 can be larger than that of the electrode in the electrode system, and the corundum protective cylinder 7 separates the experimental crucible 6 from the shielding cylinder 8, so that the stripped objects can be prevented from falling into the molten salt of the experimental crucible body 32 from the experimental crucible electrode hole 31.

The crucible 13 for comparison may be disposed around the crucible 6 for experiment, and the crucible 6 for experiment may be used for electrochemical test of molten salt corrosion experiment, and the crucible 13 for comparison may be used for conventional molten salt corrosion experiment to obtain parallel samples. There may be a plurality of comparison crucibles 13, so that a plurality of parallel samples are obtained.

The control crucible 13 was the same molten salt as the experimental crucible 6 and the samples tested were the same. The comparative crucible 13 and the experimental crucible 6 were etched under the same conditions, but since an electrode system (described later) was not applied to the comparative crucible 13, a naturally formed etched layer was obtained in the comparative crucible 13 without the influence of an applied potential. The experimenter can perform test characterization on the naturally formed corrosion layers, such as observing the surface appearance, element distribution and the like.

The crucible for comparison 13 may include a crucible body for comparison 29 and a crucible cover for comparison 28. The control crucible cover 28 can be covered on the control crucible body 29 to prevent contamination. The control crucible 13 can be placed in and taken out from the side furnace door of the reaction furnace body 1.

After the experiment, the actual etching time of the sample is prolonged by the temperature lowering process in the furnace, so that the control crucible 13 can be preferentially held by the furnace chuck and cooled outside the furnace. Since the molten salt is directly broken and the oxide layer is peeled off, the sample in the control crucible 13 can be taken out by ultrasonic cleaning with hot water.

Electrode system

As shown in fig. 1, 2, 3, 4 and 5, the electrode system in the present application may include a working electrode 10, a reference electrode 11 and a counter electrode 12. The application also provides a manufacturing method of the working electrode 10, the reference electrode 11 and the counter electrode 12.

The working electrode 10 may include an electrode shaft 14, a working electrode casing 17, high temperature cement 18, and a sealant 19. The electrode shaft 14 is preferably an iron-chromium-aluminum alloy wire, and the electrode shaft 14 may be other high temperature alloy wires.

The electrode rod and the sample in the prior art are usually mechanically connected through rivets and the like, and when the electrode rod and the sample are mechanically connected, the problems of high-temperature oxidation of a contact point and misalignment of a test result caused by poor contact usually occur. In the present application, one end of the electrode rod 14 can be welded to the sample 15 in a manner that avoids the above-mentioned problems. In order to avoid the concentrated discharge phenomenon caused by the rough surface or the edges of the sample 15, the sample 15 can be polished by sequentially using 800 # silicon carbide abrasive paper, 2000 # silicon carbide abrasive paper, 4000 # silicon carbide abrasive paper and 7000 # silicon carbide abrasive paper before welding, so that the sample 15 is smooth. At least the surface and the corners of the sample 15 protruding from the high temperature cement 18 (described later) are smooth, or the test surface 20 (described later) and the corners of the test surface 20 are smooth.

To avoid oxidation problems of the electrode rod 14, the electrode rod 14 and the weld points of the electrode rod 14 and the sample 15 may be encapsulated with a sealant 19 (described below) to seal the electrode rod 14 from air.

The specimen 15 may be an elongated cube or cylinder, for example a 4 x 2 x 40mm cube, and the welding machine is used to weld the specimen 15 to the electrode rod 14 at a relatively small area end face, for example the contact point 16. The end face of the sample 15, which is smaller in area and not welded to the electrode rod 14, serves as a test face 20, and a coating can be sprayed on the test face 20 according to research requirements. Namely, the molten salt corrosion characteristics of the sample 15 itself can be tested, and the molten salt corrosion characteristics of the coating can also be tested. Sample 15 may be, for example, an Inconel718 alloy and the coating may be, for example, a NiCoCrAlY high temperature protective coating. Alternatively, the metal containing coating may be referred to as sample 15.

The electrode rod 14 and the sample 15 are placed in a working electrode sleeve 17, and the working electrode sleeve 17 may be a mullite tube. In the prior art, most of the electrode sleeves are alumina sleeves (corundum sleeves), the alumina sleeves are easy to burst when being quenched and heated rapidly, and the mullite expansion coefficient is much smaller. The electrode made of mullite tube can resist the abrupt change of temperature. Namely, the working electrode 10 encapsulating the sample 15 can be directly inserted into the molten salt from the room temperature environment, so that the problem of solid salt corrosion of the sample 15 along with the temperature rise process of the molten salt in the traditional experiment is avoided. Moreover, the applicant found experimentally that by inserting the working electrode 10 directly into the high temperature molten salt from room temperature, rather than heating the working electrode with the molten salt, the passivation behavior in the polarization curve of the sample 15 could be measured.

The sample 15 end of the working electrode casing 17 may be sealed with high temperature cement 18. After sealing, only the end face of the sample 15 was exposed as a test face 20. The high temperature cement 18 can seal the side of the sample 15 while fixing the sample 15, and only the end face of the sample 15 is in contact with the molten salt. It will be appreciated that only the end face of sample 15 is exposed, with the test face 20 flush with the high temperature cement 18 being the preferred embodiment. The present application also includes embodiments (not shown) where the sample 15 protrudes a distance, e.g., 4mm, above the high temperature cement 18. The high-temperature cement 18 is a common material in the field and has strong tolerance to molten salt. The high temperature cement 18 may serve to secure the electrode rod 14 to the casing and to isolate the molten salt from the non-test portion of the sample 15.

The non-sample end of the working electrode sleeve 17 may be sealed by a sealant 19, and the electrode rod 14 passes through the sealant 19. The non-sample end of the working electrode casing 17 is far from the molten salt, and the influence of the molten salt on the sealing material is small, so that more sealing materials can be selected, for example, a high-temperature-resistant sealing glue with the temperature resistance of 1280 ℃ can be selected. The sealant 19 is very firm after solidification, so that the electrode rod 14 can be prevented from loosening, and the sample 15 on the electrode rod 14 can be prevented from loosening.

The working electrode 10 with two sealed ends can be placed in an environment of 10-40 ℃ for 8-12 hours, then placed in an environment of 150-300 ℃ for 2-5 hours, and taken out after cooling, so that the working electrode 10 with the sealed ends is obtained.

After the working electrode 10 is manufactured, the surface and the corner of the sample 15 protruding from the high temperature cement 18 can be polished again, or the surface flush with the high temperature cement 18 can be polished, so that the oxide layer generated on the surface of the sample 15 in the manufacturing process of the working electrode 10 can be removed. Likewise, No. 800 silicon carbide abrasive paper, No. 2000 silicon carbide abrasive paper, No. 4000 silicon carbide abrasive paper, and No. 7000 silicon carbide abrasive paper may be used in this order for polishing.

The reference electrode 11 may include a platinum wire 21 for a reference electrode, a sleeve 22 for a reference electrode, a sealant 19, and high temperature cement 18.

A platinum wire 21 for a reference electrode was put into the sleeve 22 for a reference electrode. The diameter of the platinum wire 21 for the reference electrode may be about 1mm, and the sleeve 22 for the reference electrode may be a mullite tube. One end of the reference electrode casing 22 may be sealed with high temperature cement 18 to serve as a test end. The platinum wire 21 for the reference electrode may protrude a certain distance, for example, about 1cm, from the high temperature cement 18. The other end of the sleeve 22 for the reference electrode can be sealed by a sealant 19, the platinum wire 21 for the reference electrode penetrates through the sealant 19, and the position of the platinum wire 21 for the reference electrode can be fixed after the sealant 19 is solidified.

The sealed reference electrode 11 can be placed in an environment at 10-40 ℃ for 8-12 hours, then placed in an environment at 150-300 ℃ for 2-5 hours, and taken out after cooling, so that the sealed reference electrode 11 is obtained.

The counter electrode 12 may include a platinum wire 23 for counter electrode, a platinum sheet 24, a sleeve 25 for counter electrode, high temperature cement 18, and a sealant 19.

The platinum wire 23 for the counter electrode may be welded to the platinum plate 24, and then the welded platinum wire 23 for the counter electrode and the platinum plate 24 may be put into the sleeve 25 for the counter electrode. The platinum wire 23 for the counter electrode includes, but is not limited to, a platinum wire having a diameter of 0.5mm and a length of 400mm, the platinum sheet 24 includes, but is not limited to, a platinum sheet having a diameter of 5 × 0.5 × 40mm, and the sleeve 25 for the counter electrode may be a mullite tube. One end of the platinum sheet 24 of the sleeve 25 for a counter electrode was used as a test end and sealed with high temperature cement 18. The platinum sheet 24 may protrude a distance, for example, about 15mm, from the high temperature cement 18. The other end of the sleeve 25 for the counter electrode is sealed with a sealant 19, a platinum wire 23 for the counter electrode penetrates through the sealant 19, and the position of the platinum wire 23 for the counter electrode can be fixed after the sealant 19 is solidified.

The sealed counter electrode 12 can be placed in an environment of 10-40 ℃ for 8-12 hours, then placed in an environment of 150-300 ℃ for 2-5 hours, and taken out after cooling, so that the packaged counter electrode 12 is obtained.

In the reference electrode and the counter electrode, platinum is used for replacing silver or silver chloride which is commonly used in the prior art for the material of the electrode rod, so that the problem that the electrode cannot be used in the temperature range of more than 960 ℃ is solved, and the stable measurement of the wide-temperature-range molten salt electrochemistry is realized.

During the experiment, it was necessary to keep the portion of each electrode exposed to the high temperature cement 18 completely immersed in the molten salt. The height of the electrode system can be fixed outside the furnace by clamps or other methods.

After the experiment is finished, the electrodes in the electrode system can be separated from the molten salt liquid level in time, and the situation that the electrodes are not easy to take out after the molten salt is cooled and solidified is avoided.

Electromagnetic shielding module

As shown in fig. 1, 6 and 7, the electromagnetic shielding module comprises a shell 2, a gasket 5, a shielding cylinder 8 and a furnace plug sleeve 27. The material of the above-mentioned members may be a metal, such as stainless steel or a high temperature alloy.

The shell 2 wraps the outer side of the furnace wall of the reaction furnace body 1, and the furnace plug sleeve 27 wraps the outer side of the furnace plug 9. The shell 2 and the furnace plug sleeve 27 enable the whole reaction furnace to be in an electromagnetic shielding space, and play a certain role in shielding external electromagnetic interference.

The gasket 5 is placed at the bottom of the experimental crucible 6, the shielding cylinder 8 is sleeved outside the protective cylinder 7, and the protective cylinder 7 is sleeved outside the experimental crucible 6. The gasket 5 and the shielding cylinder 8 enable the crucible 6 for experiment to be in an electromagnetic shielding space, and can shield electromagnetic interference in the furnace to a certain extent. Further, the gasket 5 is convenient for the crucible 6 for experiment to be taken out from the side furnace door. The shielding cylinder 8 made of metal is easy to generate stripping objects to pollute molten salt in the experimental crucible 6, and then the shielding cylinder 7 is designed to separate the shielding cylinder 8 from the experimental crucible 6.

The electromagnetic shielding module can solve or improve the interference problem of electromagnetic signals possibly existing in the outside and the furnace to a corrosion system, so that the experimental device can obtain a stable electrochemical test curve.

In summary, the present application includes the following advantages:

by the electromagnetic shielding module, effective electromagnetic shielding in a high-temperature molten salt electrochemical test process can be realized;

according to the method, the problem that the test result is inaccurate due to high-temperature oxidation and poor contact of a contact point in the conventional connection mode is solved or improved by welding the electrode rod and the sample;

the working electrode can be directly inserted into molten salt from normal temperature to perform electrochemical test, so that the influence of a temperature rise process on a sample is avoided, and the sample is not easy to loosen in an experimental process;

according to the method, platinum wires are used for replacing silver or silver chloride as reference electrodes, so that high-temperature electrochemical test at the temperature of over 960 ℃ is realized.

While the foregoing is directed to the preferred embodiment of the present application, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the application.

Claims

1. A method for manufacturing an electrode system of an electrochemical test system,

the electrode system of the electrochemical test system is used for carrying out electrochemical test on a sample (15), and comprises a working electrode (10), a reference electrode (11) and a counter electrode (12),

the method of manufacturing the working electrode (10) comprises:

providing an electrode rod (14), a sleeve (17) for a working electrode, high-temperature cement (18) and a sealant (19);

welding the sample (15) to one end of the electrode rod (14);

placing the electrode rod (14) and the sample (15) into the sleeve (17) for the working electrode, and enabling the sample (15) to be located at one end of the sleeve (17) for the working electrode;

sealing the end of the working electrode sleeve (17) where the sample (15) is located with the high temperature cement (18);

sealing the end of the working electrode sleeve (17) other than the sample (15) with the sealant (19), and allowing the electrode rod (14) to pass through the sealant (19); and

after the working electrode casing (17) is sealed by the high-temperature cement (18) and the sealant (19), the working electrode (10) is placed in an environment of 10-40 ℃ for 8-12 hours, then the working electrode (10) is placed in an environment of 150-300 ℃ for 2-5 hours, and the packaged working electrode (10) is obtained,

the electrode rod (14) is an iron-chromium-aluminum wire, and the sleeve (17) for the working electrode is made of mullite.

2. The method of claim 1, wherein the electrochemical test system further comprises a plurality of electrodes,

the sample (15) partially protrudes from the high temperature cement (18), or the end face of the sample (15) is flush with the high temperature cement (18).

3. The method of claim 2, wherein the step of forming the electrode system of the electrochemical test system,

before the high-temperature cement (18) encapsulates the sample (15), the sample (15) is ground, so that the surface and the edges of the sample (15) protruding out of the high-temperature cement (18) are smooth, or the surface (20) of the sample (15) which is flush with the high-temperature cement (18) and the edges of the surface (20) are smooth.

4. The method of claim 2, wherein the step of forming the electrode system of the electrochemical test system,

and in the state that the working electrode (10) is completely packaged, grinding the surface and the edges and corners of the sample (15) protruding out of the high-temperature cement (18), or grinding the surface of the sample (15) which is flush with the high-temperature cement (18).

5. The method for manufacturing an electrode system of an electrochemical test system according to claim 3 or 4,

the sample (15) was sanded using 800 # silicon carbide sandpaper, 2000 # silicon carbide sandpaper, 4000 # silicon carbide sandpaper, 7000 # silicon carbide sandpaper in this order.

6. The method of claim 1, wherein the electrochemical test system further comprises a plurality of electrodes,

and after the sample (15) is welded with the electrode rod (14), and before the working electrode is placed into the sleeve (17), the electrode rod (14) and the welding point of the electrode rod (14) and the sample (15) are wrapped by the sealant (19).

7. The method of claim 1, wherein the electrochemical test system further comprises a plurality of electrodes,

the method for manufacturing the reference electrode (11) comprises the following steps:

providing a platinum wire (21) for a reference electrode, a sleeve (22) for the reference electrode, high-temperature cement (18) and a sealant (19);

placing the platinum wire (21) for the reference electrode into the inside of the sleeve (22) for the reference electrode;

sealing one end of the reference electrode casing (22) with the high temperature cement (18);

sealing the other end of the reference electrode sleeve (22) by the sealant (19) so that the platinum wire (21) for the reference electrode penetrates through the sealant (19); and

after the sleeve (22) for the reference electrode is sealed by the high-temperature cement (18) and the sealant (19), the reference electrode (11) is placed for 8-12 hours at 10-40 ℃, and then the reference electrode (11) is placed for 2-5 hours at 150-300 ℃, so that the packaged reference electrode (11) is obtained.

8. The method of claim 7, wherein the electrochemical test system further comprises a plurality of electrodes,

the platinum wire (21) for the reference electrode partially protrudes out of the high-temperature cement (18), and the sleeve (22) for the reference electrode is made of mullite.

9. The method of claim 1, wherein the electrochemical test system further comprises a plurality of electrodes,

the method for manufacturing the counter electrode (12) comprises the following steps:

providing a platinum wire (23) for a counter electrode, a platinum sheet (24), a sleeve (25) for the counter electrode, high-temperature cement (18) and a sealant (19);

welding the platinum wire (23) for the counter electrode to the platinum sheet (24);

placing the platinum wire (23) for the counter electrode and the platinum sheet (24) into the sleeve (25) for the counter electrode so that the platinum sheet (24) is positioned at one end of the sleeve (25) for the counter electrode;

sealing one end of the sleeve (25) for the counter electrode where the platinum sheet (24) is located with the high temperature cement (18);

sealing the other end of the sleeve (25) for the counter electrode by the sealant (19), and enabling the platinum wire (23) for the counter electrode to penetrate through the sealant (19); and

after the sleeve (25) for the counter electrode is sealed by the high-temperature cement (18) and the sealant (19), the counter electrode (12) is placed for 8-12 hours at 10-40 ℃, and then the counter electrode (12) is placed for 2-5 hours at 150-300 ℃, so that the packaged counter electrode (12) is obtained.

10. The method of claim 9, wherein the step of forming the electrode system of the electrochemical test system,

the sleeve (25) for the counter electrode is made of mullite, and the platinum sheet (24) partially protrudes out of the high-temperature cement (18).