CN110186968B - Ag/AgF reference electrode suitable for fluoride fused salt and preparation method thereof - Google Patents

Ag/AgF reference electrode suitable for fluoride fused salt and preparation method thereof Download PDF

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CN110186968B
CN110186968B CN201910427198.4A CN201910427198A CN110186968B CN 110186968 B CN110186968 B CN 110186968B CN 201910427198 A CN201910427198 A CN 201910427198A CN 110186968 B CN110186968 B CN 110186968B
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agf
corundum tube
fluoride
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CN110186968A (en
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李梅
杨明帅
韩伟
王伟
杨志强
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Harbin Engineering University
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Abstract

The invention provides an Ag/AgF reference electrode suitable for fluoride fused salt and a preparation method thereof, wherein the Ag/AgF reference electrode comprises a corundum tube, a film arranged at the sealing end of the corundum tube, a sealing plug arranged at the opening end of the corundum tube, internal reference salt arranged in the corundum tube and a silver wire, wherein the silver wire penetrates through a piston and is immersed in the internal reference salt, and the silver wire is connected with a power supply anode; the Ag/AgF reference electrode has the advantages of simple structure, firmness, durability, good stability, good reversibility, good reproducibility and long service life, and is suitable for various fluoride molten salt systems below 700 ℃.

Description

Ag/AgF reference electrode suitable for fluoride fused salt and preparation method thereof
Technical Field
The invention relates to an Ag/AgF reference electrode and a preparation method thereof, in particular to an Ag/AgF reference electrode suitable for fluoride fused salt and a preparation method thereof.
Background
The fluoride molten salt has a series of advantages of good high-temperature stability, high thermal conductivity, large specific heat capacity, wide electrochemical window, low saturated steam pressure, small neutron absorption cross section and the like, is widely applied in the fields of nuclear energy, metallurgy, functional material preparation, advanced energy storage media, surface treatment technology, electronic chemicals, fine chemical engineering, molten salt battery materials and the like, and particularly has obvious application advantages in the aspects of being used as nuclear reactor coolant, molten salt electrolyte, high-temperature energy storage materials, reaction media and the like. However, due to the high temperature and strong corrosivity of fluoride molten salt, a suitable high-temperature fluoride salt reference electrode is not available at home and abroad at present, and the application and research of high-temperature fluoride salt are greatly restricted.
Reference electrodes commonly used in fluoride salts at present are quasi-reference electrodes: such as Pt, W, Mo, etc., but they do not have a definite redox couple in the molten salt, and the electrode potential is easily affected by the change of the molten salt system; another Ni/NiF2Reference electrode: the Oak Ridge laboratory in the United states designed Ni/NiF with solid lanthanum trifluoride as the membrane material2Reference electrode, but lanthanum trifluoride is readily soluble in fluoride salt, and LaF3Single crystals are easy to crack; greece Kontoyannis uses graphite (EK-90) as Ni/NiF2The diaphragm material of the reference electrode, but graphite is easy to dissolve in high-temperature molten salt, and the nickel wire contacts with graphite to generate a conductive loop, so that the service life is short; patent ZLCN201410158185.9 discloses a Ni/NiF using an insulating sleeve as the diaphragm material2The reference electrode is used for realizing ion conduction in an open pore mode, but the open pore is easy to cause material exchange of inner and outer molten salts, so that the stability of the reference electrode is influenced; patent ZLCN201410854193.7 improves Ni/NiF with graphite as diaphragm material2The reference electrode is characterized in that a pyrolytic boron nitride sleeve is additionally arranged on the inner side of graphite, and a pyrolytic boron nitride coating is attached to the outer side of the graphite, so that the problems that the graphite is easy to crack in a high-temperature environment and has long service life in reference are solved, but the preparation process is complex and the cost is high.
Disclosure of Invention
The invention aims to provide an Ag/AgF reference electrode which is good in stability, good in reversibility, simple in structure and low in price and is suitable for fluoride fused salt and a preparation method thereof.
The purpose of the invention is realized as follows:
the Ag/AgF reference electrode suitable for fluoride fused salt comprises a corundum tube, a film arranged at the sealing end of the corundum tube, a sealing plug arranged at the opening end of the corundum tube, internal reference salt arranged in the corundum tube, and a silver wire, wherein the silver wire penetrates through a piston and is immersed in the internal reference salt, and the silver wire is connected with a power supply anode.
The invention also includes such features:
the film is arranged at the position of 0.2-0.5cm of the sealing end of the corundum tube and has the thickness of 0.05-0.2 mm;
one end of the silver wire immersed in the internal reference salt is spiral and has a diameter of 0.5-2 mm;
the internal reference salt is fluoride and a mixture thereof;
the corundum tube is made of alumina, and has an inner diameter of 6-8mm and a wall thickness of 1-2 mm.
A preparation method of an Ag/AgF reference electrode suitable for fluoride fused salt comprises the following steps:
and (3) treating the corundum tube: polishing the sealed end of the corundum tube into a film;
and (3) processing the silver wires: polishing and cleaning silver wires, inserting the silver wires into a corundum tube, and drying the corundum tube in a vacuum drying oven for later use;
weighing internal reference salt: weighing fluoride fused salt, grinding, mixing uniformly, putting into a corundum tube, and drying for 24 hours in a constant-temperature drying oven at constant temperature; then the silver wire passes through the sealing plug, and the corundum tube is sealed and sealed by the sealing plug;
preparing AgF and Ag/AgF reference electrodes by dissolving silver wires in an anode: putting the corundum crucible filled with the external fused salt into a well furnace with a constant temperature of 873K, then inserting a tungsten wire sleeved with a corundum tube and the corundum tube filled with a silver wire, internal reference salt and a sealing plug into the fused external fused salt, respectively connecting the anode and the cathode of a regulated power supply with the silver wire and the tungsten wire, and dissolving the silver wire by a constant current anode: ag-e-＝Ag+。
The film is arranged at the position of 0.2-0.5cm of the sealing end of the corundum tube and has the thickness of 0.05-0.2 mm;
one end of the silver wire immersed in the internal reference salt is spiral and has a diameter of 0.5-2 mm;
the internal reference salt and the external molten salt have the same components and are both fluoride and a mixture thereof.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides an Ag/AgF reference electrode for fluoride fused salt and a preparation method thereof, wherein a corundum tube is used as a diaphragm material, and the reference electrode has the advantages of good stability, good reversibility, simple structure and low price;
the Ag/AgF reference electrode has the advantages of simple structure, firmness, durability, good stability, good reversibility, good reproducibility and long service life, and is suitable for various fluoride molten salt systems below 700 ℃.
Drawings
Fig. 1 is a cyclic voltammogram, molten salt: LiF-KF; reference electrode: Ag/AgF, working electrode and auxiliary electrode: tungsten filament, temperature: at 600 ℃, sweeping speed: 0.1V/s;
fig. 2 is an open-circuit chronopotentiometry, molten salt: LiF-KF; reference and working electrodes: Ag/AgF; auxiliary electrode: tungsten filament, temperature: 600 ℃;
fig. 3 is a cyclic voltammogram, molten salt: LiF-KF; reference electrode: Ag/AgF, working electrode and auxiliary electrode: tungsten filament, temperature: at 600 ℃, sweeping speed: 0.1V/s;
fig. 4 is an open-circuit chronopotentiometry, molten salt: LiF-KF; reference and working electrodes: Ag/AgF, auxiliary electrode: tungsten filament, temperature: 600 ℃;
fig. 5 is a cyclic voltammogram, molten salt: LiF-KF; reference electrode: Ag/AgF, working electrode and auxiliary electrode: tungsten filament, temperature: at 600 ℃, sweeping speed: 0.1V/s;
fig. 6 is an open-circuit chronopotentiometry, molten salt: LiF-KF; reference and working electrodes: Ag/AgF, auxiliary electrode: tungsten filament, temperature: at 600 ℃.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
An Ag/AgF reference electrode suitable for use in a fluoride fused salt comprising: the corundum tube has the inner diameter of 6-8mm, the wall thickness of 1-2mm, the length of the tube is about 30cm, one end of the corundum tube is sealed, and the corundum tube is made of aluminum oxide; a film with the thickness of 0.05-0.2mm at the sealing end of the corundum tube, and a film with the thickness of about 0.05-0.2mm is polished at the position of 0.2-0.5cm at the sealing end of the corundum tube. The silver wire with the spiral structure has the purity of over 99.9 percent and the diameter of 0.5-2 mm; internal reference salts, fluorides such as KF, LiF, NaF, and the like, and mixtures thereof; sealing plugs, commercially available rubber plugs; the anode was dissolved in internal reference salt to prepare AgF directly. The corundum tube sealA film with a thickness of 0.05-0.2mm at the mouth end should have the following properties: in high temperature molten salts, the thin film structure may be Li+、K+、Na+The diffusion of ions provides a good path for ion conduction. The spiral structure is formed by bending one end of the silver wire about 2cm into a spiral similar to a spring so as to increase the contact area of the silver wire and the internal reference salt. The internal reference salt has the same composition as the external molten salt, reduces the liquid contact potential, and can completely immerse the film structure after melting. The anode is dissolved in internal reference salt to directly prepare AgF, namely a corundum crucible filled with external fused salt is placed in a furnace with the constant temperature of 873K, after the external fused salt is fused, a tungsten wire sleeved with a corundum sleeve and a corundum tube filled with a silver wire, internal reference salt and a sealing plug are inserted into the fused salt, the anode and the cathode of a stabilized voltage power supply are respectively connected with the silver wire and the tungsten wire, and the constant current anode is used for dissolving Ag: ag-e-＝Ag+. The Ag/AgF reference electrode is suitable for fluoride molten salt and eutectic salt thereof below 700 ℃.
An Ag/AgF reference electrode suitable for use in a fluoride fused salt comprising the steps of:
(1) and (3) treating the corundum tube: taking one corundum tube, and polishing the part of 0.2-0.5cm of the sealing end of the corundum tube into a film with the thickness of about 0.05-0.2 mm.
(2) The silver wire treatment comprises the following steps: cutting a silver wire with the length of 35cm, polishing the surface of the silver wire by using sand paper until the silver wire is bright and has no scratch, and then sequentially cleaning the silver wire by using alcohol and distilled water through ultrasonic waves; winding one end of a silver wire into a spiral shape similar to a spring, inserting the silver wire into a corundum tube, and drying the silver wire in a vacuum drying oven for later use;
(3) weighing about 4g of fluoride fused salt, grinding and mixing uniformly by using a mortar, putting into a corundum tube, suspending in a 873K drying box, fully drying for 24h, and then sealing the corundum tube by a silver wire penetrating through a sealing plug.
(4) Preparing AgF and Ag/AgF reference electrodes by dissolving silver wires in an anode: putting the corundum crucible filled with the external fused salt into a well type furnace with the constant temperature of 873K to melt the salt, and then inserting the tungsten wire sleeved with the corundum sleeve and the corundum tube filled with the silver wire, the internal reference salt and the sealing plug into the corundum crucibleIn the molten salt, the anode and the cathode of the stabilized voltage power supply are respectively connected with a silver wire and a tungsten wire, and the constant current anode dissolves the silver wire: ag-e-＝Ag+。
The principle of the invention is as follows: ion conduction of the separator material: polishing a sealing end of the corundum tube at a position of 0.2-0.5cm into a film with the thickness of about 0.05-0.2mm, sequentially filling a silver wire, internal reference salt and a sealing plug, wherein the silver wire is connected with an anode of a stabilized voltage supply, a tungsten wire is connected with a cathode of the stabilized voltage supply, a constant current of 0.01A is dissolved at the anode, and the potential is 0.2-1.3V, so that the conduction of current is realized, and the formed film structure has the following properties: in high temperature molten salts, the thin film structure may be Li+、K+Or Na+The diffusion of ions provides a good ion conduction channel; the constant current anode dissolves, the current is the same, and different reference voltages are different: the thickness of the film varies, resulting in a difference in film resistance.
Anodic dissolution of Ag in molten salt and AgF preparation: Ag/Ag+The potential stability and reproducibility of the electric pair are good, the reversibility is good, the electric pair is very suitable to be used as a reference electric pair, and the wide application of the reference electrode in water solution, chloride fused salt and Ag/AgCl proves that Ag/Ag+Excellent characteristics of the electrical pair; taking a reference tube which is ground into a film structure, sequentially filling a silver wire, internal reference salt and a sealing plug for sealing, respectively connecting the anode and the cathode of a stabilized voltage supply with the silver wire and a tungsten wire, dissolving the silver wire in the reference salt in fluoride by a constant current 0.01A anode to generate Ag+：Ag-e-＝Ag+。
The invention adopts a commercially available corundum tube as a diaphragm material; the invention grinds the 0.2-0.5cm part of the sealing end of the corundum tube into a film with the thickness of about 0.05-0.2mm, and the film structure can be Li+、K+Or Na+The diffusion of ions provides a good ion conduction channel; therefore, the problem of current conduction between the reference internal and external molten salts is solved, and the internal reference salt is ensured to hardly generate substance exchange with a research system in the using process; the invention directly prepares the anhydrous silver fluoride in the internal reference salt by the method of dissolving silver by the anode, avoids the contact of the silver fluoride and the air, ensures the stability and the dryness of the property of the silver fluoride, and reduces the reference potential at the same timeThe overall manufacturing cost of the poles. Because the boiling point of the AgF is low, the applicable temperature of the reference electrode is below 700 ℃ in order to avoid instability of the reference electrode caused by AgF volatilization at the temperature above 700 ℃; the film consists of a corundum tube, a film with the thickness of 0.05-0.2mm at the sealing end of the corundum tube, a silver wire with a spiral structure, internal reference salt and a sealing plug, wherein AgF is directly prepared by a method of dissolving the silver wire by an anode. AgF is directly prepared by dissolving Ag in the internal reference salt through the anode, the cost is low, the contact of the AgF and the air is avoided, and the stability and the dryness of the performance of the AgF are ensured; can be applied to different fluoride molten salt systems. All raw materials used in the invention are commercially available and cheap.
The specific experimental scheme of the invention is as follows: (1) and (3) treating the corundum tube: taking one corundum tube, and polishing the part of 0.2-0.5cm of the sealing end of the corundum tube into a film with the thickness of about 0.05-0.2 mm. (2) The silver wire treatment comprises the following steps: cutting a silver wire with the length of 35cm, polishing the surface of the silver wire by using sand paper until the silver wire is bright and has no scratch, and then sequentially cleaning the silver wire by using alcohol and distilled water through ultrasonic waves; winding one end of a silver wire into a spiral shape similar to a spring, inserting the silver wire into a corundum tube, and drying the silver wire in a vacuum drying oven for later use; (3) weighing about 4g of fluoride fused salt, grinding and mixing uniformly by using a mortar, putting into a corundum tube, suspending in a 873K drying box, fully drying for 24h, and then penetrating silver wires through a sealing plug to seal the corundum tube. (4) Preparing AgF and Ag/AgF reference electrodes by dissolving silver wires in an anode: putting the corundum crucible filled with the external fused salt into a well furnace with a constant temperature of 873K to melt the salt, then inserting a tungsten wire sleeved with a corundum sleeve and a corundum tube filled with a silver wire, an internal reference salt and a sealing plug into the fused salt, respectively connecting the anode and the cathode of a stabilized voltage power supply with the silver wire and the tungsten wire, and dissolving the silver wire by a constant current anode: ag-e-＝Ag+。
The first implementation example is as follows:
in LiF-KF molten salt, corundum tube, silver wire and sealing plug are used to prepare the reference electrode, which includes the following steps:
(1) the treatment of the corundum tube comprises the following steps: a corundum tube with the length of 30cm, the outer diameter of 8cm and the wall thickness of 1cm is taken, and the position of 0.2cm of the sealing end of the corundum tube is polished into a thin film with the thickness of about 0.05 mm.
(2) The silver wire treatment comprises the following steps: cutting 35cm silver wire (purity 99.99% and diameter 1mm), polishing with sand paper until it is bright and has no scratch, and sequentially washing with ultrasonic wave containing alcohol and distilled water for 5 min; then winding one end of the silver wire into a spiral shape (the length is 2cm) similar to a spring, inserting the silver wire into a corundum tube, and placing the corundum tube into a vacuum drying oven at constant temperature 573K for drying for 24 hours for later use;
(3) weighing 1.3g of LiF and 2.8g of 2.8gKF, grinding and mixing uniformly by using a mortar, putting into a corundum tube, suspending in the air, putting into a 873K drying box, fully drying for 24h, and then penetrating a silver wire through a sealing plug to seal the corundum tube.
(4) Anodic dissolution of silver wires and preparation of Ag/AgF reference electrodes: weighing 26g of LiF and 56gKF, grinding and uniformly mixing by using a mortar, putting into a corundum crucible, and drying for 24 hours in a constant-temperature drying oven at constant temperature of 300 ℃; then putting the mixture into a well furnace with constant temperature of 873K for melting; inserting a corundum tube provided with a silver wire, an internal reference salt and a sealing plug and a tungsten wire protected by a corundum sleeve into the fused external fused salt, wherein the silver wire is connected with the anode of a stabilized voltage power supply, the tungsten wire is connected with the cathode of the stabilized voltage power supply, the silver wire is dissolved by a constant current 0.01A anode, and the anode reaction of metal silver in the fused fluoride salt is as follows: ag-e-＝Ag+And dissolving the anode for 60min to prepare the Ag/AgF reference electrode.
The potential of the reference electrode is basically stabilized after the Ag/AgF reference electrode in the embodiment 1 is placed in external molten salt for 30min, the obtained cyclic voltammetry curve is shown in figure 1, the residual current is about 3mA, the potential window is more than 2V, the reference electrode can be completely used for electrochemical measurement of fluoride molten salt, and the potential deviation is about 10mV within 100h of use; and forming a primary battery Ag | AgF-LiF-KF | AgF-KF | Ag with an Ag/AgF reference electrode with the same concentration, wherein after negative and positive polarization currents of +/-5 mA are respectively applied for 5s, the potentials respectively reach 408mV and 765mV, the polarization curves recover to be close to the equilibrium potential after 10s, and the two polarization curves basically coincide after 80s, which shows that the reference electrode can still recover to the equilibrium potential after the polarization currents are applied, thereby showing good current reversibility.
Example two was performed:
in LiF-KF molten salt, silver wire, corundum tube and sealing plug are used to prepare the reference electrode, which comprises the following steps:
(1) treating the corundum tube;
(2) processing the silver wire;
(3) weighing the reference salt;
(4) anodic dissolution of silver wires and preparation of Ag/AgF reference electrodes: the anode was dissolved for 90min at constant current of 0.01A.
The potential of the reference electrode is basically stabilized after the Ag/AgF reference electrode of the embodiment example 2 is placed in the external molten salt for 30min, the obtained cyclic voltammetry curve is shown in figure 3, the residual current is about 3mA, the potential window is more than 2V, the reference electrode can be completely used for electrochemical measurement of fluoride molten salt, and the potential deviation is about 8mV within 100h of use; and the primary battery Ag | AgF-LiF-KF | AgF-KF | Ag is formed by the primary battery and another Ag/AgF reference electrode, as shown in FIG. 4, after plus or minus 5mA cathode/anode currents are respectively applied for 5s, the potentials respectively reach 362mV and minus 1097mV, the polarization curves recover to be close to the equilibrium potential after 30s, and the two polarization curves basically coincide after 170s, which indicates that the reference electrode can still recover to the equilibrium potential after the polarization currents are applied, thereby showing good current reversibility.
Example three was performed:
in LiF-KF molten salt, silver wire, corundum tube and sealing plug are used to prepare the reference electrode, which comprises the following steps:
(1) treating the corundum tube;
(2) processing the silver wire;
(3) weighing the reference salt;
(4) anodic dissolution of silver wires and preparation of Ag/AgF reference electrodes: dissolving the anode at constant current of 0.01A for 120 min.
The potential of the reference electrode is basically stabilized after the Ag/AgF reference electrode of the embodiment example 3 is placed in the external molten salt for 30min, the obtained cyclic voltammetry curve is shown in figure 5, the residual current is about 5mA, the potential window is more than 2V, the reference electrode can be completely used for electrochemical measurement of fluoride molten salt, and the potential deviation is about 5mV within 100h of use; and forming a primary battery Ag | AgF-LiF-KF-AgF-KF | Ag with an Ag/AgF reference electrode with the same concentration, wherein after a cathode and anode current of +/-5 mA is applied for 5s respectively, the potential reaches 548mV and-1140 mV respectively, a polarization curve is recovered to be close to a balance potential after 25s, and two polarization curves are basically superposed after 70s, which shows that the reference electrode can still recover to the balance potential after the polarization current is applied, thereby showing good current reversibility.
The use method of the invention comprises the following steps: connecting an electrochemical workstation according to a three-electrode system, taking an Ag/AgF reference electrode as a reference electrode, taking a tungsten wire as a working electrode and an auxiliary electrode, measuring the residual current and the potential window of the electrochemical workstation by using a cyclic voltammetry method, measuring the reversibility of the electrochemical workstation by using a time potential method, and recording the stability and the service life of the electrochemical workstation.
In summary, the following steps: the invention provides an Ag/AgF reference electrode for fluoride fused salt and a preparation method thereof, which is characterized in that a corundum tube 1 with one sealed end is taken, and the part with 0.2-0.5cm of the sealed end is polished into a film 2 with the thickness of about 0.05-0.2 mm; cutting a silver wire 3, bending about 2cm of one end of the silver wire into a spiral shape similar to a spring, and inserting the silver wire into a corundum tube; weighing internal reference fluoride salt 4, grinding and mixing uniformly, and putting into a corundum tube inserted with silver wires; taking out the sealing plug 5, and sealing the corundum tube by the silver wire passing through the sealing plug; the anode and cathode of the voltage-stabilized power supply are respectively connected with silver wire and tungsten wire, and the silver wire anode is dissolved in fluoride reference salt to produce Ag by electrifying+Thus, a half-cell Ag-AgF-XF reference electrode is formed; the Ag/AgF reference electrode has the advantages of simple structure, small membrane resistance, short ion conduction time, very good electrode potential reproducibility and stability, good reversibility and good recovery property, and the used raw materials are commercially available and have low price.

Claims (10)

1. An Ag/AgF reference electrode suitable for fluoride fused salt is characterized by comprising a corundum tube, a thin film arranged at the sealing end of the corundum tube, a sealing plug arranged at the opening end of the corundum tube, internal reference salt arranged in the corundum tube and a silver wire, wherein the silver wire penetrates through a piston and is immersed in the internal reference salt and is connected with a power supply anode;
the preparation method comprises the following steps:
and (3) treating the corundum tube: polishing the sealed end of the corundum tube into a film;
and (3) processing the silver wires: polishing and cleaning silver wires, inserting the silver wires into a corundum tube, and drying the corundum tube in a vacuum drying oven for later use;
weighing internal reference salt: weighing fluoride fused salt, grinding, mixing uniformly, putting into a corundum tube, and drying for 24 hours in a constant-temperature drying oven at constant temperature; then the silver wire passes through the sealing plug, and the corundum tube is sealed and sealed by the sealing plug;
preparing AgF and Ag/AgF reference electrodes by dissolving silver wires in an anode: putting the corundum crucible filled with the external fused salt into a well furnace with a constant temperature of 873K, then inserting a tungsten wire sleeved with a corundum tube and the corundum tube filled with a silver wire, internal reference salt and a sealing plug into the fused external fused salt, respectively connecting the anode and the cathode of a regulated power supply with the silver wire and the tungsten wire, and dissolving the silver wire by a constant current anode: ag-e-＝Ag+。
2. The Ag/AgF reference electrode suitable for fluoride fused salts according to claim 1, wherein the thin film is arranged at the position of 0.2-0.5cm from the sealing end of the corundum tube and has a thickness of 0.05-0.2 mm.
3. The Ag/AgF reference electrode suitable for fluoride fused salts according to claim 1 or 2, wherein one end of the silver wire immersed in the internal reference salt is spiral and has a diameter of 0.5-2 mm.
4. The Ag/AgF reference electrode suitable for use with fluoride fused salts according to claim 1 or 2, wherein the internal reference salt is fluoride and mixtures thereof.
5. The Ag/AgF reference electrode suitable for fluoride fused salts according to claim 1 or 2, wherein the material of the corundum tube is alumina, and the inner diameter is 6-8mm and the wall thickness is 1-2 mm.
6. A preparation method of an Ag/AgF reference electrode suitable for fluoride fused salt is characterized by comprising the following steps:
and (3) treating the corundum tube: polishing the sealed end of the corundum tube into a film;
and (3) processing the silver wires: polishing and cleaning silver wires, inserting the silver wires into a corundum tube, and drying the corundum tube in a vacuum drying oven for later use;
weighing internal reference salt: weighing fluoride fused salt, grinding, mixing uniformly, putting into a corundum tube, and drying for 24 hours in a constant-temperature drying oven at constant temperature; then the silver wire passes through the sealing plug, and the corundum tube is sealed and sealed by the sealing plug;
preparing AgF and Ag/AgF reference electrodes by dissolving silver wires in an anode: putting the corundum crucible filled with the external fused salt into a well furnace with a constant temperature of 873K, then inserting a tungsten wire sleeved with a corundum tube and the corundum tube filled with a silver wire, internal reference salt and a sealing plug into the fused external fused salt, respectively connecting the anode and the cathode of a regulated power supply with the silver wire and the tungsten wire, and dissolving the silver wire by a constant current anode: ag-e-＝Ag+。
7. The method for preparing an Ag/AgF reference electrode suitable for fluoride fused salts as claimed in claim 6, wherein the thin film is disposed at 0.2-0.5cm of the sealed end of the corundum tube and has a thickness of 0.05-0.2 mm.
8. The method for preparing an Ag/AgF reference electrode suitable for fluoride fused salts according to claim 6 or 7, wherein one end of the silver wire immersed in the internal reference salt is spiral and has a diameter of 0.5-2 mm.
9. The method for preparing the Ag/AgF reference electrode suitable for fluoride molten salt according to claim 6 or 7, wherein the inner reference salt and the outer molten salt are the same in composition and are both fluoride and a mixture thereof.
10. The method for preparing the Ag/AgF reference electrode suitable for fluoride molten salt according to claim 8, wherein the inner reference salt and the outer molten salt have the same composition and are both fluoride and a mixture thereof.
CN201910427198.4A 2019-05-22 2019-05-22 Ag/AgF reference electrode suitable for fluoride fused salt and preparation method thereof Active CN110186968B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0393188A1 (en) * 1987-11-24 1990-10-24 Terumo Kabushiki Kaisha Reference electrode
CN202351203U (en) * 2011-11-16 2012-07-25 钢铁研究总院青岛海洋腐蚀研究所 Miniature seawater silver halide reference electrode
CN104090004A (en) * 2014-04-19 2014-10-08 中国科学院上海应用物理研究所 Ni/NiF2 reference electrode used for molten fluoride, and making method thereof
CN105806773A (en) * 2014-12-31 2016-07-27 国核（北京）科学技术研究院有限公司 High-temperature villiaumite reference electrode and manufacturing method thereof
CN107238641A (en) * 2016-03-28 2017-10-10 梅特勒-托利多仪器（上海）有限公司 A kind of reference electrode system

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0393188A1 (en) * 1987-11-24 1990-10-24 Terumo Kabushiki Kaisha Reference electrode
CN202351203U (en) * 2011-11-16 2012-07-25 钢铁研究总院青岛海洋腐蚀研究所 Miniature seawater silver halide reference electrode
CN104090004A (en) * 2014-04-19 2014-10-08 中国科学院上海应用物理研究所 Ni/NiF2 reference electrode used for molten fluoride, and making method thereof
CN105806773A (en) * 2014-12-31 2016-07-27 国核（北京）科学技术研究院有限公司 High-temperature villiaumite reference electrode and manufacturing method thereof
CN107238641A (en) * 2016-03-28 2017-10-10 梅特勒-托利多仪器（上海）有限公司 A kind of reference electrode system

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
A Robust Alumina Membrane Reference Electrode for High Temperature Molten Salts;Han Wang等;《Journal of The Electrochemical Society》;20120814;第159卷(第9期);第H740-H746页 *
PYROLYTIC BORON NITRIDE COATED GRAPHITE AS A CONTAINER OF REFERENCE ELECTRODES FOR MOLTEN FLUORIDES;CHRISTOS G .等;《Electrochimica Acta》;19951031;第40卷(第15期);第2537-2551页 *
用于熔盐体系的莫来石隔膜Ag/AgCl参比电极的性能研究;林如山 等;《核化学与放射化学》;20191031;第41卷(第5期);第447-451页 *

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