CN219839765U - reference electrode - Google Patents

Abstract

The utility model provides a reference electrode, which comprises an electrode sleeve, an electrode core, an electrode cable and an antifouling component, wherein the electrode core is arranged in the electrode sleeve, and the electrode cable is electrically connected with the electrode core; the anti-fouling component comprises an anti-fouling anode, an anti-fouling cathode, an anode cable and a cathode cable, wherein the anti-fouling anode is arranged in the electrode sleeve, the anti-fouling cathode is arranged on the electrode sleeve, the anode cable is electrically connected with the anti-fouling anode, and the cathode cable is electrically connected with the anti-fouling cathode; the reference electrode can be subjected to electrolytic antifouling. According to the reference electrode provided by the utility model, the anti-fouling component is arranged to electrolyze seawater to generate the effective chlorine, so that biofouling is avoided, and the service life of the reference electrode is prolonged.

Description

Reference electrode

Technical Field

The utility model relates to the technical field of electrochemistry, in particular to a reference electrode.

Background

The reference electrode is used as a reference electrode for measuring various electrode potentials, and has wide application in various technical fields such as electrochemical protection. In seawater environment, the most commonly used reference electrode is silver/silver chloride reference electrode (i.e. Ag/AgCl reference electrode; a solid Ag/AgCl electrode core as disclosed in patent CN201010585794.4, the main components of which are Ag and AgCl), silver/silver halide reference electrode (i.e. Ag/AgX reference electrode; a hot dip coated silver/silver halide reference electrode as disclosed in patent CN 20080015054. X, the main components of which are Ag, agCl and AgBr), copper/copper sulfate reference electrode, high purity zinc reference electrode, etc. The silver/silver chloride reference electrode has the advantages of stable potential, good reproducibility, firmness, durability and the like, and is the reference electrode which is most widely applied in the cathodic protection of marine structures such as ships, ocean platforms and the like.

Because a large amount of pollutants and impurities exist in the marine environment, calcium, magnesium plasma, marine organisms and the like in the seawater can be attached to the surface of the reference electrode, so that the activity of the reference electrode is reduced; in addition, although the chemical properties of silver/silver chloride and silver/silver halide are stable, in the long-term use process, the reference electrode is used as a cathode, weak leakage current still causes AgCl or AgX in the electrode to react to generate Ag simple substance, when the proportion of the Ag simple substance is increased to a certain range, the electrode is invalid, so that the service life of the reference electrode is influenced (related research shows that when the mass percentage of AgCl on the surface of the Ag/AgCl reference electrode is lower than 8%, the reference electrode is invalid, and in the practical engineering application, the Ag/AgCl reference electrode is gradually invalid after being used for 5 years, so that the long-term potential measurement requirements of marine structures such as ocean platforms cannot be met).

Disclosure of Invention

The utility model aims to provide a reference electrode, which is used for generating effective chlorine by electrolyzing seawater through arranging an anti-fouling component, so that biofouling is avoided, and the service life of the reference electrode is prolonged.

The utility model provides a reference electrode which is used in a seawater environment and comprises an electrode sleeve, an electrode core, an electrode cable and an antifouling component, wherein the electrode core is arranged in the electrode sleeve, and the electrode cable is electrically connected with the electrode core; the electrode sleeve is provided with a runner which is communicated with the inner cavity of the electrode sleeve and is used for allowing external seawater to enter the electrode sleeve; the anti-fouling assembly comprises an anti-fouling anode, an anti-fouling cathode, an anode cable and a cathode cable, wherein the anti-fouling anode is arranged in the electrode sleeve, the anti-fouling cathode is arranged on the electrode sleeve, the anode cable is electrically connected with the anti-fouling anode, and the cathode cable is electrically connected with the anti-fouling cathode; the reference electrode is capable of electrolytic antifouling; when the reference electrode is used for electrolytic pollution prevention, the anode cable and the cathode cable are respectively and electrically connected with the anode and the cathode of a direct current power supply so as to electrolyze the seawater in the electrode sleeve, thereby generating available chlorine in the seawater in and/or near the electrode sleeve.

Further, a partition plate is arranged in the electrode sleeve, the partition plate divides the inner cavity of the electrode sleeve into an electrode cavity and a sealing cavity which are adjacently arranged, the flow channel is arranged corresponding to the electrode cavity and communicated with the electrode cavity, the flow channel is used for allowing external seawater to enter the electrode cavity, and the anti-pollution anode is arranged in the electrode cavity; the electrode wire is characterized in that a perforation is arranged on the partition board, one end of the electrode core is positioned in the electrode cavity, the other end of the electrode core penetrates through the perforation and then stretches into the sealing cavity, and the connection position of the electrode wire and the electrode core is positioned in the sealing cavity.

Further, the reference electrode also includes a sealing envelope at least partially filled between the outer side wall of the electrode core and the inner wall of the perforation to seal a gap between the outer side wall of the electrode core and the inner wall of the perforation.

Further, the sealing cavity is filled with sealing filler, the sealing filler seals the connection position of the electrode cable and the electrode core, and one end of the electrode cable penetrates through the sealing filler and then extends out of the electrode sleeve.

Further, the anode cable and the cathode cable extend from the electrode cavity to the sealing cavity and then extend out of the electrode sleeve through the sealing filler.

Further, the electrode sleeve comprises a sleeve body, the electrode core is arranged in the sleeve body, and the anti-pollution anode is fixed on the inner wall of the sleeve body; the flow channel is an opening arranged at the bottom of the sleeve body, the opening is communicated with the inner cavity of the sleeve body, and the anti-pollution cathode is fixed at the bottom of the sleeve body.

Further, the electrode sleeve comprises a sleeve body and a cover plate, the electrode core is arranged in the sleeve body, and the anti-pollution anode is fixed on the inner wall of the sleeve body; the bottom of the sleeve body is provided with an opening, and the cover plate is arranged at the opening; the runner is a through hole arranged on the cover plate, and the through hole is communicated with the inner cavity of the sleeve body; the anti-pollution cathode is fixed at the bottom of the sleeve body or on the cover plate.

Further, the antifouling anode is a titanium-based oxide anode, the antifouling cathode is made of titanium or hastelloy, and the area ratio of the antifouling anode to the antifouling cathode is 2:1 to 1:2.

further, the electrode sleeve is of a cylindrical or conical cylindrical structure, the electrode core is arranged at the central position in the electrode sleeve, the anti-pollution anode is of a cylindrical or conical cylindrical structure which surrounds the electrode core and is used as the center, and the anti-pollution anode is of a cylindrical or conical cylindrical or circular ring structure which surrounds the electrode core and is used as the center.

Further, the electrolytic antifouling method of the reference electrode comprises the following steps:

the anode cable is electrically connected with the positive electrode of the direct current power supply, and the cathode cable is electrically connected with the negative electrode of the direct current power supply; and periodically supplying power to the antifouling anode and the antifouling cathode through the direct-current power supply to intermittently electrolyze the seawater in the electrode sleeve, so as to generate available chlorine in the seawater in and/or near the electrode sleeve.

Further, when the seawater in the electrode sleeve is electrolyzed intermittently, the effective chlorine concentration in the seawater in the electrode sleeve is controlled to be between 0.5 and 1.5ppm when the seawater is electrolyzed each time, and the interval time between the electrolysis is not more than 72 hours.

Further, the electrode core is a silver/silver chloride electrode or a silver/silver halide electrode, and the reference electrode can also perform in-situ electrolytic regeneration; when the reference electrode is subjected to in-situ electrolytic regeneration, the electrode cable and the cathode cable are respectively and electrically connected with the anode and the cathode of the direct current power supply so as to apply reverse polarization current to the electrode core, so that the elemental silver on the electrode core is converted into silver chloride.

Further, the in-situ electrolytic regeneration method of the reference electrode comprises the following steps:

the electrode cable is electrically connected with the positive electrode of the direct current power supply, and the cathode cable is electrically connected with the negative electrode of the direct current power supply; and applying reverse polarization current to the electrode core through the direct current power supply so as to convert the elemental silver on the electrode core into silver chloride.

Further, when reverse polarization current is applied, the current density is controlled to be 3-30 mA/cm ² The polarization time is between 1 and 10 hours.

According to the reference electrode provided by the utility model, the anti-fouling component is arranged to electrolyze seawater to generate the effective chlorine, so that marine organisms are prevented from adhering and growing in the electrode sleeve and on the electrode core, the effective anti-fouling of the internal cavity of the reference electrode is realized, and the service life of the reference electrode is prolonged. Meanwhile, the anti-pollution anode is positioned inside the electrode sleeve, so that generated effective chlorine can be effectively dispersed inside the electrode sleeve (when seawater is electrolyzed, the effective chlorine is generated on the anti-pollution anode), and the anti-pollution anode can be prevented or reduced from being subjected to hydraulic flushing and mechanical damage, and the service life is long.

Drawings

Fig. 1 is a schematic cross-sectional view of a reference electrode in an embodiment of the utility model.

Fig. 2 is a schematic cross-sectional view of the sleeve of fig. 1.

Fig. 3 is a schematic cross-sectional view of the cover plate of fig. 1.

Fig. 4 is a schematic plan view of the cover plate in fig. 1.

FIG. 5 is a schematic diagram showing the electrical connection relationship between a reference electrode and a DC power supply during electrolytic antifouling.

Fig. 6 is a schematic diagram showing an electrical connection relationship between a reference electrode and a dc power supply during in-situ electrolytic regeneration in an embodiment of the present utility model.

Fig. 7 is a schematic cross-sectional view of a reference electrode in another embodiment of the utility model.

Detailed Description

The following describes in further detail the embodiments of the present utility model with reference to the drawings and examples. The following examples are illustrative of the utility model and are not intended to limit the scope of the utility model.

The terms "first," "second," "third," "fourth" and the like in the description and in the claims, if any, are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order.

The terms upper, lower, left, right, front, rear, top, bottom and the like (if any) in the description and in the claims are used for descriptive purposes and not necessarily for describing relative positions of structures in the figures and in describing relative positions of structures. It should be understood that the use of directional terms should not be construed to limit the scope of the utility model as claimed.

As shown in fig. 1 and 5, the reference electrode provided by the embodiment of the utility model is used in a seawater environment, and can be particularly used in cathodic protection of marine structures such as ships, ocean platforms and the like. The reference electrode comprises an electrode sleeve 1, an electrode core 2, an electrode cable 6 and an antifouling component 3, wherein the electrode core 2 is arranged in the electrode sleeve 1, and the electrode cable 6 is electrically connected with the electrode core 2; the electrode sleeve 1 is provided with a runner which is communicated with the inner cavity of the electrode sleeve 1 and is used for allowing external seawater to enter the electrode sleeve 1; the antifouling module 3 includes an antifouling anode 31, an antifouling cathode 32, an anode cable 33 and a cathode cable 34, the antifouling anode 31 is arranged in the electrode sleeve 1, the antifouling cathode 32 is arranged on the electrode sleeve 1, the anode cable 33 is electrically connected with the antifouling anode 31, and the cathode cable 34 is electrically connected with the antifouling cathode 32. The reference electrode can carry out electrolytic antifouling; when the reference electrode is used for electrolytic antifouling, the anode cable 33 and the cathode cable 34 are respectively used for being electrically connected with the anode and the cathode of the direct current power supply 7, and the seawater in the electrode sleeve 1 is electrolyzed by utilizing the antifouling anode 31 and the antifouling cathode 32, so that effective chlorine (comprising hypochlorous acid, sodium hypochlorite, chlorine and the like) is generated in the seawater in the electrode sleeve 1 and/or in the seawater near the electrode sleeve 1, the effective chlorine can kill marine organisms in the seawater and/or inhibit the growth and propagation of the marine organisms, thereby avoiding biofouling in the electrode sleeve 1 and prolonging the service life of the reference electrode.

Specifically, the reference electrode provided in this embodiment is configured to electrolyze seawater to generate effective chlorine by setting the anti-fouling component 3, so as to avoid marine organisms from adhering and growing in the electrode sleeve 1 and on the electrode core 2, realize effective anti-fouling of the internal cavity of the reference electrode, and prolong the service life of the reference electrode. Meanwhile, the anti-fouling anode 31 is positioned inside the electrode sleeve 1, so that generated effective chlorine can be effectively dispersed inside the electrode sleeve 1 (when seawater is electrolyzed, the effective chlorine is generated on the anti-fouling anode 31), and the anti-fouling anode 31 can be prevented or reduced from being subjected to hydraulic flushing and mechanical damage, and the service life of the anti-fouling anode is prolonged.

As shown in fig. 6, as an embodiment, the electrode core 2 is a silver/silver chloride electrode (whose main components are Ag and AgCl) or a silver/silver halide electrode (whose main components are Ag, agCl and AgBr or other silver halides). The reference electrode can also perform in-situ electrolytic regeneration; when the reference electrode is undergoing in-situ electrolytic regeneration, the electrode cable 6 and the cathode cable 34 are respectively used for being electrically connected with the positive electrode and the negative electrode of the direct current power supply 7 so as to apply reverse polarization current to the electrode core 2, so that the elemental silver on the electrode core 2 is converted into silver chloride.

Specifically, due to the addition of the anti-fouling component 3, when the electrode core 2 of the reference electrode is disabled due to reduction of silver chloride or silver halide (namely, the silver chloride or silver halide in the electrode core 2 is converted into elemental silver), the elemental silver is converted into AgCl by in-situ electrolysis of the electrode core 2 and the anti-fouling cathode 32, so that in-situ polarization regeneration of the electrode core 2 is realized, and the service life of the reference electrode is greatly prolonged.

When the reference electrode has only an electrolytic antifouling function, the electrode core 2 may be a silver/silver chloride electrode or a silver/silver halide electrode, or may be another type of electrode (e.g., a high-purity zinc electrode, etc.); when the reference electrode has both an electrolytic antifouling function and an in-situ electrolytic regeneration function, the electrode core 2 is typically a silver/silver chloride electrode or a silver/silver halide electrode (the main components in the silver chloride electrode and the silver halide electrode are typically silver and silver chloride).

When the reference electrode is subjected to electrolytic antifouling and in-situ electrolytic regeneration, the dc power supply 7 used for both may be the same power supply or different power supplies.

As an embodiment, the electrode core 2 may be prepared by a hot dip coating method or a powder pressing method, or may be prepared by other methods such as a thermal decomposition method.

As an embodiment, the electrode sheath 1 is made of an insulating and corrosion-resistant material, such as nylon, PVC, PE, etc.

As shown in fig. 1, as an embodiment, the anti-fouling cathode 32 is fixed on the electrode sleeve 1, and the anti-fouling cathode 32 is disposed outside the electrode sleeve 1 or at the flow channel, so that the precipitate generated on the anti-fouling cathode 32 can fall off in time (since the seawater contains calcium, magnesium and other ions, when the seawater is electrolyzed, the precipitate such as calcium, magnesium and the like is generated on the anti-fouling cathode 32), and the blockage caused by the deposition of the precipitate is avoided. When the anti-fouling cathode 32 is arranged outside the electrode sleeve 1, the sediment on the anti-fouling cathode 32 can be directly dropped off; when the anti-fouling cathode 32 is arranged at the flow channel, the sediment on the anti-fouling cathode 32 can be discharged out of the electrode sleeve 1 through the flow channel.

As shown in fig. 1 and 2, as an embodiment, a separator 13 is disposed in the electrode sleeve 1, the separator 13 and the electrode sleeve 1 are integrally configured, the separator 13 divides the inner cavity of the electrode sleeve 1 into an electrode cavity 111 and a sealing cavity 112 which are adjacently disposed, a flow channel is disposed corresponding to the electrode cavity 111 and is communicated with the electrode cavity 111, the flow channel is used for allowing external seawater to enter the electrode cavity 111, and an anti-fouling anode 31 is disposed in the electrode cavity 111. The separator 13 is provided with a perforation 131, one end of the electrode core 2 is positioned in the electrode cavity 111, the other end of the electrode core 2 passes through the perforation 131 and then stretches into the sealing cavity 112, and the connection position (namely, wiring position) of the electrode cable 6 and the electrode core 2 is positioned in the sealing cavity 112.

Specifically, in order to prevent corrosion/erosion of the connection location of the electrode cable 6 and the electrode core 2 (if the connection location of the electrode cable 6 and the electrode core 2 is corroded, the service life of the reference electrode is affected, the resistance value of the electrode core 2 is affected, and the accuracy of reference electrode potential measurement is further affected), a partition plate 13 is arranged in the electrode sleeve 1 to divide the inner cavity of the electrode sleeve 1 into an electrode cavity 111 and a sealing cavity 112, and the connection location of the electrode cable 6 and the electrode core 2 is located in the sealing cavity 112, so that corrosion/erosion of the connection location of the electrode cable 6 and the electrode core 2 is avoided; the anti-pollution anode 31 is arranged in the electrode cavity 111, and external seawater can enter the electrode cavity 111 for exchange, so that the normal electrolytic anti-pollution function of the reference electrode is not affected.

As shown in fig. 1 and 2, as an embodiment, the reference electrode further includes a sealing case 4, and the sealing case 4 is at least partially filled between the outer sidewall of the electrode core 2 and the inner wall of the through hole 131 to seal the gap between the outer sidewall of the electrode core 2 and the inner wall of the through hole 131, thereby preventing seawater in the electrode cavity 111 from entering the sealing cavity 112 through the gap between the outer sidewall of the electrode core 2 and the inner wall of the through hole 131. Meanwhile, the sealing box 4 is also partially positioned in the sealing cavity 112 and connected between the electrode core 2 and the separator 13, and the sealing box 4 can also play a role in fixing the electrode core 2 on the electrode sleeve 1.

As shown in fig. 1 and 2, as an embodiment, the sealing cavity 112 is filled with the sealing filler 5, the sealing filler 5 further seals the sealing cavity 112, the sealing filler 5 seals the connection position between the electrode cable 6 and the electrode core 2 (i.e., the connection position between the electrode cable 6 and the electrode core 2 is buried in the sealing filler 5), and one end of the electrode cable 6 extends out of the electrode sleeve 1 after passing through the sealing filler 5 (i.e., the electrode cable 6 is led out from above the electrode sleeve 1). The sealing filler 5 can be made of epoxy resin material or other sealing materials resistant to seawater.

As shown in fig. 1 and 2, as an embodiment, the anode cable 33 and the cathode cable 34 extend from the electrode cavity 111 into the sealing cavity 112 and then extend out of the electrode sleeve 1 through the sealing filler 5 (i.e., the anode cable 33 and the cathode cable 34 are led out from above the electrode sleeve 1). As shown in fig. 1, the anode cable 33 and the cathode cable 34 may extend from the inside of the electrode chamber 111 through the seal box 4 into the seal chamber 112; as shown in fig. 7, the anode cable 33 and the cathode cable 34 may also extend from the inside of the electrode chamber 111 through the separator 13 into the sealing chamber 112.

Specifically, as shown in fig. 1, the top of the electrode sleeve 1 is provided with an opening, so that the sealing box 4, the sealing filler 5 and the like can be conveniently added into the sealing cavity 112 through the top opening when the reference electrode is manufactured; meanwhile, in actual installation and use, a spool (not shown) can be connected with the top opening of the electrode sleeve 1, and the electrode cable 6, the anode cable 33 and the cathode cable 34 can be routed from the spool, so that the service life of the cable is prolonged, and the top of the electrode sleeve 1 is sealed.

As shown in fig. 1 to 4, as an embodiment, the electrode sheath 1 includes a sheath body 11 and a cover plate 12, the electrode core 2 is disposed in the sheath body 11, and the anti-fouling anode 31 is fixed on the inner wall of the sheath body 11. The bottom of the sleeve body 11 is provided with an opening 110, and the cover plate 12 is arranged at the opening 110; the runner is a through hole 121 arranged on the cover plate 12, and the through hole 121 is communicated with the inner cavity of the sleeve body 11, namely, external seawater can enter the sleeve body 11 through the through hole 121. The anti-fouling cathode 32 is fixed to the bottom of the casing 11, and the anti-fouling cathode 32 is located outside the casing 11 (the anti-fouling cathode 32 is specifically fixed to the bottom wall of the casing 11). Of course, the anti-fouling cathode 32 may be fixed to the cover plate 12 (for example, fixed to the lower surface of the cover plate 12).

As shown in fig. 4, as an embodiment, the cover plate 12 is provided with a plurality of through holes 121, and the plurality of through holes 121 are spaced around the center of the cover plate 12.

As shown in fig. 7, as another embodiment, the electrode sheath 1 includes a sheath body 11, the electrode core 2 is disposed in the sheath body 11, and the anti-fouling anode 31 is fixed to the inner wall of the sheath body 11. The runner is an opening 110 arranged at the bottom of the sleeve body 11, the opening 110 is communicated with the inner cavity of the sleeve body 11, namely, external seawater can enter the sleeve body 11 through the opening 110. The anti-fouling cathode 32 is fixed at the bottom of the sleeve 11, and the anti-fouling cathode 32 may be disposed on the inner wall of the sleeve 11 corresponding to the opening 110, or may be disposed on the bottom wall of the sleeve 11.

As one embodiment, the anti-fouling anode 31 is a titanium-based oxide anode; the anti-fouling cathode 32 is made of titanium or hastelloy, so that the anti-fouling cathode has the advantages of high strength and corrosion resistance. The antifouling anode 31 and the antifouling cathode 32 may have a plate-like or mesh-like structure.

As one embodiment, the area ratio of the antifouling anode 31 to the antifouling cathode 32 is 2:1 to 1:2, so that a proper amount of available chlorine can be generated by electrolysis, and a good electrolytic antifouling effect is achieved.

As shown in fig. 1, in one embodiment, the electrode sheath 1 is cylindrical, the electrode core 2 is disposed at a central position in the electrode sheath 1, the anti-fouling anode 31 is a cylindrical structure centered around the electrode core 2, and the anti-fouling cathode 32 is a circular ring structure centered around the electrode core 2, so that effective chlorine can be uniformly generated by electrolysis, and the anti-fouling effect can be improved.

As shown in fig. 7, in another embodiment, the electrode sheath 1 has a conical cylindrical structure, the electrode core 2 is disposed at a central position in the electrode sheath 1, the anti-fouling anode 31 has a conical cylindrical structure centered around the electrode core 2, and the anti-fouling cathode 32 has a conical cylindrical structure centered around the electrode core 2. Of course, the anti-fouling cathode 32 may have a circular ring structure. The shape of the anti-fouling anode 31 and the anti-fouling cathode 32 may be determined according to the shape of the electrode sheath 1.

As shown in fig. 5, as an embodiment, the electrolytic antifouling method of the reference electrode includes the steps of:

the anode cable 33 is electrically connected to the positive electrode of the dc power supply 7, and the cathode cable 34 is electrically connected to the negative electrode of the dc power supply 7; the direct current power supply 7 periodically supplies power to the antifouling anode 31 and the antifouling cathode 32 to intermittently electrolyze the seawater in the electrode sheath 1, thereby generating effective chlorine in the seawater in the electrode sheath 1 and/or in the vicinity of the electrode sheath 1.

As an embodiment, when intermittently electrolyzing the seawater in the electrode sleeve 1, the effective chlorine concentration in the seawater in the electrode sleeve 1 is controlled to be between 0.5 and 1.5ppm when the electrolysis is performed each time according to the volume of the inner cavity of the electrode sleeve 1 (namely the volume of the electrode cavity 111), and the interval time between the electrolysis is not more than 72 hours, so that a good electrolytic antifouling effect is achieved.

As shown in fig. 6, as an embodiment, the in-situ electrolytic regeneration method of the reference electrode includes the steps of:

when the potential of the reference electrode deviates from the standard electrode potential (+1.5-9.5 mV, relative to the saturated calomel electrode) by more than a certain value (for example, 5 mV), the electrode cable 6 is electrically connected with the positive electrode of the direct current power supply 7, and the cathode cable 34 is electrically connected with the negative electrode of the direct current power supply 7; a reverse polarization current is applied to the electrode core 2 by the direct current power supply 7 to convert the elemental silver on the electrode core 2 into silver chloride.

As one embodiment, the current density is controlled to be 3-30 mA/cm when the reverse polarization current is applied ² Between 1 and 10 hours of polarization time (i.e., the time per in situ electrolysis).

According to the reference electrode provided by the embodiment of the utility model, the anti-fouling component 3 is arranged to electrolyze seawater to generate the effective chlorine, so that marine organisms are prevented from adhering and growing in the electrode sleeve 1 and on the electrode core 2, the effective anti-fouling of the internal cavity of the reference electrode is realized, and the service life of the reference electrode is prolonged. Meanwhile, the anti-pollution anode 31 is positioned inside the electrode sleeve 1, so that generated effective chlorine can be effectively dispersed inside the electrode sleeve 1, the anti-pollution anode 31 can be prevented or reduced from being subjected to hydraulic flushing and mechanical damage, and the service life of the anti-pollution anode is prolonged. Meanwhile, due to the addition of the anti-fouling component 3, when the electrode core 2 of the reference electrode is reduced and failed due to silver chloride or silver halide (namely, the silver chloride or silver halide in the electrode core 2 is converted into elemental silver), the elemental silver is converted into AgCl by in-situ electrolysis of the electrode core 2 and the anti-fouling cathode 32, so that in-situ polarization regeneration of the electrode core 2 is realized, and the service life of the reference electrode is greatly prolonged.

Example 1

As shown in fig. 1, the reference electrode provided in this embodiment includes an electrode sleeve 1, an electrode core 2, an anti-fouling component 3, a sealing box 4, a sealing filler 5 and an electrode cable 6, the anti-fouling component 3 includes an anti-fouling anode 31, an anti-fouling cathode 32, an anode cable 33 and a cathode cable 34, and the electrode core 2 is a silver/silver chloride electrode.

The electrode sleeve 1 is made of insulating plastic materials, including but not limited to nylon, PVC, PE and the like, and is cylindrical. The anti-pollution anode 31 is a plate-type titanium-based oxide anode, is cylindrical and is fixed on the inner side wall of the electrode sleeve 1; the anti-fouling cathode 32 is made of hastelloy plate, is circular and is fixed at the bottom end of the electrode sleeve 1. The top of the electrode sleeve 1 is filled with epoxy resin sealing filler 5, a cover plate 12 is arranged at the bottom of the electrode sleeve 1, and a through hole 121 is formed in the cover plate 12 so that seawater can enter the electrode sleeve 1.

When in use, the reference electrode is wholly immersed in seawater, and the seawater enters the electrode sleeve 1 through the through holes 121 on the cover plate 12. When in operation, the electrode core 2 is used for potential measurement, and the electrode core 2 is connected with a potentiostat (not shown) through an electrode cable 6, so that the potentiostat is used as a signal source for automatic control of the potentiostat to adjust the magnitude of protection current, and the structure is in a good protection state.

When the electrolysis is carried out, the direct current power supply 7 is used for supplying power to the anti-fouling anode 31 and the anti-fouling cathode 32 once every 72 hours, and the electrolysis sea water generates available chlorine; according to the calculation of the inner cavity volume of the electrode sleeve 1, the concentration of the effective chlorine generated by electrolysis is about 1.0ppm, the generated effective chlorine is dispersed in the electrode sleeve 1, the attachment growth of marine organisms in the cavity is prevented, and the effective antifouling effect of the reference electrode is realized.

When the potential of the reference electrode deviates from the standard electrode potential (+1.5-9.5 mV, relative to the saturated calomel electrode) by more than 5mV, the electrode core 2 is connected with the positive electrode of the direct current power supply 7, the anti-pollution cathode 32 is connected with the negative electrode of the direct current power supply 7, and polarized current is applied, wherein the current density is equal to20mA/cm ² The polarization time is 1h, the simple substance silver is converted into AgCl, the in-situ polarization regeneration is realized, and the service life of the reference electrode is prolonged.

Example two

As shown in fig. 7, the reference electrode provided in this embodiment includes an electrode sleeve 1, an electrode core 2, an anti-fouling component 3, a sealing box 4, a sealing filler 5 and an electrode cable 6, the anti-fouling component 3 includes an anti-fouling anode 31, an anti-fouling cathode 32, an anode cable 33 and a cathode cable 34, and the electrode core 2 is a silver/silver chloride electrode.

The electrode sleeve 1 is made of insulating plastic, and is made of nylon, PVC, PE and the like, and is cone-shaped. The anti-pollution anode 31 is a reticular titanium-based oxide anode, is in a conical cylinder shape and is fixed on the inner side wall of the electrode sleeve 1; the anti-fouling cathode 32 adopts titanium mesh, is in a conical cylinder shape and is fixed at the bottom end of the electrode sleeve 1. The top of the electrode sleeve 1 is filled with epoxy resin sealing filler 5, and the bottom of the electrode sleeve 1 is provided with an opening 110 for seawater to enter the electrode sleeve 1.

In use, the reference electrode is immersed entirely in seawater, which enters the electrode housing 1 through the bottom opening 110. When in operation, the electrode core 2 is used for potential measurement, and the electrode core 2 is connected with a potentiostat (not shown) through an electrode cable 6, so that the potentiostat is used as a signal source for automatic control of the potentiostat to adjust the magnitude of protection current, and the structure is in a good protection state.

When the electrolysis is carried out, the direct current power supply 7 is used for supplying power to the anti-fouling anode 31 and the anti-fouling cathode 32 once every 24 hours, and the electrolysis sea water generates available chlorine; according to the calculation of the inner cavity volume of the electrode sleeve 1, the concentration of the effective chlorine generated by electrolysis is about 1.5ppm, and the generated effective chlorine is dispersed in the electrode sleeve 1 to prevent marine organisms from adhering and growing in the cavity, so that the effective antifouling effect of the reference electrode is realized.

When the potential of the reference electrode deviates from the standard electrode potential (+1.5-9.5 mV, relative to the saturated calomel electrode) by more than 5mV, the electrode core 2 is connected with the positive electrode of the direct current power supply 7, the anti-pollution cathode 32 is connected with the negative electrode of the direct current power supply 7, and polarized current is applied, and the current density is 15mA/cm ² Polarization time is 4h, and simple substance silver is converted into AgCl, and the silver is solidIn-situ polarization regeneration is performed, and the service life of the reference electrode is prolonged.

The foregoing is merely illustrative of the present utility model, and the present utility model is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present utility model. Therefore, the protection scope of the present utility model shall be subject to the protection scope of the claims.

Claims (10)

1. The reference electrode is used in a seawater environment and is characterized by comprising an electrode sleeve (1), an electrode core (2), an electrode cable (6) and an antifouling component (3), wherein the electrode core (2) is arranged in the electrode sleeve (1), and the electrode cable (6) is electrically connected with the electrode core (2); the electrode sleeve (1) is provided with a flow passage which is communicated with the inner cavity of the electrode sleeve (1) and is used for allowing external seawater to enter the electrode sleeve (1); the anti-fouling assembly (3) comprises an anti-fouling anode (31), an anti-fouling cathode (32), an anode cable (33) and a cathode cable (34), wherein the anti-fouling anode (31) is arranged in the electrode sleeve (1), the anti-fouling cathode (32) is arranged on the electrode sleeve (1), the anode cable (33) is electrically connected with the anti-fouling anode (31), and the cathode cable (34) is electrically connected with the anti-fouling cathode (32); the reference electrode is capable of electrolytic antifouling; when the reference electrode is used for electrolytic pollution prevention, the anode cable (33) and the cathode cable (34) are respectively used for being electrically connected with the positive electrode and the negative electrode of the direct current power supply (7) so as to electrolyze the seawater in the electrode sleeve (1), thereby generating available chlorine in the seawater in the electrode sleeve (1) and/or nearby the electrode sleeve (1).

2. The reference electrode according to claim 1, wherein a partition board (13) is arranged in the electrode sleeve (1), the partition board (13) divides the inner cavity of the electrode sleeve (1) into an electrode cavity (111) and a sealing cavity (112) which are adjacently arranged, the flow channel is arranged corresponding to the electrode cavity (111) and is communicated with the electrode cavity (111), the flow channel is used for allowing external seawater to enter the electrode cavity (111), and the anti-pollution anode (31) is arranged in the electrode cavity (111); the electrode assembly is characterized in that a perforation (131) is formed in the partition plate (13), one end of the electrode core (2) is located in the electrode cavity (111), the other end of the electrode core (2) penetrates through the perforation (131) and then stretches into the sealing cavity (112), and the connection position of the electrode cable (6) and the electrode core (2) is located in the sealing cavity (112).

3. The reference electrode of claim 2, further comprising a sealing capsule (4), the sealing capsule (4) at least partially filling between the outer side wall of the electrode core (2) and the inner wall of the perforation (131) to seal a gap between the outer side wall of the electrode core (2) and the inner wall of the perforation (131).

4. The reference electrode according to claim 2, wherein the sealing cavity (112) is filled with a sealing filler (5), the sealing filler (5) seals the connection position of the electrode cable (6) and the electrode core (2), and one end of the electrode cable (6) passes through the sealing filler (5) and then extends out of the electrode sleeve (1).

5. The reference electrode according to claim 4, characterized in that the anode cable (33) and the cathode cable (34) each extend from within the electrode cavity (111) into the sealing cavity (112) and then through the sealing filler (5) out of the electrode sheath (1).

6. The reference electrode according to claim 1, wherein the electrode sheath (1) comprises a sheath body (11), the electrode core (2) is arranged in the sheath body (11), and the anti-fouling anode (31) is fixed on the inner wall of the sheath body (11); the runner is arranged at an opening (110) at the bottom of the sleeve body (11), the opening (110) is communicated with an inner cavity of the sleeve body (11), and the anti-pollution cathode (32) is fixed at the bottom of the sleeve body (11).

7. The reference electrode according to claim 1, wherein the electrode sheath (1) comprises a sheath body (11) and a cover plate (12), the electrode core (2) is arranged in the sheath body (11), and the anti-fouling anode (31) is fixed on the inner wall of the sheath body (11); an opening (110) is formed in the bottom of the sleeve body (11), and the cover plate (12) is arranged at the opening (110); the flow channel is a through hole (121) arranged on the cover plate (12), and the through hole (121) is communicated with the inner cavity of the sleeve body (11); the anti-fouling cathode (32) is fixed on the bottom of the sleeve body (11) or the cover plate (12).

8. The reference electrode according to claim 1, wherein the anti-fouling anode (31) is a titanium-based oxide anode, the anti-fouling cathode (32) is made of titanium or hastelloy, and the area ratio of the anti-fouling anode (31) to the anti-fouling cathode (32) is 2:1 to 1:2.

9. the reference electrode according to claim 1, wherein the electrode sheath (1) has a cylindrical or conical cylindrical structure, the electrode core (2) is disposed at a central position within the electrode sheath (1), the anti-fouling anode (31) has a cylindrical or conical cylindrical structure centered around the electrode core (2), and the anti-fouling cathode (32) has a cylindrical or conical cylindrical or circular ring structure centered around the electrode core (2).

10. The reference electrode according to claim 1, characterized in that the electrode core (2) is a silver/silver chloride electrode or a silver/silver halide electrode, which reference electrode is also capable of in situ electrolytic regeneration; when the reference electrode is subjected to in-situ electrolytic regeneration, the electrode cable (6) and the cathode cable (34) are respectively and electrically connected with the positive electrode and the negative electrode of the direct current power supply (7) so as to apply reverse polarization current to the electrode core (2) to convert the simple substance silver on the electrode core (2) into silver chloride.