reference electrode

Abstract

The application provides a reference electrode, which comprises an electrode sleeve, an electrode core, an electrode cable and an anti-fouling assembly, the electrode core is arranged in the electrode sleeve, and the electrode cable is electrically connected with the electrode core; the anti-fouling assembly comprises an anti-fouling anode, an anti-fouling cathode, an anode cable and a cathode cable, 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 used for electrolysis anti-fouling. The reference electrode provided by the application can generate effective chlorine by electrolysis of seawater through the anti-fouling assembly, so that biological fouling is avoided, and the service life of the reference electrode is improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of electrochemistry, in particular to a reference electrode. BACKGROUND

[0002] The reference electrode is an electrode used as a reference for comparison when measuring the potential of various electrodes, and is widely used in many technical fields such as electrochemical protection. In seawater environment, the most commonly used reference electrodes include silver / silver chloride reference electrode (i.e. Ag / AgCl reference electrode; such as a solid Ag / AgCl electrode core disclosed in patent CN201010585794.4, which mainly comprises Ag and AgCl), silver / halide silver reference electrode (i.e. Ag / AgX reference electrode; such as a hot-dip coated silver / halide silver reference electrode disclosed in patent CN200810015054.X, which mainly comprises Ag, AgCl and AgBr), copper / copper sulfate reference electrode, high-purity zinc reference electrode, etc. Among them, the silver / silver chloride reference electrode has the advantages of stable potential, good reproducibility, and solid durability, and is the most widely used reference electrode in the cathodic protection of marine structures such as ships and offshore platforms.

[0003] Due to the presence of a large amount of pollutants and impurities in the marine environment, calcium, magnesium ions and marine organisms in seawater will adhere to the surface of the reference electrode, thereby reducing the activity of the reference electrode. In addition, although the chemical properties of silver / silver chloride and silver / halide silver are relatively stable, during long-term use, as a cathode, the reference electrode will still cause the AgCl or AgX in the electrode to react to form Ag single element through a weak leakage current. When the proportion of Ag single element increases to a certain range, the electrode will fail, thereby affecting the service life of the reference electrode (related studies show that when the mass percentage of AgCl on the surface of the Ag / AgCl reference electrode is less than 8%, the reference electrode will fail; in actual engineering application, the Ag / AgCl reference electrode will gradually fail after 5 years of use, which cannot meet the long-term potential measurement requirements of marine structures such as offshore platforms). SUMMARY

[0004] The purpose of the present application is to provide a reference electrode, which generates effective chlorine by electrolyzing seawater through the setting of the anti-fouling assembly, thereby avoiding biological fouling and improving the service life of the reference electrode.

[0005] The application provides a reference electrode for seawater environment, which comprises an electrode sleeve, an electrode core, an electrode cable and an anti-fouling assembly, the electrode core is arranged in the electrode sleeve, and the electrode cable is electrically connected with the electrode core; a flow channel is arranged on the electrode sleeve and communicates with the inner cavity of the electrode sleeve, and the flow channel 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, 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 perform electrolytic anti-fouling; when the reference electrode performs electrolytic anti-fouling, the anode cable and the cathode cable are respectively electrically connected with the positive and negative poles of a direct-current power supply to electrolyze seawater in the electrode sleeve, so that effective chlorine is generated in the seawater in the electrode sleeve and / or near the electrode sleeve.

[0006] 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 arranged adjacently, the flow channel is arranged corresponding to the electrode cavity and communicates with the electrode cavity, the flow channel is used for allowing external seawater to enter the electrode cavity, and the anti-fouling anode is arranged in the electrode cavity; a perforation is arranged on the partition plate, one end of the electrode core is located in the electrode cavity, the other end of the electrode core extends into the sealing cavity through the perforation, and the connection position of the electrode cable and the electrode core is located in the sealing cavity.

[0007] Further, the reference electrode further comprises a sealing envelope, the sealing envelope is at least partially filled between the outer side wall of the electrode core and the inner wall of the perforation to seal the gap between the outer side wall of the electrode core and the inner wall of the perforation.

[0008] Further, the sealing cavity is filled with a sealing filler, the sealing filler seals the connection position of the electrode cable and the electrode core, and one end of the electrode cable extends out of the electrode sleeve through the sealing filler.

[0009] Further, the anode cable and the cathode cable both extend from the electrode cavity to the sealing cavity and then extend out of the electrode sleeve through the sealing filler.

[0010] Further, the electrode sleeve comprises a sleeve body, the electrode core is arranged in the sleeve body, and the anti-fouling 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 communicates with the inner cavity of the sleeve body, and the anti-fouling cathode is fixed at the bottom of the sleeve body.

[0011] Further, the electrode sleeve comprises a sleeve body and a cover plate, the electrode core is arranged in the sleeve body, and the anti-fouling 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 flow channel is a through hole arranged on the cover plate, and the through hole is communicated with the inner cavity of the sleeve body; and the anti-fouling cathode is fixed on the bottom of the sleeve body or the cover plate.

[0012] Further, the anti-fouling anode is a titanium-based oxide anode, the anti-fouling cathode is made of titanium or hastelloy, and the area ratio of the anti-fouling anode to the anti-fouling cathode is 2:1-1:2.

[0013] Further, the electrode sleeve is in a cylindrical or conical cylindrical structure, the electrode core is arranged at the center position in the electrode sleeve, the anti-fouling anode is in a cylindrical or conical cylindrical structure around the electrode core as the center, and the anti-fouling cathode is in a cylindrical or conical cylindrical or circular ring structure around the electrode core as the center.

[0014] Further, the electrolytic anti-fouling method of the reference electrode comprises the following steps.

[0015] The anode cable is electrically connected with the positive pole of a direct current power supply, the cathode cable is electrically connected with the negative pole of the direct current power supply, and the anti-fouling anode and the anti-fouling cathode are periodically powered by the direct current power supply to intermittently electrolyze seawater in the electrode sleeve, so that effective chlorine is generated in the seawater in the electrode sleeve and / or near the electrode sleeve.

[0016] Further, when the seawater in the electrode sleeve is intermittently electrolyzed, the concentration of effective chlorine in the seawater in the electrode sleeve is controlled to be between 0.5-1.5 ppm during each electrolysis, and the interval time between each two electrolyses is not more than 72 hours.

[0017] Further, the electrode core is a silver / silver chloride electrode or a silver / silver halide electrode, and the reference electrode can also be regenerated by in-situ electrolysis; when the reference electrode is regenerated by in-situ electrolysis, the electrode cable and the cathode cable are respectively used for electrical connection with the positive pole and the negative pole of a direct current power supply to apply a reverse polarization current to the electrode core, so that elemental silver on the electrode core is converted into silver chloride.

[0018] Further, the in-situ electrolytic regeneration method of the reference electrode comprises the following steps.

[0019] The electrode cable is electrically connected with the positive pole of a direct current power supply, the cathode cable is electrically connected with the negative pole of the direct current power supply, and a reverse polarization current is applied to the electrode core by the direct current power supply to convert elemental silver on the electrode core into silver chloride.

[0020] Further, the control current density is between 3-30 mA / cm 2 and the polarization time is between 1-10 hours.

[0021] The reference electrode provided by the application generates effective chlorine by electrolyzing seawater through the anti-fouling assembly, thereby avoiding the attachment and growth of marine organisms in the electrode sleeve and on the electrode core, realizing effective anti-fouling of the internal cavity of the reference electrode, and prolonging the service life of the reference electrode. Meanwhile, the anti-fouling anode is located inside the electrode sleeve, which not only enables the generated effective chlorine to be effectively dispersed in the electrode sleeve (effective chlorine is generated on the anti-fouling anode when seawater is electrolyzed), but also avoids or reduces the anti-fouling anode from being eroded by water and mechanically damaged, thereby prolonging the service life. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 Fig. 1 is a cross-sectional view of the reference electrode in an embodiment of the application.

[0023] Figure 2 Fig. 2 is a cross-sectional view of the inner sleeve in an embodiment of the application. Figure 1

[0024] Figure 3 Fig. 3 is a cross-sectional view of the cover plate in an embodiment of the application. Figure 1

[0025] Figure 4 Fig. 4 is a plan view of the cover plate in an embodiment of the application. Figure 1

[0026] Figure 5 Fig. 5 is a schematic view of the electrical connection relationship between the reference electrode in an embodiment of the application and a direct current power source when electrolyzing for anti-fouling.

[0027] Figure 6 Fig. 6 is a schematic view of the electrical connection relationship between the reference electrode in an embodiment of the application and a direct current power source when electrolyzing in situ for regeneration.

[0028] Figure 7 Fig. 7 is a cross-sectional view of the reference electrode in another embodiment of the application. DETAILED DESCRIPTION

[0029] The specific embodiments of the application will be further described in detail below with reference to the accompanying drawings and embodiments. The following embodiments are used to illustrate the application, but are not used to limit the scope of the application.

[0030] The terms "first", "second", "third", "fourth" and the like (if any) in the specification and claims of the application are used to distinguish similar objects, and do not necessarily have to describe a specific order or sequence.

[0031] ​​​The up, down, left, right, front, back, top, bottom and other (if any) orientation words involved in the description and claims of the present application are defined according to the position of the structure in the drawing and the position of the structure relative to each other in the drawing, only for the purpose of expressing the clarity and convenience of the technical scheme. It should be understood that the use of orientation words should not limit the scope of the application claimed.

[0032] As shown in Figure 1 and Figure 5 The reference electrode provided by the embodiment of the present application is used in seawater environment, and can be used in cathodic protection of marine structures such as ships and offshore platforms. The reference electrode comprises an electrode sleeve 1, an electrode core 2, an electrode cable 6 and an anti-fouling assembly 3. 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 channel, which is in communication 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. 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 can perform electrolytic anti-fouling. When the reference electrode performs electrolytic anti-fouling, the anode cable 33 and the cathode cable 34 are respectively electrically connected with the positive and negative poles of a direct current power supply 7, and the anti-fouling anode 31 and the anti-fouling cathode 32 are used to electrolyze seawater in the electrode sleeve 1, so that effective chlorine (including hypochlorous acid, sodium hypochlorite, chlorine gas, etc.) is generated in the seawater in the electrode sleeve 1 and / or the seawater near the electrode sleeve 1. The effective chlorine can kill marine organisms in the seawater and / or inhibit the growth and reproduction of the marine organisms, thereby avoiding biological fouling inside the electrode sleeve 1 and prolonging the service life of the reference electrode.

[0033] Specifically, the reference electrode provided by the embodiment generates effective chlorine by setting the anti-fouling assembly 3 to electrolyze seawater, so as to avoid the attachment and growth of marine organisms 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. At the same time, the anti-fouling anode 31 is located inside the electrode sleeve 1, which not only enables the generated effective chlorine to be effectively dispersed in the electrode sleeve 1 (the effective chlorine is generated on the anti-fouling anode 31 when seawater is electrolyzed), but also avoids or reduces the water scouring and mechanical damage of the anti-fouling anode 31, thereby prolonging the service life of the anti-fouling anode 31.

[0034] As shown in Figure 6As shown, in one 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, AgBr, or other silver halides). The reference electrode can also be regenerated in situ; when the reference electrode is regenerated in situ, the electrode cable 6 and the cathode cable 34 are respectively connected to the positive and negative terminals of the DC power supply 7 to apply a reverse polarization current to the electrode core 2, so that the elemental silver on the electrode core 2 is converted into silver chloride.

[0035] Specifically, due to the addition of the anti-fouling component 3, when the reference electrode core 2 fails due to the reduction of silver chloride or silver halide (i.e., 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, thereby realizing the in-situ polarization regeneration of the electrode core 2 and significantly improving the service life of the reference electrode.

[0036] It should be noted that when the reference electrode only has the function of electrolytic antifouling, the electrode core 2 can be a silver / silver chloride electrode or a silver / silver halide electrode, or other types of electrodes (such as high-purity zinc electrodes); when the reference electrode has both the function of electrolytic antifouling and the function of in-situ electrolytic regeneration, the electrode core 2 is generally a silver / silver chloride electrode or a silver / silver halide electrode (the main components of silver chloride electrodes and silver halide electrodes are generally silver and silver chloride).

[0037] It should be noted that when the reference electrode is undergoing electrolytic antifouling and in-situ electrolytic regeneration, the DC power supply 7 used for both can be the same power supply or different power supplies.

[0038] As one implementation method, the electrode core 2 can be prepared by hot dip coating or powder pressing, or by other methods such as thermal decomposition.

[0039] In one implementation, the electrode sleeve 1 is made of an insulating and corrosion-resistant material, such as nylon, PVC, PE, etc.

[0040] like Figure 1 As shown, in one embodiment, the antifouling cathode 32 is fixed to the electrode sleeve 1, and the antifouling cathode 32 is disposed outside the electrode sleeve 1 or in the flow channel, so that the precipitates generated on the antifouling cathode 32 can be removed in a timely manner (because seawater contains calcium, magnesium and other ions, calcium, magnesium and other precipitates will be generated on the antifouling cathode 32 during seawater electrolysis), avoiding the accumulation of precipitates and blockage. When the antifouling cathode 32 is disposed outside the electrode sleeve 1, the precipitates on the antifouling cathode 32 can be removed directly; when the antifouling cathode 32 is disposed in the flow channel, the precipitates on the antifouling cathode 32 can be discharged to the outside of the electrode sleeve 1 through the flow channel.

[0041] like Figure 1and Figure 2 As shown in FIG. 1, as an embodiment, the electrode sleeve 1 is provided with a partition plate 13, the partition plate 13 is in an integral structure with the electrode sleeve 1, the partition plate 13 divides the inner cavity of the electrode sleeve 1 into an electrode cavity 111 and a sealing cavity 112 arranged adjacently, a flow channel corresponding to the electrode cavity 111 is arranged and communicates with the electrode cavity 111, the flow channel is used for allowing external seawater to enter the electrode cavity 111, and the antifouling anode 31 is arranged in the electrode cavity 111. The partition plate 13 is provided with a through hole 131, one end of the electrode core 2 is located in the electrode cavity 111, the other end of the electrode core 2 extends into the sealing cavity 112 after passing through the through hole 131, and the connection position (i.e., the wiring position) of the electrode cable 6 and the electrode core 2 is located in the sealing cavity 112.

[0042] Specifically, in order to prevent the wiring position of the electrode cable 6 and the electrode core 2 from being rusted / corroded (if the wiring position of the electrode cable 6 and the electrode core 2 is rusted, not only the service life of the reference electrode will be affected, but also the resistance value of the electrode core 2 will be affected, and then the accuracy of the reference electrode potential measurement will be affected), the partition plate 13 is arranged in the electrode sleeve 1, the inner cavity of the electrode sleeve 1 is divided into the electrode cavity 111 and the sealing cavity 112, the connection position of the electrode cable 6 and the electrode core 2 is located in the sealing cavity 112, so that the wiring position of the two is prevented from being rusted / corroded; and the antifouling anode 31 is arranged in the electrode cavity 111, so that the external seawater can enter the electrode cavity 111 for exchange, and the normal electrolytic antifouling function of the reference electrode is not affected.

[0043] As shown in FIG. 1, as an embodiment, the electrode sleeve 1 is provided with a partition plate 13, the partition plate 13 is in an integral structure with the electrode sleeve 1, the partition plate 13 divides the inner cavity of the electrode sleeve 1 into an electrode cavity 111 and a sealing cavity 112 arranged adjacently, a flow channel corresponding to the electrode cavity 111 is arranged and communicates with the electrode cavity 111, the flow channel is used for allowing external seawater to enter the electrode cavity 111, and the antifouling anode 31 is arranged in the electrode cavity 111. The partition plate 13 is provided with a through hole 131, one end of the electrode core 2 is located in the electrode cavity 111, the other end of the electrode core 2 extends into the sealing cavity 112 after passing through the through hole 131, and the connection position (i.e., the wiring position) of the electrode cable 6 and the electrode core 2 is located in the sealing cavity 112. Figure 1 and Figure 2 As shown in FIG. 1, as an embodiment, the reference electrode further comprises a sealing envelope 4, the sealing envelope 4 is at least partially filled between the outer side wall of the electrode core 2 and the inner wall of the through hole 131, so as to seal the gap between the outer side wall of the electrode core 2 and the inner wall of the through hole 131, thereby preventing the seawater in the electrode cavity 111 from entering the sealing cavity 112 through the gap between the outer side wall of the electrode core 2 and the inner wall of the through hole 131. At the same time, a part of the sealing envelope 4 is located in the sealing cavity 112 and connected between the electrode core 2 and the partition plate 13, and the sealing envelope 4 can also fix the electrode core 2 on the electrode sleeve 1.

[0044] As shown in FIG. 1, as an embodiment, the electrode sleeve 1 is provided with a partition plate 13, the partition plate 13 is in an integral structure with the electrode sleeve 1, the partition plate 13 divides the inner cavity of the electrode sleeve 1 into an electrode cavity 111 and a sealing cavity 112 arranged adjacently, a flow channel corresponding to the electrode cavity 111 is arranged and communicates with the electrode cavity 111, the flow channel is used for allowing external seawater to enter the electrode cavity 111, and the antifouling anode 31 is arranged in the electrode cavity 111. The partition plate 13 is provided with a through hole 131, one end of the electrode core 2 is located in the electrode cavity 111, the other end of the electrode core 2 extends into the sealing cavity 112 after passing through the through hole 131, and the connection position (i.e., the wiring position) of the electrode cable 6 and the electrode core 2 is located in the sealing cavity 112. Figure 1 and Figure 2 As shown in FIG. 1, as an embodiment, the reference electrode further comprises a sealing envelope 4, the sealing envelope 4 is at least partially filled between the outer side wall of the electrode core 2 and the inner wall of the through hole 131, so as to seal the gap between the outer side wall of the electrode core 2 and the inner wall of the through hole 131, thereby preventing the seawater in the electrode cavity 111 from entering the sealing cavity 112 through the gap between the outer side wall of the electrode core 2 and the inner wall of the through hole 131. At the same time, a part of the sealing envelope 4 is located in the sealing cavity 112 and connected between the electrode core 2 and the partition plate 13, and the sealing envelope 4 can also fix the electrode core 2 on the electrode sleeve 1.

[0045] As shown in Figure 1 and Figure 2 As an embodiment, the anode cable 33 and the cathode cable 34 both extend from the electrode cavity 111 to the sealed cavity 112 and then pass through the sealing filler 5 to the outside of the electrode sleeve 1 (i.e. the anode cable 33 and the cathode cable 34 are drawn out from above the electrode sleeve 1). As shown in Figure 1 , the anode cable 33 and the cathode cable 34 can extend from the electrode cavity 111 to the sealed cavity 112 after passing through the sealing filler 4; as shown in Figure 7 , the anode cable 33 and the cathode cable 34 can also extend from the electrode cavity 111 to the sealed cavity 112 after passing through the partition plate 13.

[0046] Specifically, as shown in Figure 1 , the top of the electrode sleeve 1 is provided with an opening, so as to facilitate the addition of the sealing filler 4 and the sealing filler 5 into the sealed cavity 112 through the top opening when the reference electrode is manufactured; meanwhile, when actually installed and used, a wire tube (not shown in the figure) can be connected to the top opening position of the electrode sleeve 1, and the electrode cable 6, the anode cable 33 and the cathode cable 34 can be routed from the wire tube, so as to improve the service life of the cable and seal the top of the electrode sleeve 1.

[0047] As shown in Figures 1 to 4 , as an embodiment, the electrode sleeve 1 comprises a sleeve body 11 and a cover plate 12, the electrode core 2 is arranged in the sleeve body 11, and the anti-fouling anode 31 is fixed on the inner wall of the sleeve 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 flow channel is a through hole 121 arranged on the cover plate 12, and the through hole 121 is in communication with the inner cavity of the sleeve body 11, i.e. the seawater outside can enter the sleeve body 11 through the through hole 121. The anti-fouling cathode 32 is fixed on the bottom of the sleeve body 11, and the anti-fouling cathode 32 is located outside the sleeve body 11 (the anti-fouling cathode 32 is specifically fixed on the bottom wall of the sleeve body 11). Of course, the anti-fouling cathode 32 can also be fixed on the cover plate 12 (for example, on the lower surface of the cover plate 12).

[0048] As shown in Figure 4 , as an embodiment, a plurality of through holes 121 are arranged on the cover plate 12, and the plurality of through holes 121 are arranged at intervals around the center of the cover plate 12.

[0049] As shown in Figure 7As shown, in another embodiment, the electrode sleeve 1 includes a sleeve body 11, an electrode core 2 disposed inside the sleeve body 11, and an antifouling anode 31 fixed to the inner wall of the sleeve body 11. The flow channel is an opening 110 disposed at the bottom of the sleeve body 11, which communicates with the inner cavity of the sleeve body 11, allowing external seawater to enter the sleeve body 11 through the opening 110. The antifouling cathode 32 is fixed to the bottom of the sleeve body 11. The antifouling cathode 32 can be disposed on the inner wall of the sleeve body 11 corresponding to the opening 110, or it can be disposed on the bottom wall of the sleeve body 11.

[0050] In one embodiment, the anti-fouling anode 31 is a titanium-based oxide anode; the anti-fouling cathode 32 is made of titanium or Hastelloy, thus possessing the advantages of high strength and corrosion resistance. The anti-fouling anode 31 and the anti-fouling cathode 32 can adopt a plate-like or mesh-like structure.

[0051] As one implementation method, the area ratio of the anti-fouling anode 31 to the anti-fouling cathode 32 is 2:1 to 1:2, thereby enabling the electrolysis to generate an appropriate amount of available chlorine and achieve a good electrolytic anti-fouling effect.

[0052] like Figure 1 As shown, in one embodiment, the electrode sleeve 1 is cylindrical, the electrode core 2 is located at the center of the electrode sleeve 1, the anti-fouling anode 31 is a cylindrical structure surrounding the electrode core 2, and the anti-fouling cathode 32 is an annular structure surrounding the electrode core 2, thereby enabling uniform electrolysis to generate effective chlorine and improving the anti-fouling effect.

[0053] like Figure 7 As shown, in another embodiment, the electrode sleeve 1 has a conical cylindrical structure, the electrode core 2 is located at the center of the electrode sleeve 1, the anti-fouling anode 31 is a conical cylindrical structure surrounding the electrode core 2, and the anti-fouling cathode 32 is a conical cylindrical structure surrounding the electrode core 2. Of course, the anti-fouling cathode 32 can also be an annular structure. The shapes of the anti-fouling anode 31 and the anti-fouling cathode 32 can be determined according to the shape of the electrode sleeve 1.

[0054] like Figure 5 As shown, as one embodiment, the electrolytic antifouling method for the reference electrode includes the following steps:

[0055] The anode cable 33 is electrically connected to the positive terminal of the DC power supply 7, and the cathode cable 34 is electrically connected to the negative terminal of the DC power supply 7. The DC power supply 7 periodically supplies power to the antifouling anode 31 and the antifouling cathode 32 to intermittently electrolyze the seawater inside the electrode sleeve 1, thereby generating effective chlorine in the seawater inside and / or near the electrode sleeve 1.

[0056] As an embodiment, when the seawater in the electrode sleeve 1 is electrolyzed intermittently, the concentration of the effective chlorine in the seawater in the electrode sleeve 1 is controlled to be between 0.5 and 1.5 ppm per electrolysis, and the interval between two electrolyzations is not more than 72 hours, according to the volume of the inner cavity of the electrode sleeve 1 (i.e. the volume of the electrode cavity 111), so that a good electrolytic antifouling effect is achieved.

[0057] As shown in Figure 6 As an embodiment, the in-situ electrolytic regeneration method of the reference electrode comprises the following steps:

[0058] 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 to the positive pole of the direct current power supply 7, and the cathode cable 34 is electrically connected to the negative pole 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, so that the elemental silver on the electrode core 2 is converted into silver chloride.

[0059] As an embodiment, when the reverse polarization current is applied, the current density is controlled to be between 3 and 30 mA / cm 2 , and the polarization time (i.e. the time of each in-situ electrolysis) is between 1 and 10 hours.

[0060] The reference electrode provided by the embodiment of the present application generates effective chlorine by electrolyzing seawater through the antifouling assembly 3, so that the attachment and growth of marine organisms in the electrode sleeve 1 and on the electrode core 2 are avoided, the effective antifouling of the internal cavity of the reference electrode is achieved, and the service life of the reference electrode is prolonged. At the same time, the antifouling anode 31 is located inside the electrode sleeve 1, which not only enables the generated effective chlorine to be effectively dispersed in the electrode sleeve 1, but also avoids or reduces the water scouring and mechanical damage of the antifouling anode 31, thereby prolonging the service life of the antifouling anode 31. At the same time, since the antifouling assembly 3 is added, when the electrode core 2 of the reference electrode is reduced and disabled due to silver chloride or silver halide (i.e. 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 antifouling cathode 32, the in-situ polarization regeneration of the electrode core 2 is achieved, and the service life of the reference electrode is greatly improved.

[0061] Embodiment One

[0062] As shown in Figure 1 The reference electrode provided by the embodiment comprises an electrode sleeve 1, an electrode core 2, an antifouling assembly 3, a sealing envelope 4, a sealing filler 5, and an electrode cable 6. The antifouling assembly 3 comprises an antifouling anode 31, an antifouling cathode 32, an anode cable 33, and a cathode cable 34. The electrode core 2 is a silver / silver chloride electrode.

[0063] The electrode sleeve 1 is made of insulating plastic material, including but not limited to nylon, PVC, PE, etc., and is in a cylindrical shape. The anti-fouling anode 31 is a plate-type titanium-based oxide anode, in a cylindrical shape, fixed to the inner side wall of the electrode sleeve 1; the anti-fouling cathode 32 is a Hastelloy plate, in a circular ring shape, fixed to 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 a cover plate 12 having a through hole 121 for seawater to enter the inside of the electrode sleeve 1.

[0064] In use, the reference electrode is entirely immersed in seawater, and the seawater enters the inside of the electrode sleeve 1 through the through hole 121 in the cover plate 12. In operation, the electrode core 2 is used for potential measurement, and the electrode core 2 is connected to a constant potential instrument (not shown) through the electrode cable 6, thereby serving as a signal source automatically controlled by the constant potential instrument to adjust the size of the protection current, so that the structure is in a good protection state.

[0065] In electrolytic anti-fouling, the direct current power supply 7 is used to supply power to the anti-fouling anode 31 and the anti-fouling cathode 32 once every 72 hours, and effective chlorine is generated by electrolyzing seawater; according to the volume of the inner cavity of the electrode sleeve 1, the concentration of the effective chlorine generated by electrolysis is about 1.0 ppm, and the effective chlorine generated is dispersed in the inside of the electrode sleeve 1, preventing the attachment and growth of marine organisms in the cavity, and realizing effective anti-fouling of the reference electrode.

[0066] When the potential deviation of the reference electrode from the standard electrode potential (+1.5-9.5 mV, relative to the saturated calomel electrode) exceeds 5 mV, the electrode core 2 is connected to the positive electrode of the direct current power supply 7, the anti-fouling cathode 32 is connected to the negative electrode of the direct current power supply 7, a polarization current is applied, the current density is 20 mA / cm 2 , the polarization time is 1 h, the elemental silver is converted into AgCl, in-situ polarization regeneration is realized, and the service life of the reference electrode is prolonged.

[0067] Example Two

[0068] As shown in Figure 7 , the reference electrode provided by the present embodiment includes an electrode sleeve 1, an electrode core 2, an anti-fouling assembly 3, a sealing box 4, a sealing filler 5, and an electrode cable 6. The anti-fouling assembly 3 includes an anti-fouling anode 31, an anti-fouling cathode 32, an anode cable 33, and a cathode cable 34. The electrode core 2 is a silver / silver chloride electrode.

[0069] The electrode sleeve 1 is made of insulating plastic material, including but not limited to nylon, PVC, PE, etc., and is in a cylindrical shape. The anti-fouling anode 31 is a plate-type titanium-based oxide anode, in a cylindrical shape, fixed to the inner side wall of the electrode sleeve 1; the anti-fouling cathode 32 is a Hastelloy plate, in a circular ring shape, fixed to 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 a cover plate 12 having a through hole 121 for seawater to enter the inside of the electrode sleeve 1.

[0070] In use, the reference electrode is entirely immersed in seawater, and seawater enters the interior of the electrode sleeve 1 through the opening 110 at the bottom. In operation, the electrode core 2 is used for potential measurement, and the electrode core 2 is connected to a constant potential instrument (not shown in the figure) through the electrode cable 6, so as to serve as a signal source automatically controlled by the constant potential instrument, to adjust the size of the protection current, so that the structure is in a good protection state.

[0071] In electrolytic antifouling, the direct current power supply 7 is used to supply power to the antifouling anode 31 and the antifouling cathode 32 once every 24 hours, and effective chlorine is generated by electrolyzing seawater; according to the volume of the inner cavity of the electrode sleeve 1, the concentration of the effective chlorine generated by electrolysis is about 1.5 ppm, and the effective chlorine generated is dispersed in the interior of the electrode sleeve 1, to prevent marine organisms from adhering and growing in the interior of the cavity, and to realize effective antifouling of the reference electrode.

[0072] When the potential offset of the reference electrode from the standard electrode potential (+1.5-9.5 mV, relative to the saturated calomel electrode) exceeds 5 mV, the electrode core 2 is connected to the positive electrode of the direct current power supply 7, the antifouling cathode 32 is connected to the negative electrode of the direct current power supply 7, a polarization current is applied, the current density is 15 mA / cm 2 , the polarization time is 4 h, elemental silver is converted into AgCl, in-situ polarization regeneration is realized, and the service life of the reference electrode is prolonged.

[0073] The above is only a specific embodiment of the present application, but the protection scope of the present application is not limited to this, any person skilled in the art can easily think of changes or replacements within the technical range disclosed by the present application, which should be covered within the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims

1. A reference electrode for use in a seawater environment, characterized in that, The reference electrode includes an electrode sleeve (1), an electrode core (2), an electrode cable (6), and an antifouling component (3). The electrode core (2) is disposed inside the electrode sleeve (1), and the electrode cable (6) is electrically connected to the electrode core (2). The electrode sleeve (1) is provided with a flow channel, which communicates with the inner cavity of the electrode sleeve (1) and is used to allow external seawater to enter the electrode sleeve (1). The antifouling component (3) includes an antifouling anode (31), an antifouling cathode (32), an anode cable (33), and a cathode cable (34). The antifouling anode (31) is disposed inside the electrode sleeve (1), and the antifouling cathode (32) is disposed on the electrode sleeve (1). The antifouling cathode (32) is disposed outside the electrode sleeve (1) or at the flow channel; the antifouling anode (31) and the antifouling cathode (32) are plate-shaped or mesh-shaped structures; the anode cable (33) is electrically connected to the antifouling anode (31), and the cathode cable (34) is electrically connected to the antifouling cathode (32); the reference electrode is capable of electrolytic antifouling; when the reference electrode is performing electrolytic antifouling, the anode cable (33) and the cathode cable (34) are respectively used to be electrically connected to the positive and negative poles of the DC power supply (7) to electrolyze the seawater in the electrode sleeve (1), thereby generating effective chlorine in the seawater in the electrode sleeve (1) and / or near the electrode sleeve (1).

2. The reference electrode as described in claim 1, characterized in that, The electrode sleeve (1) is provided with a partition (13), which divides the inner cavity of the electrode sleeve (1) into an adjacent electrode cavity (111) and a sealing cavity (112). The flow channel is provided corresponding to the electrode cavity (111) and communicates with the electrode cavity (111). The flow channel is used to allow external seawater to enter the electrode cavity (111). The antifouling anode (31) is provided in the electrode cavity (111). The partition (13) is provided with a perforation (131). One end of the electrode core (2) is located in the electrode cavity (111), and the other end of the electrode core (2) passes through the perforation (131) and extends into the sealing cavity (112). The connection position of the electrode cable (6) and the electrode core (2) is located in the sealing cavity (112).

3. The reference electrode as described in claim 2, characterized in that, The reference electrode also includes a sealing box (4), which at least partially fills the space between the outer wall of the electrode core (2) and the inner wall of the perforation (131) to seal the gap between the outer wall of the electrode core (2) and the inner wall of the perforation (131).

4. The reference electrode as described in claim 2, characterized in that, The sealed cavity (112) is filled with sealing filler (5), which seals the connection between the electrode cable (6) and the electrode core (2), and one end of the electrode cable (6) passes through the sealing filler (5) and extends out of the electrode sleeve (1).

5. The reference electrode as described in claim 4, characterized in that, Both the anode cable (33) and the cathode cable (34) extend from the electrode cavity (111) into the sealing cavity (112) and then pass through the sealing filler (5) to extend out of the electrode sleeve (1).

6. The reference electrode as claimed in claim 1, characterized in that, The electrode sleeve (1) includes a sleeve body (11), the electrode core (2) is disposed inside the sleeve body (11), the anti-fouling anode (31) is fixed on the inner wall of the sleeve body (11), the flow channel is an opening (110) disposed at the bottom of the sleeve body (11), the opening (110) communicates with the inner cavity of the sleeve body (11), and the anti-fouling cathode (32) is fixed at the bottom of the sleeve body (11).

7. The reference electrode as claimed in claim 1, characterized in that, The electrode sleeve (1) includes a sleeve body (11) and a cover plate (12). The electrode core (2) is disposed inside the sleeve body (11). The anti-fouling anode (31) is fixed on the inner wall of the sleeve body (11). The bottom of the sleeve body (11) is provided with an opening (110). The cover plate (12) is disposed at the opening (110). The flow channel is a through hole (121) disposed on the cover plate (12). The through hole (121) communicates 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 on the cover plate (12).

8. The reference electrode as claimed in claim 1, characterized in that, The anti-fouling anode (31) is a titanium-based oxide anode, and the anti-fouling cathode (32) is made of titanium or Hastelloy. 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 as claimed in claim 1, characterized in that, The electrode sleeve (1) is a cylindrical or conical structure, the electrode core (2) is located at the center of the electrode sleeve (1), the anti-fouling anode (31) is a cylindrical or conical structure surrounding the electrode core (2), and the anti-fouling cathode (32) is a cylindrical, conical, or annular structure surrounding the electrode core (2).

10. The reference electrode as claimed in claim 1, characterized in that, The electrolytic antifouling method for the reference electrode includes the following steps: The anode cable (33) is electrically connected to the positive terminal of the DC power supply (7), and the cathode cable (34) is electrically connected to the negative terminal of the DC power supply (7). The DC power supply (7) periodically supplies power to the antifouling anode (31) and the antifouling cathode (32) to intermittently electrolyze the seawater in the electrode sleeve (1), thereby generating effective chlorine in the seawater in and / or near the electrode sleeve (1).

11. The reference electrode as claimed in claim 10, characterized in that, When the seawater in the electrode sleeve (1) is electrolyzed intermittently, the effective chlorine concentration in the seawater in the electrode sleeve (1) is controlled to be between 0.5 and 1.5 ppm during each electrolysis, and the interval between two electrolysis cycles does not exceed 72 hours.

12. The reference electrode as claimed in claim 1, characterized in that, The electrode core (2) is a silver / silver chloride electrode or a silver / silver halide electrode. The reference electrode can also be regenerated in situ. When the reference electrode is regenerated in situ, the electrode cable (6) and the cathode cable (34) are respectively connected to the positive and negative poles of the DC power supply (7) to apply a reverse polarization current to the electrode core (2) so that the elemental silver on the electrode core (2) is converted into silver chloride.

13. The reference electrode as claimed in claim 12, characterized in that, The in-situ electrolytic regeneration method for the reference electrode includes the following steps: Connect the electrode cable (6) to the positive terminal of the DC power supply (7) and connect the cathode cable (34) to the negative terminal of the DC power supply (7); apply a reverse polarization current to the electrode core (2) through the DC power supply (7) so that the elemental silver on the electrode core (2) is converted into silver chloride.

14. The reference electrode as claimed in claim 13, characterized in that, When a reverse polarization current is applied, the current density is controlled to be between 3 and 30 mA / cm². 2 The polarization time is between 1 and 10 hours.

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