Ultralow-permeability anti-freezing gel copper sulfate reference electrode

Abstract

The invention discloses an ultra-low permeability type anti-freezing gel copper sulfate reference electrode which comprises an insulating cylinder, one end of the insulating cylinder is connected with an insulating cylinder cover, a through hole is formed in the insulating cylinder cover, the other end of the insulating cylinder is connected with one end of a micro-permeability ceramic cylinder, and a first insulating layer is arranged at the other end of the micro-permeability ceramic cylinder in a sealed mode; a reference electrode inner cavity is defined by the insulating cylinder cover, the insulating cylinder, the micro-infiltration ceramic cylinder and the first insulating layer jointly, a copper rod is arranged in the inner cavity, one end of the copper rod is located in the through hole and connected with a wire extending to the outer side of the insulating cylinder cover, and the joint of the wire and the copper rod is located in the through hole and provided with a second insulating layer; the second insulating layer is hermetically arranged in the through hole, and the inner cavity of the reference electrode on the outer side of the copper rod is filled with saturated copper sulfate gel. The invention aims to provide the ultralow-permeability anti-freezing gel copper sulfate reference electrode which has the advantages of long service life, low temperature resistance, ultralow permeability, simple structure, small volume, low pollution to soil environment and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of cathodic protection, and particularly to a long-lasting buried copper sulfate reference electrode. Background Art

[0002] Copper sulfate reference electrodes are commonly used to measure the natural potential and cathodic protection potential of buried metal pipelines, measure stray currents in the soil, and can also be used to measure the potential of cable metal sheaths and steel bars in concrete, etc.

[0003] Most of the existing copper sulfate reference electrodes in China adopt the form of saturated copper sulfate solution, with characteristics such as high loss rate and short lifespan. Even the existing gel-type copper sulfate reference electrodes mostly use gelling agents or low-temperature resistant agents such as carbomer and ethylene glycol, and still have problems such as short lifespan and the penetration of the medium being toxic and polluting the soil. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide an ultra-low permeability anti-freeze gel copper sulfate reference electrode, which has a long lifespan, low-temperature resistance, and ultra-low permeability performance, and also has the advantages of simple structure, small volume, and low environmental pollution to the soil.

[0005] The ultra-low permeability anti-freeze gel copper sulfate reference electrode of the present invention includes an insulating cylinder. One end of the insulating cylinder is hermetically connected to an insulating cylinder cover, and a through hole is provided on the insulating cylinder cover. The other end of the insulating cylinder is hermetically connected to one end of a micro-permeable ceramic cylinder. The other end of the micro-permeable ceramic cylinder is hermetically provided with a first insulating layer. The insulating cylinder cover, the insulating cylinder, the micro-permeable ceramic cylinder, and the first insulating layer together enclose a reference electrode inner cavity. A copper rod is provided in the reference electrode inner cavity. One end of the copper rod is located in the through hole. One end of the copper rod is connected to a wire extending outside the insulating cylinder cover. The connection between the wire and the copper rod is located in the through hole. A second insulating layer is provided at the connection between the wire and the copper rod, and the second insulating layer is hermetically provided in the through hole. The reference electrode inner cavity outside the copper rod is filled with saturated copper sulfate gel.

[0006] In the ultra-low permeability anti-freeze gel copper sulfate reference electrode of the present invention, a cylindrical flange is fixedly provided on the side of the insulating cylinder cover connected to the insulating cylinder. The cylindrical flange is inserted into the barrel mouth at one end of the insulating cylinder, and the insulating cylinder cover and the insulating cylinder are hermetically bonded by low-temperature glue.

[0007] In the ultra-low permeability anti-freeze gel copper sulfate reference electrode of the present invention, one end of the micro-permeable ceramic cylinder is inserted into the barrel mouth at the other end of the insulating cylinder, and the micro-permeable ceramic cylinder and the insulating cylinder are hermetically bonded by low-temperature glue.

[0008] The invention discloses an ultra-low permeability antifreeze gel copper sulfate reference electrode, wherein the first insulating layer comprises a polyvinyl chloride sheet and an epoxy adhesive layer bonded to each other, and the epoxy adhesive layer is arranged closer to the tube opening at the other end of the micro-permeability ceramic tube than the polyvinyl chloride sheet.

[0009] The invention discloses an ultra-low permeability antifreeze gel copper sulfate reference electrode, wherein the micro-permeable ceramic is an aluminum oxide or zirconium oxide microporous ceramic with a pore size of 1-5 μm and a porosity of 10%.

[0010] The invention discloses an ultra-low permeability antifreeze gel copper sulfate reference electrode, wherein the insulating tube, the insulating tube cover and the cylindrical flange are all made of ABS plastic, the second insulating layer is made of polyurethane glue, and the wire is made of copper.

[0011] The ultra-low permeability antifreeze gel copper sulfate reference electrode of the present invention, wherein the end surface of the other end of the micro-permeability ceramic tube is sealed by an insulating material.

[0012] The invention discloses an ultra-low permeability antifreeze gel copper sulfate reference electrode, wherein the saturated copper sulfate gel comprises the following components: 250-300 g / L of copper sulfate pentahydrate powder, 10-12 g / L of T2 copper powder, 0.5-1 g / L of polyacrylamide polymer, 500-800 g / L of glycerol and 450-500 g / L of deionized water.

[0013] The invention discloses an ultra-low permeability antifreeze gel copper sulfate reference electrode, wherein the saturated copper sulfate gel is prepared by the following method: firstly, 500-800 parts by weight of glycerol is added to 450-500 parts by weight of deionized water, and stirred at room temperature to obtain a low-temperature solvent; then, 250-300 parts by weight of copper sulfate pentahydrate powder and 10-12 parts by weight of T2 copper powder are added to the low-temperature solvent, and then, the mixture is stirred sufficiently to make the copper sulfate reach a saturated state to obtain a saturated copper sulfate solution; and finally, 0.5-1 parts by weight of polyacrylamide polymer is added to the saturated copper sulfate solution, and stirred at room temperature to obtain a saturated copper sulfate gel.

[0014] The difference between the ultra-low permeability anti-freezing gel copper sulfate reference electrode of the present invention and the prior art lies in that the insulating cylinder cover, insulating cylinder, micro-permeable ceramic and the first insulating layer in the ultra-low permeability anti-freezing gel copper sulfate reference electrode of the present invention jointly enclose the inner cavity of the reference electrode. A copper rod is arranged in the inner cavity, and one end of the copper rod is located in the through hole of the insulating cylinder cover. One end of the copper rod is connected to a wire, and a second insulating layer is arranged in the through hole. The second insulating layer can both insulate and seal the connection of the copper rod and the wire, and can also insulate and seal the inner cavity of the reference electrode. A saturated copper sulfate gel is filled in the inner cavity of the reference electrode outside the copper rod. The micro-permeable ceramic cylinder constitutes an ion channel to ensure the transmission of the electrical channel. At the same time, the micro-permeable ceramic cylinder has a smaller pore diameter, which can prevent the ionic copper sulfate in the gel from flowing into the soil to the greatest extent. In addition, the saturated copper sulfate gel has the characteristics of low temperature resistance and difficult loss of ionic copper sulfate. It can be seen that the present invention has a long service life, low temperature resistance and ultra-low permeability performance, and has the advantages of simple structure, small volume and low environmental pollution to the soil.

[0015] The present invention will be further described below with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 is the front view of the ultra-low permeability anti-freezing gel copper sulfate reference electrode of the present invention;

[0017] Figure 2 is the top view of the ultra-low permeability anti-freezing gel copper sulfate reference electrode of the present invention;

[0018] Figure 3 is the bottom view of the ultra-low permeability anti-freezing gel copper sulfate reference electrode of the present invention;

[0019] Figure 4 is the front cross-sectional view of the ultra-low permeability anti-freezing gel copper sulfate reference electrode of the present invention.

[0020] In the figure: 1. Insulating cylinder; 2. Insulating cylinder cover; 3. Tubular flange; 4. Micro-permeable ceramic cylinder; 5. Saturated copper sulfate gel; 6. Copper rod; 7. Wire; 8. Second insulating layer; 9. Polyvinyl chloride sheet; 10. Epoxy adhesive layer; 11. First insulating layer. DETAILED DESCRIPTION OF THE INVENTION

[0021] As Figure 1 shown and in combination with Figures 2-4As shown in the figure, the ultra-low permeability anti-freezing gel copper sulfate reference electrode of the present invention includes an insulating cylinder 1. One end of the insulating cylinder 1 (the upper end shown in the figure) is hermetically connected to an insulating cylinder cover 2 by a low-temperature glue. A through hole is provided on the insulating cylinder cover 2. The other end of the insulating cylinder 1 (the lower end shown in the figure) is hermetically connected to one end of a micro-permeable ceramic cylinder 4 (the upper end shown in the figure) by a low-temperature glue. The other end of the micro-permeable ceramic cylinder 4 (the lower end shown in the figure) is hermetically provided with a first insulating layer 11. The insulating cylinder cover 2, the insulating cylinder 1, the micro-permeable ceramic cylinder 4 and the first insulating layer 11 together enclose a reference electrode inner cavity. A copper rod 6 is provided in the reference electrode inner cavity. One end of the copper rod 6 (the upper end shown in the figure) is located in the through hole. One end of the copper rod 6 is connected to a wire 7 extending outside the insulating cylinder cover 2. The connection part of the wire 7 and the copper rod 6 is located in the through hole. A second insulating layer 8 is provided at the connection part of the wire 7 and the copper rod 6. The second insulating layer 8 is hermetically arranged in the through hole. A saturated copper sulfate gel 5 is filled in the reference electrode inner cavity outside the copper rod 6.

[0022] As Figure 4 shown in the figure, the whole of the copper rod 6 is located in the reference electrode inner cavity. The copper rod 6 is arranged vertically, and the upper end of the copper rod 6 is arranged in the through hole to be connected to the wire 7. The second insulating layer 8 has two functions: one is to insulate and seal the connection part of the copper rod 6 and the wire 7, and the other is to insulate and seal the through hole, that is, to insulate and seal the inner cavity of the reference electrode.

[0023] As Figures 1-4 shown in the figure, the insulating cylinder cover 2, the insulating cylinder 1, the micro-permeable ceramic and the first insulating layer 11 in the ultra-low permeability anti-freezing gel copper sulfate reference electrode of the present invention together enclose the inner cavity of the reference electrode. A copper rod 6 is provided in the inner cavity. One end of the copper rod 6 (the upper end shown in the figure) is located in the through hole of the insulating cylinder cover 2. One end of the copper rod 6 is connected to a copper wire 7. And a second insulating layer 8 is provided in the through hole. The second insulating layer 8 can both insulate and seal the connection part of the copper rod 6 and the copper wire 7 and insulate and seal the inner cavity of the reference electrode. A saturated copper sulfate gel 5 is filled in the reference electrode inner cavity outside the copper rod 6. The micro-permeable ceramic cylinder 4 constitutes an ion channel to ensure the transmission of the electrical channel. At the same time, the micro-permeable ceramic cylinder 4 has a smaller pore diameter, which can prevent the ionic copper sulfate in the gel from flowing into the soil to the greatest extent. In addition, the saturated copper sulfate gel 5 has the characteristics of low temperature resistance and difficult loss of ionic copper sulfate. It can be seen that the present invention has a long service life, low temperature resistance and ultra-low permeability performance, and has the advantages of simple structure, small volume and low environmental pollution to the soil.

[0024] As Figure 4As shown in the figure, the ultra-low permeability anti-freezing gel copper sulfate reference electrode of the present invention, wherein a cylindrical flange 3 is fixedly provided on one side (the lower side shown in the figure) of the insulating cylinder cover 2 connected to the insulating cylinder 1. The cylindrical flange 3 and the insulating cylinder cover 2 are of an integrally formed structure. The cylindrical flange 3 is inserted into the cylinder mouth at one end (the upper end shown in the figure) of the insulating cylinder 1. The insulating cylinder cover 2 and the insulating cylinder 1 are hermetically bonded by a low-temperature glue. The cylindrical flange 3 abuts against the inner cylinder wall of the insulating cylinder 1. The lower side surface of the insulating cylinder cover 2 outside the cylindrical flange 3 abuts against the upper cylinder mouth end surface of the insulating cylinder 1. And the parts where the cylindrical flange 3 abuts against the insulating cylinder 1 and the parts where the insulating cylinder cover 2 abuts against the insulating cylinder 1 are hermetically bonded by a low-temperature glue.

[0025] As Figure 4 shown in the figure, the ultra-low permeability anti-freezing gel copper sulfate reference electrode of the present invention, wherein one end (the upper end shown in the figure) of the micro-permeable ceramic cylinder 4 is inserted into the cylinder mouth at the other end (the lower end shown in the figure) of the insulating cylinder 1. The micro-permeable ceramic cylinder 4 and the insulating cylinder 1 are hermetically bonded by a low-temperature glue. The outer cylinder wall at the upper end of the micro-permeable ceramic cylinder 4 abuts against the inner cylinder wall at the lower end of the insulating cylinder 1, and the two are hermetically bonded by a low-temperature glue.

[0026] As Figure 4 shown in the figure, the ultra-low permeability anti-freezing gel copper sulfate reference electrode of the present invention, wherein the first insulating layer 11 includes a polyvinyl chloride sheet 9 and an epoxy glue layer 10 that are adhesively bonded to each other. The epoxy glue layer 10 is arranged closer to the cylinder mouth at the other end (the lower end shown in the figure) of the micro-permeable ceramic cylinder 4 than the polyvinyl chloride sheet 9. That is to say, the first insulating layer 11 belongs to a double-layer insulation seal. After the inner cavity of the reference electrode is filled with saturated copper sulfate gel 5, the polyvinyl chloride sheet 9 is first sealed in the lower cylinder mouth of the micro-permeable ceramic cylinder 4, and then the epoxy glue layer 10 is injected outside the polyvinyl chloride sheet 9. The epoxy glue layer 10 is adhesively bonded to the polyvinyl chloride sheet 9 and seals the lower cylinder mouth of the micro-permeable ceramic cylinder 4. The epoxy glue has good low-temperature resistance.

[0027] For the ultra-low permeability anti-freezing gel copper sulfate reference electrode of the present invention, the micro-permeable ceramic is alumina or zirconia microporous ceramic with a pore diameter of 1-5 μm and a porosity of 10%.

[0028] For the ultra-low permeability anti-freezing gel copper sulfate reference electrode of the present invention, the materials of the insulating cylinder 1, the insulating cylinder cover 2 and the cylindrical flange 3 are all ABS plastics. The material of the second insulating layer 8 is polyurethane glue. The material of the wire 7 is copper. ABS plastic is a low-temperature resistant insulating material.

[0029] As Figure 4As shown in the ultra-low permeability antifreeze gel copper sulfate reference electrode of the present invention, the end surface of the other end (the lower end shown in the figure) of the micro-permeable ceramic tube 4 is sealed by an insulating material. The insulating material is a low-temperature insulating glue, which is applied to the lower end surface of the micro-permeable ceramic tube 4 to prevent ionic copper sulfate from seeping out from the lower end surface of the micro-permeable ceramic tube 4, because the reference electrode is in accordance with Figure 4 It is buried in the soil in the orientation shown, that is, after burial, the insulating tube 1, the micro-infiltration ceramic tube 4 and the copper rod 6 are arranged vertically, so that the pressure of the saturated copper sulfate gel 5 borne by the lower end face of the micro-infiltration ceramic tube 4 is the largest, and relative to the side of the micro-infiltration ceramic tube 4, the ionic copper sulfate is also more likely to seep into the soil from the lower end face of the micro-infiltration ceramic tube 4, and the lower end face of the micro-infiltration ceramic tube 4 is sealed by low-temperature insulating glue, which can further prevent the ionic copper sulfate from penetrating through the micro-infiltration ceramic tube 4 and seeping into the soil, thereby enhancing the ultra-low permeability performance of the reference electrode.

[0030] The ultra-low osmotic antifreeze gel copper sulfate reference electrode of the present invention, wherein the saturated copper sulfate gel 5 comprises the following components: 250-300 g / L of copper sulfate pentahydrate powder, 10-12 g / L of T2 copper powder, 0.5-1 g / L of polyacrylamide polymer, 500-800 g / L of glycerol and 450-500 g / L of deionized water.

[0031] The ultra-low permeability antifreeze gel copper sulfate reference electrode of the present invention, wherein the saturated copper sulfate gel 5 is prepared by the following method: first, 500-800 parts by weight of glycerol is added to 450-500 parts by weight of deionized water, and stirred at room temperature (20°C) to obtain a low-temperature solvent, then 250-300 parts by weight of copper sulfate pentahydrate powder and 10-12 parts by weight of T2 copper powder are added to the low-temperature solvent, and then the copper sulfate is fully stirred to reach a saturated state to obtain a saturated copper sulfate solution, and finally 0.5-1 parts by weight of polyacrylamide polymer is added to the saturated copper sulfate solution, and stirred at room temperature (20°C) to obtain the saturated copper sulfate gel 5.

[0032] When the saturated copper sulfate gel 5 is obtained by stirring at room temperature 20°C, it is necessary to stir for 50 minutes, and high temperature heating > 40°C is strictly prohibited during this process.

[0033] Research on the permeability of micro-permeable ceramics: In the experiment, the wall thickness of the micro-permeable ceramic cylinder 4 was 5 mm. According to Darcy's law, the seepage flow rate of the micro-permeable ceramic cylinder 4, that is, the loss rate of the gel, can be calculated. Darcy's law is Q = K×A×(h2 - h1) / L, where Q is the seepage flow rate, L is the seepage length, A is the cross-sectional area perpendicular to the water flow direction, h2 - h1 is the head difference between the upstream and downstream, and K is the permeability coefficient. Although the lower end face of the micro-permeable ceramic cylinder 4 is sealed with low-temperature insulating glue during actual use, it is still calculated as if the lower end face of the micro-permeable ceramic cylinder 4 is not sealed during the experiment calculation. The gel loss rate obtained through laboratory simulation calculation is 2 - 3%, which is basically consistent with the on-site burial and excavation test data for 1 year.

[0034] Research on the potential stability of saturated copper sulfate gel 5 in a low-temperature environment: The prepared saturated copper sulfate gel 5 was placed in a glass test tube and then placed in a -20°C test chamber. The electrode potential of the gel reference electrode relative to the saturated calomel electrode was measured and recorded over time using a multimeter. Test results: Within 72 hours, the potential fluctuation between the two did not exceed 4 mV, meeting the industry standard requirements for the stability of the reference potential (±5 mV). Thus, it can be seen that the saturated copper sulfate gel 5 in the present invention has good anti-freezing properties, that is, low-temperature resistance.

[0035] The copper rod 6 and the copper wire 7 are electrically connected through soldering or mechanical connection, and the electrical connection between the two is insulated and sealed by a second insulating layer 8 made of polyurethane glue. Polyurethane glue has good low-temperature resistance.

[0036] The present invention can be applied to high-cold regions such as Northeast and Northwest China, and can measure the potential of buried metal pipelines long-term, stably, reliably, and accurately, with the advantages of long life and low-temperature resistance. In addition, the present invention also has the following advantages:

[0037] (1) Low-temperature resistance: Existing copper sulfate reference electrodes are not suitable for use in low-temperature environments (below 0°C), while the insulating cylinder cover 2, the cylindrical flange 3 thereon, the insulating cylinder 1, the first insulating layer 11, and the second insulating layer 8 in the present invention are all made of low-temperature resistant materials, and both the micro-permeable ceramic cylinder 4 and the saturated copper sulfate gel 5 have low-temperature resistance. In addition, when the insulating cylinder 1 is connected to the insulating cylinder cover 2 and the micro-permeable ceramic cylinder 4 respectively, low-temperature glue is used for bonding. Therefore, the present invention can be used in low-temperature environments (such as -20°C) with good anti-freezing properties.

[0038] (2) Soaking problem: Existing copper sulfate reference electrodes need to be soaked in water before use because copper sulfate is a solid powder under normal conditions, and the existing copper sulfate reference electrodes contain copper sulfate in its normal state, so it needs to be soaked in water to become an ionic state. However, in the present invention, it is a saturated copper sulfate gel 5, and the copper sulfate is already in an ionic state, so there is no need to soak it in water.

[0039] (3) Leakage (penetration) problem: In the existing copper sulfate reference electrode, the penetration rate at the micro-permeable end is too high, resulting in copper sulfate leakage and pollution to the soil environment. Compared with the existing ones, the present invention has ultra-low permeability for two reasons: First, the gel-state ionic copper sulfate is not easily lost; second, due to the structure of the micro-permeable ceramic with small pore size, the ionic copper sulfate is not easily permeated.

[0040] (4) Service life problem: For long-distance pipelines, the existing buried copper sulfate reference electrodes have a short service life. Generally, the service life is 5 - 10 years; under the condition of smaller external dimensions and convenient replacement, the service life of the present invention reaches more than 25 years.

[0041] It should be noted that the orientation or positional relationship indicated by the terms "center", "upper", "lower", "front", "rear", "left", "right", "middle", etc. is based on the orientation or positional relationship shown in the drawings. It is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as a limitation to the present invention.

[0042] In the description of the present invention, it should be noted that unless otherwise clearly specified and defined, the terms "connected" and "connected" should be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be directly connected or indirectly connected through an intermediate medium. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0043] The embodiments described above are only used to describe the preferred embodiments of the present invention, and do not limit the scope of the present invention. Without departing from the design spirit of the present invention, various deformations and improvements made by those of ordinary skill in the art to the technical solutions of the present invention shall fall within the protection scope determined by the claims of the present invention.

Claims

1. An ultra-low permeability antifreeze gel copper sulfate reference electrode, characterized in that: It includes an insulating cylinder, one end of the insulating cylinder is sealed with an insulating cylinder cover, a through hole is opened on the insulating cylinder cover, the other end of the insulating cylinder is sealed with one end of a micro-infiltration ceramic cylinder, the other end of the micro-infiltration ceramic cylinder is sealed with a first insulating layer, the insulating cylinder cover, the insulating cylinder, the micro-infiltration ceramic cylinder and the first insulating layer together form a reference electrode cavity, a copper rod is arranged in the reference electrode cavity, one end of the copper rod is located in the through hole, one end of the copper rod is connected to a wire extending to the outside of the insulating cylinder cover, the connection between the wire and the copper rod is located in the through hole, the connection between the wire and the copper rod is provided with a second insulating layer, the second insulating layer is sealed in the through hole, and the reference electrode cavity outside the copper rod is filled with saturated copper sulfate gel.

2. The ultra-low permeability antifreeze gel copper sulfate reference electrode according to claim 1, characterized in that: A cylindrical flange is fixedly provided on one side of the insulating cylinder cover connected to the insulating cylinder. The cylindrical flange is inserted into a cylinder opening at one end of the insulating cylinder. The insulating cylinder cover and the insulating cylinder are sealed and bonded by low-temperature glue.

3. The ultra-low permeability antifreeze gel copper sulfate reference electrode according to claim 2, characterized in that: One end of the micro-infiltration ceramic tube is inserted into the tube opening of the other end of the insulating tube, and the micro-infiltration ceramic tube and the insulating tube are sealed and bonded by low-temperature glue.

4. The ultra-low osmotic antifreeze gel copper sulfate reference electrode according to claim 3, characterized in that: The first insulating layer includes a polyvinyl chloride sheet and an epoxy adhesive layer bonded to each other, and the epoxy adhesive layer is arranged closer to the tube opening at the other end of the micro-infiltration ceramic tube than the polyvinyl chloride sheet.

5. The ultra-low osmotic antifreeze gel copper sulfate reference electrode according to claim 4, characterized in that: The microporous ceramic is an aluminum oxide or zirconium oxide microporous ceramic with a pore size of 1-5 μm and a porosity of 10%.

6. The ultra-low osmotic antifreeze gel copper sulfate reference electrode according to claim 5, characterized in that: The insulating tube, the insulating tube cover and the cylindrical flange are all made of ABS plastic, the second insulating layer is made of polyurethane glue, and the wire is made of copper.

7. The ultra-low osmotic antifreeze gel copper sulfate reference electrode according to claim 6, characterized in that: The end surface of the other end of the micro-permeable ceramic tube is sealed by an insulating material.

8. The ultra-low osmotic antifreeze gel copper sulfate reference electrode according to any one of claims 1 to 7, characterized in that: The saturated copper sulfate gel comprises the following components: 250-300 g / L of copper sulfate pentahydrate powder, 10-12 g / L of T2 copper powder, 0.5-1 g / L of polyacrylamide polymer, 500-800 g / L of glycerol and 450-500 g / L of deionized water.

9. The ultra-low osmotic antifreeze gel copper sulfate reference electrode according to claim 8, characterized in that: The saturated copper sulfate gel is prepared by the following method: first, 500-800 parts by weight of glycerol is added to 450-500 parts by weight of deionized water, and stirred at room temperature to obtain a low-temperature solvent; then, 250-300 parts by weight of copper sulfate pentahydrate powder and 10-12 parts by weight of T2 copper powder are added to the low-temperature solvent, and then, the mixture is stirred sufficiently to saturate the copper sulfate to obtain a saturated copper sulfate solution; finally, 0.5-1 parts by weight of polyacrylamide polymer is added to the saturated copper sulfate solution, and stirred at room temperature to obtain a saturated copper sulfate gel.

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