CN216247771U

CN216247771U - Shell, novel reference electrode and novel external power supply type anode system for electrochemical field

Info

Publication number: CN216247771U
Application number: CN202122534936.0U
Authority: CN
Inventors: 张兴莉
Original assignee: Individual
Current assignee: Li Tao
Priority date: 2021-10-20
Filing date: 2021-10-20
Publication date: 2022-04-08
Anticipated expiration: 2031-10-20

Abstract

The utility model relates to the field of electrochemistry, and particularly discloses a shell, a novel reference electrode and a novel external power supply type anode system which are used in the field of electrochemistry. The first through hole is filled with a reverse osmosis layer and an electromagnetic-proof layer; the surface of the shell is provided with a metal layer. The novel reference electrode adopting the shell is arranged in the shell accommodating cavity, and an electrode and an electrolyte solution of the novel reference electrode are arranged in the shell accommodating cavity; one end of the electrode is immersed in the electrolyte solution, and the other end of the electrode is led out from the shell by a lead; the service life of the novel reference electrode is greatly prolonged, and the potential of the internal electrode can be isolated from the influence of electromagnetic interference outside the shell. The novel external power supply type anode system adopts the shell, and a polarized electrode and an anode of the anode system are arranged in the shell accommodating cavity; one end of each electrode is immersed in the electrolyte solution, the anode is connected with the anode of the potentiostat, and the polarized electrodes are connected with the cathode and the cathode of the potentiostat; the novel anode system can avoid anode corrosion to other metal bodies around.

Description

Shell, novel reference electrode and novel external power supply type anode system for electrochemical field

Technical Field

The utility model relates to the field of electrochemistry, in particular to a shell, a novel reference electrode and a novel externally-powered anode system used in the field of electrochemistry.

Background

The reference electrode is an electrode that is used as a reference for comparison when measuring various electrode potentials. The electrode potential of the electrode to be measured can be calculated by constituting a galvanic cell by the electrode to be measured and a reference electrode of which the electrode potential value is precisely known, and measuring the electromotive force value of the galvanic cell. The reference electrode is a device commonly used in the electrochemical technology field, and the variety is relatively wide, and in this case, the reference electrode is illustrated by comparing the commonly used reference electrode of silver-silver chloride and copper-copper sulfate. Silver-silver chloride reference electrodes are used more often in fresh water and seawater environments, and copper-copper sulfate reference electrodes are used more often in soil. Taking a silver-silver chloride reference electrode as an example, when the reference electrode is soaked in a fresh water or seawater environment, appropriate water and water quantity are injected through a water injection port in advance, the water injection port is sealed by a plug, a water body is mixed with KCL crystals stored in the inner space of the electrode to form a KCL saturated solution, and the silver-silver chloride electrode is soaked in the KCL saturated solution to form a stable natural corrosion potential on the silver-silver chloride electrode; the electrode lead-out wire is electrically connected with a metal object to be detected in an electrolyte environment through a voltmeter, and the potential difference between the metal object to be detected and the reference electrode is obtained. Known from the working principle of the reference electrode, a certain amount of undissolved KCL crystals always exist in the internal space of the electrode, so that the silver-silver chloride electrode is always soaked in a KCL saturated solution, and the potential of the reference electrode is always in a stable state. The working principle of the copper-copper sulfate reference electrode is similar, the KCL crystal is replaced by the copper sulfate crystal, and the internal electrode is replaced by pure copper.

Micron-sized porous ceramic materials are embedded in through holes at the bottom of the shell of the reference electrode and are used as ion electric channels of electrolyte inside and outside the reference electrode. Although the inner salt solution and the undissolved salt solid are isolated in the inner cavity of the shell by the porous material at the bottom, the pore diameter of the porous material reaches the micron level, and the porous material has good permeation effect. The internal salt solution and the salt solid can gradually leak to the outside of the reference electrode through the porous material to form a good and smooth ion channel, and the porous material at the moment becomes a salt bridge. However, if the leakage amount reaches a certain degree, the salt solution in the reference electrode is no longer a saturated solution, and the reference electrode cannot guarantee the accuracy of the measured data. It is therefore necessary to check the reference electrode, which is in operation in the field, after a certain period of use, to see if any salt solids remain in the reference electrode. However, for the reference electrode which is thrown into the marine environment or buried deeply in the ground, the inspection and maintenance work obviously becomes very difficult, and usually, the theoretical error of the reference electrode can only be passively corrected until the reference electrode fails.

In addition, when the reference electrode works in an electrolyte environment, direct current or alternating current stray current interference exists or a strong alternating current circuit exists nearby, the internal electrode of the reference electrode is greatly interfered, the potential can greatly shift, and the measured data loses significance at the moment.

The noun explains: a flat ceramic reverse osmosis membrane. The traditional reverse osmosis membrane is generally made of high molecular materials, is an organic membrane, does not have acid, alkali and salt which can cause chemical reaction in use, and has limited use scenes. The flat ceramic reverse osmosis membrane is an inorganic membrane, is a solid-gas separation material which is prepared by raw materials such as alumina, zirconia, silica and the like through a series of special processes and has a porous structure, has the advantages of good chemical stability, acid and alkali resistance, high temperature resistance, strong antimicrobial capability, high separation precision, large mechanical strength, easy regeneration, long service life and the like which are incomparable with organic membranes, and can further apply a reference electrode to harsh environments such as sewage treatment, electroplating and the like. The filtration precision of the membrane can cover microfiltration, ultrafiltration and even nanofiltration, the filtration pore size can be adjusted from 10 nanometers to 10 micrometers according to different filterable media, the pore size distribution is narrow, and the surface of the membrane can be modified by different materials, so that the filtration precision and the filtration flux are increased. The structure of the flat ceramic reverse osmosis membrane comprises a fine filtration membrane with the lowest pore diameter reaching the nanometer level and the average pore diameter, and a substrate layer with larger pore diameter and mainly used for increasing the strength of the fine filtration membrane and prolonging the service life of the fine filtration membrane, wherein the substrate layer is also made of porous ceramic materials.

The noun explains: a faraday cage. A Faraday Cage (Cage) is a Cage formed of metal or good conductor named electromagnetic founder, uk physicist michael-Faraday last name, a device used to demonstrate principles of equipotential, electrostatic shielding and high voltage live operation. The faraday cage firstly has an electrostatic shielding function. The electrostatic shield is divided into an outer shield and a full shield. The external shield means that the external electric field cannot have any influence on the internal space. If there is a charged body in the cavity conductor, during the static balance, if the outer shell is not grounded, the outer surface will generate the same amount and same number of induced charges as the internal charged body, at this moment, the cavity conductor can only shield the external electric field, but can not shield the influence of the internal charged body to the outside, so called as external shield. However, if the housing is grounded, even if a charged body exists inside, the algebraic sum of the charges induced on the inner surface and the charges charged on the charged body is zero, and the induced charges generated on the outer surface flow into the ground through the ground wire. The external environment can not influence the inside of the shell, and the influence of the internal charged body on the external environment is eliminated, so the shielding is called full shielding.

The faraday cage must also be noted in practical applications: (1) similar electrostatic shielding can be achieved by replacing the metal housing with a metal screen, but the shielding effect with a metal screen is not completely complete. (2) In electrostatic equilibrium, no charge flows in the ground line, but if the charge inside the shielded enclosure changes over time, or the charge near the charged body outside the enclosure changes over time, there will be a current in the ground line. The shield may also present residual charges, in which case the shielding will again be incomplete and incomplete.

The noun explains: an external power supply type anode. The anode of the external power supply forms a driving force for protective current and comes from the output of the potentiostat, when in use, the anode is connected to the anode of the potentiostat, the cathode of the potentiostat is connected to the protected cathode, and the cathode obtains the protective current from the anode through the working electrolyte solution. The advantages are that: where higher currents are required, particularly for protection of bare or poorly coated structures; all conductive electrolyte solutions; protection for large heat exchangers, oil heating processors and other containers in the water tank; the inner wall of the water storage tank. The disadvantages are as follows: the protective current emitted from the anode also becomes a source of interference of direct current stray current of other nearby metal bodies, and the metal bodies are rapidly corroded.

SUMMERY OF THE UTILITY MODEL

The utility model aims to overcome at least one defect of the prior art, and provides a shell used in the electrochemical field and a novel reference electrode formed based on the shell, which are used for solving the problems of the prior reference electrode that the internal electrolyte solution leaks too fast to cause short service life, thereby achieving the effect of prolonging the service life of the reference electrode; and the problem that the measured data loses significance due to the fact that the potential of the reference electrode changes when alternating current and direct current stray current interference exists in the electrolyte environment where the reference electrode works or strong alternating current electromagnetic interference exists nearby the reference electrode is solved. And the novel external power supply type anode system formed based on the shell solves the problem that the conventional external power supply type anode system can quickly corrode other nearby metal bodies.

The utility model provides a shell used in the field of electrochemistry. The first through hole is filled with a reverse osmosis layer and an electromagnetic-proof layer; the surface of the shell is covered with a metal layer.

The novel reference electrode adopts the shell and comprises a reference electrode and electrolyte solution which is attached to the reference electrode, and both the reference electrode and the electrolyte solution are arranged in the accommodating cavity of the shell; one end of the reference electrode is immersed in the electrolyte solution, and the other end of the reference electrode is led out of the shell by a lead.

The filling material in the first through hole of the shell is divided into two parts, namely a reverse osmosis layer and an electromagnetic-proof layer.

The reverse osmosis layer is made of the same material and structure as the flat ceramic reverse osmosis membrane, and the structure of the reverse osmosis layer comprises a fine filtration layer and a substrate layer. According to different actual tasks, the filtering pore diameters of the fine filtering layers can be selected from numerical values with different sizes and suitable for actual working requirements. Under the premise of ensuring that the internal electrolyte solution and the external electrolyte solution still can be in sufficient contact through a reverse osmosis layer, the salt bridge effect cannot be damaged and the current can smoothly pass through the reverse osmosis layer, the mutual permeation speed of the internal electrolyte solution and the external electrolyte solution of the reference electrode is controlled to be at a lower value as much as possible (for example, in a silver-silver chloride reference electrode, the recommended filtration pore diameter is 30-50 nanometers), so that the service life of the reference electrode can be greatly prolonged compared with the prior use of a micron-sized porous material, and the smooth completion of the measurement work of the reference electrode is also ensured. Meanwhile, large-diameter molecular colloids, microorganisms and organic matters in the external environment can be effectively isolated and permeate into the internal space of the reference electrode, so that the electrode and electrolyte solution in the reference electrode are polluted. The plate ceramic reverse osmosis membrane is used as a reverse osmosis layer, so that the reference electrode can be further applied to harsh environments such as sewage treatment, electroplating and the like.

The reverse osmosis layer may also be replaced with a solid electrolyte material or an organic reverse osmosis membrane. When a certain solid electrolyte or organic reverse osmosis membrane can be in the electrolyte environment used by the reference electrode and the electrolyte solution environment stored in the internal space of the reference electrode, enough chemical and mechanical stability can be kept, and enough electric conductivity can be ensured, namely the solid electrolyte or organic reverse osmosis membrane can be used as a reverse osmosis layer.

The type of electrode and electrolyte solution of the reference electrode is not limited in this embodiment, and in principle, the above-described housing can be used for the reference electrode using a porous material for the internal and external separation of the housing.

The electromagnetic shielding layer comprises a plurality of electromagnetic shielding layers and a plurality of insulating layers; several insulating layers are distributed between the two electromagnetic shielding layers. The preferred structure is composed of an insulating layer and two electromagnetic shielding layers; the insulating layer is positioned between the two electromagnetic shielding layers. The insulating layer is made of porous non-conductive material with micron-sized pore diameter. The electromagnetic shielding layer is formed by overlapping a plurality of layers of metal nets; the insulating layer ensures that the two electromagnetic shielding layers are not in electrical contact.

The electromagnetic shielding layer is at least two layers, and the structure can effectively isolate the mutual influence of alternating current/direct current interference in the environments of internal electrolyte solution and external electrolyte solution, thereby ensuring that the potential of the reference electrode is kept stable. The structure of the double-layer metal net can effectively solve the problem that the single-layer metal net is incomplete and incomplete in shielding electromagnetic interference. Further, if a higher level of shielding effect is to be achieved, the number of layers of the electromagnetic shielding layer and the insulating layer may be increased.

The aperture on the insulating layer material is the micron order, and the aperture on the electromagnetic shield layer material is the millimeter level, all is greater than the aperture of reverse osmosis layer far away, more can not cause the influence to the infiltration of molecule and ion, exchange, so can not influence the unobstructed of reference electrode measurement return circuit.

The surface of the shell is additionally provided with a fully-covered and tightly-embedded metal layer or is coated with a metal coating, and the metal layer prevents alternating electromagnetic interference emitted by a strong alternating current circuit near the reference electrode from entering the shell. The new metal layer or metal coating can be replaced by other good electric conductors.

Compared with the prior art, the utility model has the beneficial effects that:

the filling material filled in the first through hole is a combined structure of the reverse osmosis layer and the electromagnetic-proof layer, the reverse osmosis layer selects a proper membrane aperture, the mutual permeation speed of electrolyte solutions inside and outside the reference electrode can be delayed as much as possible on the premise that the measurement current can smoothly pass through, the permeation speed of the electrolyte solution inside the reference electrode and the permeation speed of the electrolyte solution outside the reference electrode into the external environment are greatly delayed, the permeation speed of the electrolyte solution outside the reference electrode into the internal environment of the reference electrode is also delayed, the pollution of the electrolyte solution inside the reference electrode by the electrolyte solution outside the reference electrode is also delayed, and the service life of the reference electrode can be greatly prolonged.

According to the scheme, the shielding layer is arranged in the first through hole filling material, and the metal layer or the metal coating (or other good electrical conductor layer) is added on the outer side of the shell, so that the influence of electromagnetic interference in an external electrolyte solution environment on the potential of the reference electrode is avoided, and the electrode potential is ensured to be stable when the reference electrode works.

The utility model further provides a novel external power supply type anode system formed based on the shell, and the novel external power supply type anode system is used for solving the problem that the conventional external power supply type anode system can quickly corrode other nearby metal bodies.

The novel external power supply type anode system adopts the shell, and a polarized electrode, an external power supply type anode and an attached electrolyte solution of the anode system are uniformly distributed in an accommodating cavity of the shell; one end of each electrode is immersed in the electrolyte solution, the other end of each electrode is led out from the shell by a lead, the anode of the external power supply is connected with the anode of the constant potential rectifier, and the polarized electrode and the protected cathode are connected with the cathode of the constant potential rectifier.

The shell structure in this scheme and the characteristics of its work in outside electrolyte have decided that the casing possesses the full shielding function simultaneously for be in the casing and hold the inside plus power formula positive pole in chamber, can't cause the corrosive effect to other metal bodies near.

Drawings

Fig. 1 is a structural view of embodiment 1 of the present invention.

Fig. 2 is a structural view of embodiment 2 of the present invention.

Description of reference numerals: the device comprises a shell 10, a sealing cover 11, a first through hole 12, a second through hole 13, a reverse osmosis layer 20, a substrate layer 21, a fine filter layer 22, an electromagnetic shielding layer 30, an electromagnetic shielding layer 31, an insulating layer 32, a metal layer 40, an electrode 51, an electrolyte solution 52, an electrolyte solid 53, a potentiostat 61, an external power supply type anode 62, a polarizing electrode 63 and a cathode 64.

Detailed Description

The drawings are only for purposes of illustration and are not to be construed as limiting the utility model. For a better understanding of the following embodiments, certain features of the drawings may be omitted, enlarged or reduced, and do not represent the size of an actual product; it will be understood by those skilled in the art that certain well-known structures in the drawings and descriptions thereof may be omitted.

Example 1

As shown in fig. 1, the present embodiment is a novel silver-silver chloride reference electrode, which comprises a housing 10, an electrode 51 and an electrolyte solution 52. The housing 10 has a receiving cavity therein, and the surface of the housing 10 is provided with a first through hole 12. The first through hole 12 is filled with a reverse osmosis layer 20 and an electromagnetic-proof layer 30; the surface of the housing 10 is covered with a metal layer 40. An electrode 51 and an electrolyte solution 52 are disposed in the housing chamber of the case 10; one end of the electrode 51 is immersed in the electrolyte solution 52, and the other end of the electrode 51 is led out of the case 10 by a lead wire.

The electrode 51 of this example is a silver-silver chloride reference electrode, the electrolyte solution 52 is a KCL solution, and the bottom of the electrolyte solution 52 has undissolved electrolyte solids 53(KCL crystals). The upper end of the housing 10 is provided with a sealing cover 11. The sealing cover 11 is provided with a second through hole 13 for water injection. The lower end of the housing 10 is provided with a first through-hole 12. The wires are led out from the sealing cover 11. Before use, the sealing cover 11 is opened, the appropriate amount of KCL crystals are filled in the reference electrode, the sealing cover 11 is sealed, and the appropriate amount of water is injected from the second through hole 13 and then sealed.

The filler of the first through hole 12 adopts a structure of an anti-permeation layer 20+ an anti-electromagnetic layer 30.

The reverse osmosis layer 20 is fabricated based on the technology of flat ceramic reverse osmosis membranes. The structure of the electrode comprises a fine filtering layer 22 and a substrate layer 21, and the pore diameter of a filtering hole of the fine filtering layer 22 is selected properly, so that the mutual permeation speed of electrolyte solutions inside and outside the reference electrode can be slowed down as much as possible on the premise that the electrolyte solution inside the reference electrode is fully contacted with the electrolyte solution in the external environment, the reverse osmosis layer 20 still can play a role of a salt bridge, and the measurement current can smoothly pass through, so that the electrolyte solution 52 inside the reference electrode permeates at a speed as slow as possible and is lost to the external environment, and the electrolyte solution in the external environment can not easily permeate into the reference electrode. The combined action greatly prolongs the service life of the reference electrode. Taking the silver-silver chloride reference electrode described in this example as an example, the filtration pore size is preferably 30 to 50 nm. In addition, the reverse osmosis layer 20 can further enable the reference electrode to be applied to environments with very harsh use conditions in sewage treatment, electroplating, electrolysis industries and the like.

In other embodiments, the reverse osmosis layer 20 may also be made of a solid electrolyte material or an organic reverse osmosis membrane, which would more perfectly account for the loss of the electrolyte solution 52. However, the solid electrolyte or organic reverse osmosis membrane is required to be capable of maintaining sufficient chemical and mechanical stability in the internal and external electrolyte environments of the reference electrode, and also to ensure sufficient electrical conductivity, otherwise, the solid electrolyte or organic reverse osmosis membrane cannot be used.

The first through hole 12 is further filled with an electromagnetic shielding layer 30 for shielding the influence of alternating/direct current stray currents in the reference electrode and in the external electrolyte environment. The preferred structure of the electromagnetic shielding layer 30 is composed of an insulating layer 32 and two electromagnetic shielding layers 31; the insulating layer 32 is located between the two electromagnetic shielding layers 31 and ensures that there is no electrical contact between the two electromagnetic shielding layers 31. The insulating layer 32 is made of a non-conductive porous material. The electromagnetic shielding layer 31 is formed by overlapping a plurality of layers of metal nets, and the mesh specification is required to be 220 meshes or even more than 400 meshes.

Further, the aperture on its material of insulating layer 32 is the micron order, and the aperture on its material of electromagnetic shield layer 31 is the millimeter level, all is greater than the aperture of reverse osmosis layer 20 far away, more can not cause the influence to the infiltration of molecule and ion, exchange, also can not influence measuring current's the smooth degree of passing through yet.

Furthermore, a faraday cage structure with a double-layer metal mesh structure is formed by combining one insulating layer 32 and two electromagnetic shielding layers 31, so that the problem that the electromagnetic interference shielding effect of a single-layer metal mesh is incomplete can be solved greatly. Further, if a higher level of shielding effect is to be achieved, the number of layers of the electromagnetic shielding layer 31 can be increased from two layers to three layers, or even more, but the insulating layer 32 must be used between each two electromagnetic shielding layers 31 for electrical insulation.

The housing 10 is formed by adding a metal layer 40 on the surface of a conventional reference electrode housing. The added metal layer 40 is a metal coating or a metal shell composed of metal sheets. The metal layer 40 provides the housing 10 with resistance to the ingress of strong alternating electromagnetic interference, which may be present in the ambient environment, into the interior of the housing 10. The metal layer 40 cooperates with the anti-electromagnetic layer 30 to prevent the potential of the reference electrode from being affected by various electromagnetic interferences in the external environment, thereby ensuring that the potential of the reference electrode is stabilized at the initially designed potential at any time. In other embodiments, the metal layer 40 may be replaced by other good electrical conductors.

The sealing cover 11 is provided with a second through hole 13, and the second channel is connected with the external environment through a pipeline and used for supplementing water and chemicals inside the shell 10 and ensuring smooth work of the system.

Example 2

As shown in FIG. 2, this embodiment is a new anode system with external power source. The existing external power supply type anode can emit a direct current electric field to the surrounding environment when the anode works, and becomes a source of steady-state direct current stray current interference of other metal pieces near the anode, so that the metal pieces are quickly corroded. The anode system of the present embodiment solves the above problems by employing the casing as described in embodiment 1.

A novel external power supply type anode system comprises a shell 10, a potentiostat 61, an external power supply type anode 62, a polarizing electrode 63 and a protected cathode 64. The anode 62 and the polarized electrode 63 of the external power supply are respectively connected with the anode and the cathode of the potentiostat 61, and the cathode 64 is electrically connected with the polarized electrode 63. An external power type anode 62 and a polarized electrode 63 are arranged inside the shell 10, and the external power type anode 62 and the polarized electrode 63 are immersed into the electrolyte solution 52 at one end and led out of the shell 10 by a lead at the other end.

The housing 10 is in the external electrolyte solution and is in fact entirely grounded, so that a full shielding effect is also achieved. I.e. the electromagnetic interference inside the casing 10 can not leak into the electrolyte solution outside the casing 10, so that the external power type anode 62 inside the casing 10 can not corrode other metal parts outside the casing 10.

The polarizing electrode 63 and the protected cathode 64 can protect the cathode 64 because the filling material in the first through hole 12 of the housing 10 can pass the polarizing current smoothly and the conductive wire can be electrically connected to form a complete polarizing loop.

The electrolyte solution 52 needs to be replaced with a type having high conductivity and low electrode corrosion.

It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the technical solutions of the present invention, and are not intended to limit the specific embodiments of the present invention. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention claims should be included in the protection scope of the present invention claims.

Claims

1. A shell used in the field of electrochemistry is provided with an accommodating cavity inside and a first through hole, and is characterized in that a reverse osmosis layer and an anti-electromagnetic layer are filled in the first through hole; the surface of the shell is covered with a metal layer.

2. The housing as claimed in claim 1, wherein the reverse osmosis layer is a flat ceramic reverse osmosis membrane material, and comprises a substrate layer with supporting function and a fine filtration layer with nano-scale pore size.

3. The housing of claim 1, wherein the reverse osmosis layer is made of a solid electrolyte material or an organic reverse osmosis membrane.

4. The housing of claim 1, wherein the electromagnetic shielding layer comprises a plurality of electromagnetic shielding layers and a plurality of insulating layers; several insulating layers are distributed between the two electromagnetic shielding layers.

5. The housing for electrochemical field of claim 4, wherein the electromagnetic shielding layer is formed by stacking a plurality of metal meshes; the insulating layer is made of porous non-conductive material.

6. A casing for use in the field of electrochemistry according to claim 1, characterized in that said metal layer is a metal coating or a metal casing consisting of metal sheets.

7. A novel reference electrode comprising a reference electrode and an associated electrolyte solution, characterized in that a housing according to any one of claims 1 to 6 is used; a reference electrode and an electrolyte solution are disposed in the receiving cavity of the housing; one end of the reference electrode is immersed in the internal electrolyte solution, and the other end of the reference electrode is led out of the shell by a lead.

8. A novel externally powered anode system comprising polarized electrodes, an externally powered anode, a potentiostat and an associated electrolyte solution, characterized in that a housing according to any of claims 1 to 6 is used; the polarized electrode, the external power supply type anode and the electrolyte solution are arranged in the accommodating cavity of the shell; the uniform ends of the two electrodes are immersed into the internal electrolyte solution, the other end of the two electrodes is led out from the shell by a lead, the anode of the external power supply type is connected with the anode of the constant potential rectifier, and the polarized electrode and the protected cathode are connected with the cathode of the constant potential rectifier.