CN116543982B - Microelectrode preparation method and microelectrode - Google Patents
Microelectrode preparation method and microelectrode Download PDFInfo
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- CN116543982B CN116543982B CN202310293431.0A CN202310293431A CN116543982B CN 116543982 B CN116543982 B CN 116543982B CN 202310293431 A CN202310293431 A CN 202310293431A CN 116543982 B CN116543982 B CN 116543982B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 239000000523 sample Substances 0.000 claims abstract description 287
- 229910052751 metal Inorganic materials 0.000 claims abstract description 280
- 239000002184 metal Substances 0.000 claims abstract description 280
- 238000000576 coating method Methods 0.000 claims abstract description 151
- 239000011248 coating agent Substances 0.000 claims abstract description 142
- 239000007788 liquid Substances 0.000 claims abstract description 76
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 238000002484 cyclic voltammetry Methods 0.000 claims abstract description 15
- 238000012360 testing method Methods 0.000 claims abstract description 13
- 239000007888 film coating Substances 0.000 claims abstract description 12
- 238000009501 film coating Methods 0.000 claims abstract description 12
- 230000005484 gravity Effects 0.000 claims abstract description 11
- 230000009471 action Effects 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 229910000851 Alloy steel Inorganic materials 0.000 claims description 3
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 3
- DMFGNRRURHSENX-UHFFFAOYSA-N beryllium copper Chemical compound [Be].[Cu] DMFGNRRURHSENX-UHFFFAOYSA-N 0.000 claims description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- 239000002904 solvent Substances 0.000 description 15
- 238000005498 polishing Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 7
- 238000010884 ion-beam technique Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 241001391944 Commicarpus scandens Species 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/06—Insulating conductors or cables
- H01B13/16—Insulating conductors or cables by passing through or dipping in a liquid bath; by spraying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B1/00—Devices without movable or flexible elements, e.g. microcapillary devices
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0016—Apparatus or processes specially adapted for manufacturing conductors or cables for heat treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/0009—Details relating to the conductive cores
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/02—Disposition of insulation
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Measuring Leads Or Probes (AREA)
Abstract
The invention relates to a microelectrode preparation method and a microelectrode. The preparation method of the microelectrode comprises the following steps: lifting and drawing the top of the metal probe by the film coating equipment to keep the metal probe in a vertical state; controlling the lifting film coating equipment to drive the metal probe to be inserted into the coating liquid along the vertical direction; controlling the lifting coating equipment to drive the metal probe to be pulled out of the coating liquid; the coating liquid on the outer wall of the metal probe exposes the tip of the metal probe under the action of gravity and surface tension, and the coating liquid is coated on the outer wall of the metal probe to form an insulating layer; standing the coated metal probe, and transferring the metal probe after standing to an incubator to convert the insulating layer into a glassy coating; repeating the coating steps until the peak current in the cyclic voltammetry test of the metal probe is smaller than a preset current value, and forming a microelectrode by the coated metal probe. Simplifying the preparation process and reducing the manufacturing cost.
Description
Technical Field
The invention relates to the technical field of electrochemical microelectrodes, in particular to a microelectrode preparation method and a microelectrode.
Background
In electrochemical studies, microelectrodes are often required to measure the reactivity at the reaction interface sites. In addition, the microelectrode can be directly connected with an electrode material on the metal surface with extremely small size and used for measuring the reaction characteristics of the electrode material under microscopic conditions. Therefore, a metal having a small feature size is required as a probe to realize the function of the microelectrode. In general, only a part of the metal probe with a very small tip is exposed for electrochemical experiments, and the rest part of the metal probe is coated with an insulating layer to avoid contact with electrolyte and only serves as a current collector for providing electrons.
In the traditional scheme, a platinum wire (with the diameter of more than 10 micrometers) is generally adopted as a metal carrier, and polytetrafluoroethylene or glass is coated on the whole platinum wire. And (3) cutting off the whole platinum wire, and polishing and grinding the tip of the platinum wire to make the surface smooth, thereby obtaining the microelectrode. When the platinum wire is adopted to manufacture the microelectrode, the surface of the platinum wire is required to be polished, the operation process is complex, in addition, the platinum wire is extremely easy to break in the processing process, and the preparation process difficulty is high. In addition, some researchers have coated the surface with an amorphous fluororesin solution, but the coated probe needs to be cut by a FIB/SEM (focused ion beam scanning electron microscope) instrument, which is costly, and thus the processing cost of the solution is high.
That is, the existing microelectrode has the problems of complex preparation process, great difficulty and high cost, and is inconvenient for forming and manufacturing the microelectrode.
Disclosure of Invention
Based on the above, it is necessary to provide a microelectrode preparation method and a microelectrode which can simplify the preparation process and reduce the preparation difficulty and the production cost, aiming at the problems of complex preparation process, high difficulty and high cost of the conventional microelectrode.
A method of preparing a microelectrode comprising:
lifting and drawing the top of the metal probe by the film coating equipment to keep the metal probe in a vertical state;
controlling the lifting film coating equipment to drive the metal probe to be inserted into the coating liquid along the vertical direction;
controlling the lifting coating equipment to drive the metal probe to be pulled out of the coating liquid;
the coating liquid on the outer wall of the metal probe exposes the tip of the metal probe under the action of gravity and surface tension, and the coating liquid is coated on the outer wall of the metal probe to form an insulating layer;
standing the coated metal probe, and transferring the metal probe after standing to an incubator to convert the insulating layer into a glassy coating;
repeating the coating steps until the peak current in the cyclic voltammetry test of the metal probe is smaller than a preset current value, and forming a microelectrode by the coated metal probe.
In one embodiment, the method for preparing the microelectrode further comprises the following steps before the metal probe is pulled out of the coating liquid:
the metal probe is placed in the coating liquid for a first preset time.
In one embodiment, the step of standing the coated metal probe comprises:
and placing the coated metal probe in a room temperature environment for standing for a second preset time, or placing the coated metal probe in a heating device for standing for a third preset time, and controlling the heating device to heat at a first preset temperature.
In an embodiment, the step of pulling the coating film to pull the metal probe out of the coating liquid includes:
the lifting coating equipment controls the metal probe to be pulled out of the coating liquid along the vertical direction;
the lifting speed of the metal probe is controlled to be greater than 100mm/min by the lifting film coating equipment.
In one embodiment, in the incubator, the step of converting the insulating layer into the glassy state comprises:
placing the metal probe after standing in the incubator;
controlling the temperature of the incubator to rise to a second preset temperature;
and heating the coated metal probe in the incubator for a fourth preset time, and taking out the metal probe.
In one embodiment, the step of detecting the peak current in the cyclic voltammetry of the metal probe is less than a predetermined current value comprises:
taking the microelectrode as a working electrode, and setting a counter electrode;
and performing cyclic voltammetry in the range of 0.01-4.3V relative to the working electrode and the counter electrode to obtain the peak current of the metal probe.
In one embodiment, the metal probe is inserted into the coating solution to a depth of greater than 1cm.
In one embodiment, the tip of the metal probe has a diameter dimension of less than 20 microns.
In one embodiment, the metal probe is made of tungsten, tungsten steel alloy or beryllium copper alloy.
The microelectrode comprises a metal probe and an insulating layer, wherein the insulating layer is coated on the outer wall of the metal probe by adopting the microelectrode preparation method according to any technical characteristics.
After the scheme is adopted, the invention has at least the following technical effects:
according to the microelectrode preparation method and the microelectrode, when the microelectrode is prepared by using the preparation method, the metal probe is installed on the lifting film coating equipment, and the metal probe is ensured to be arranged along the vertical direction. After the metal probe is installed on the lifting coating equipment, the lifting coating equipment drives the metal probe to be inserted into the coating liquid, and then the lifting coating equipment lifts the metal probe so that the metal probe is pulled out of the coating liquid. After the metal probe is pulled out, the coating liquid is attached to the surface of the metal probe, the coating liquid can be subjected to surface tension on the surface of the metal probe due to the small size of the metal probe, and meanwhile, the coating liquid can be subjected to gravity on the surface of the metal probe, so that the coating liquid can be coated on the outer wall of the metal probe, and an insulating layer of spherical liquid drops is formed above the tip of the metal probe to expose the tip of the metal probe. The coated metal probe is transferred to an incubator after standing, and the incubator heats the coated metal probe, so that the insulating layer of the metal probe is converted into a glass state, and the insulating layer is ensured to be uniform and smooth and have better viscosity. And taking the metal probe out of the incubator, and repeatedly executing the coating process until the peak current in the cyclic voltammetry test of the metal probe is smaller than a preset current value, and stopping coating, wherein the coated metal probe forms a microelectrode.
According to the microelectrode preparation method, the microelectrode is prepared by adopting the metal probe, the metal probe is provided with the tip, the tip of the metal probe is exposed after the insulation layer is arranged on the outer wall of the metal probe by adopting the lifting film coating equipment, the metal probe can be used as the microelectrode without polishing, the preparation process is simplified, the problem of breakage caused by polishing is avoided, and the preparation difficulty is reduced. Meanwhile, the metal probe is coated by a lifting coating method, cutting by a focused ion beam scanning electron microscope is not needed, manufacturing cost is reduced, and preparation of the microelectrode is facilitated.
Drawings
FIG. 1 is a schematic illustration of a metal probe insert coating solution according to an embodiment of the present invention;
FIG. 2 is a schematic view of the metal probe of FIG. 1 pulled out of the coating solution and made into a microelectrode;
FIG. 3 is a flow chart of microelectrode preparation according to one embodiment of the present invention;
FIG. 4 is a flow chart of removing the solvent from the outer wall of the metal probe in the process of preparing the microelectrode shown in FIG. 3;
FIG. 5 is a flow chart showing the process of preparing the microelectrode shown in FIG. 3, in which the metal probe is pulled up from the coating liquid;
fig. 6 is a flow chart of cyclic voltammetry testing of microelectrodes in the process of preparing microelectrodes shown in fig. 3.
Wherein: 100. a metal probe; 110. a probe body; 120. a needle tip; 200. an insulating layer; 300. and (5) coating liquid.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to the appended drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, whereby the invention is not limited to the specific embodiments disclosed below.
In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the device or element being referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the present invention.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present invention, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
In the present invention, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; either directly or indirectly, through intermediaries, or both, may be in communication with each other or in interaction with each other, unless expressly defined otherwise. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In the present invention, unless expressly stated or limited otherwise, a first feature "up" or "down" a second feature may be the first and second features in direct contact, or the first and second features in indirect contact via an intervening medium. Moreover, a first feature being "above," "over" and "on" a second feature may be a first feature being directly above or obliquely above the second feature, or simply indicating that the first feature is level higher than the second feature. The first feature being "under", "below" and "beneath" the second feature may be the first feature being directly under or obliquely below the second feature, or simply indicating that the first feature is less level than the second feature.
It will be understood that when an element is referred to as being "fixed" or "disposed" on another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. The terms "vertical," "horizontal," "upper," "lower," "left," "right," and the like are used herein for illustrative purposes only and are not meant to be the only embodiment.
Referring to fig. 1 to 3, the present invention provides a method for manufacturing a microelectrode. The preparation method of the microelectrode is used for preparing the microelectrode in the electrochemical field. The microelectrode is used for carrying out an electrochemical experiment so as to meet the requirements of the electrochemical experiment. It will be appreciated that in conventional solutions, a platinum wire (more than 10 microns in diameter) is typically used as the metal carrier, and polytetrafluoroethylene or glass is coated over the entire platinum wire. And (3) cutting off the whole platinum wire, and polishing and grinding the tip of the platinum wire to make the surface smooth, thereby obtaining the microelectrode. When the platinum wire is adopted to manufacture the microelectrode, the surface of the platinum wire is required to be polished, the operation process is complex, in addition, the platinum wire is extremely easy to break in the processing process, and the preparation process difficulty is high. In addition, some researchers have coated the surface with an amorphous fluororesin solution, but the coated probe needs to be cut by a FIB/SEM (focused ion beam scanning electron microscope) instrument, which is costly, and thus the processing cost of the solution is high.
Therefore, the present invention provides a novel microelectrode manufacturing method, which uses a metal probe 100 as a substrate, coats an insulating layer 200 on the surface of the metal probe 100, and exposes a tip 120 of the metal probe 100, thereby forming a microelectrode. The microelectrode prepared by the preparation method can be directly used without polishing, reduces the processing difficulty, does not need to use FIB/SEM (focused ion beam scanning electron microscope) for cutting, and reduces the cost. The following describes a specific method for preparing an embodiment of the microelectrode.
Referring to fig. 1 to 3, in an embodiment, a method of manufacturing a microelectrode includes:
s1: the lifting and coating equipment clamps the top of the metal probe 100 to keep the metal probe 100 in a vertical state;
s2: controlling the lifting coating equipment to drive the metal probe 100 to be inserted into the coating liquid 300 along the vertical direction;
s3: controlling the lifting coating equipment to drive the metal probe 100 to be pulled out of the coating liquid 300;
s4: the coating solution 300 on the outer wall of the metal probe 100 exposes the tip 120 of the metal probe 100 under the action of gravity and surface tension, and the coating solution 300 is coated on the outer wall of the metal probe 100 to form an insulating layer 200;
s5: standing the coated metal probe 100, and transferring the metal probe 100 to an incubator to convert the insulating layer 200 into a glassy coating;
s6: repeating the coating steps until the peak current in the cyclic voltammetry test of the metal probe 100 is smaller than a preset current value, and forming a microelectrode by the coated metal probe 100.
It will be appreciated that the metal probe 100 requires only a very small portion of the tip 120 to be exposed for electrochemical experiments, and the remainder to be coated with the insulating layer 200 to avoid contact with the electrolyte, acting only as a current collector for providing electrons. Therefore, the preparation method of the microelectrode of the present invention realizes that the insulating layer 200 is coated on the outer side of the metal probe 100, and exposes the tip 120 of the metal probe 100, thereby reducing the processing difficulty and the processing cost and facilitating the preparation of the microelectrode. In the preparation method of the microelectrode, the insulating layer 200 is coated on the surface of the metal probe 100 by a lifting coating method.
Specifically, the metal probe 100 is inserted into the coating liquid 300, and then the metal probe 100 is pulled out from the coating liquid 300, and the coating liquid 300 adheres to the outer wall of the metal probe 100, and the insulating layer 200 is formed on the outer wall of the metal probe 100 by the action of gravity and surface tension. The pull coating method mounts the metal probe 100 using a pull coating apparatus, and the pull coating apparatus drives the metal probe 100 to be inserted into the coating liquid 300 and pulls the metal probe 100 out of the coating liquid 300. The pulling coating apparatus is an existing apparatus, and the fixture of the pulling coating apparatus can achieve reliable clamping of the metal probe 100, which is not described herein.
The bottom of the metal probe 100 is a tip 120, and a jig for pulling the coating apparatus grips the bottom of the metal probe 100 so that the metal probe 100 is disposed in a vertical direction. That is, the metal probe 100 is clamped by the clamp of the lifting coating apparatus in the vertical direction, and when the lifting coating apparatus drives the metal probe 100 to be inserted into and pulled out of the coating liquid 300, the metal probe 100 is also in the vertical direction, so that the coating liquid 300 can be ensured to be substantially uniformly coated on the outer wall of the metal probe 100 at the same height position, thereby ensuring the coating effect of the insulating layer 200 on the metal probe 100.
In addition, the microelectrode of the present invention is prepared by using the metal probe 100 as a needle body, and the bottom of the metal probe 100 is a needle tip 120. That is, the end of the metal probe 100 is a tip. After the microelectrode is prepared by using the metal probe 100, the tip 120 of the metal probe 100 is directly the tip of the microelectrode, so that an electrochemical experiment can be directly performed by using the tip, the end of the microelectrode is not required to be polished, the preparation steps of the microelectrode are simplified, the preparation difficulty is reduced, and the breakage in the polishing process is avoided.
The metal probe 100 is pulled up by the pulling-up coating apparatus, so that the coating liquid 300 will adhere to the outer wall of the metal probe 100 after the metal probe 100 is pulled out from the coating liquid 300. Because the tip 120 of the metal probe 100 is small, the metal probe 100 may generate a surface tension at the tip 120, and at the same time, the metal probe 100 is lifted in a vertical direction, and the coating liquid 300 attached to the outer wall of the metal probe 100 may also be subjected to a gravity force. The coating liquid 300 on the outer wall of the metal probe 100 forms liquid drops at the needle tip 120 under the action of gravity and surface tension, and exposes the needle tip 120 of the metal probe 100. That is, the metal probe 100 has metal exposed at the tip 120, which facilitates the electrochemical experiments at a later stage.
The metal probe 100 pulled out from the coating liquid 300 is left to stand to remove most of the solvent of the outer wall of the metal probe 100. It can be appreciated that after the metal probe 100 is kept stand, the solvent coated on the outer wall of the metal probe 100 gradually volatilizes, so as to remove most of the solvent, so that the residual coating liquid 300 is coated on the outer wall of the metal probe 100 to form the insulating layer 200. The coated metal probe 100 is placed in an incubator, the incubator is heated, the temperature in the incubator is increased to be higher than the glass transition temperature of the coating liquid 300, the coating liquid 300 is heated, after a period of heating, all solvents are removed, the insulating layer 200 is converted into a glassy state, the insulating layer 200 which is more uniform, smoother and better in adhesiveness is obtained, and the coating effect and the insulating effect of the insulating layer 200 on the metal probe 100 are ensured. The incubator is an existing device and will not be described in detail herein.
The metal probe 100 completes one coating process according to steps S1 to S5. And, the steps S1 to S5 are repeatedly performed to coat the metal probe 100 a plurality of times until the peak current of the voltammetric cycle test of the metal probe 100 is less than the preset current value, indicating that the metal probe 100 is coated, the insulating layer 200 is coated on the outer side of the metal probe 100 accurately, and a microelectrode is formed, which can be subjected to an electrochemical experiment. The voltammetric cycle test method herein is an electrochemical research method. The method controls the potential of the microelectrode to scan repeatedly with a triangular waveform once or a plurality of times at different rates along with time, and the potential range is that different reduction and oxidation reactions can be alternately generated on the microelectrode, and a current-potential curve is recorded for judging the microscopic reaction process of the surface of the microelectrode.
Referring to fig. 1 to 3, when the microelectrode is manufactured by the microelectrode manufacturing method according to the above embodiment, the metal probe 100 is installed in the lifting coating apparatus in the vertical direction, and the lifting coating apparatus is controlled to drive the metal probe 100 to be inserted into the coating liquid 300, so that the outer wall of the metal probe 100 is sufficiently contacted with the coating liquid 300. Subsequently, the metal probe 100 is pulled up by the pulling-up coating apparatus, so that the metal probe 100 is pulled out from the coating liquid 300. At this time, a part of the coating liquid 300 adheres to the outer wall of the metal probe 100, and the coating liquid 300 forms droplets at the tip 120 under the action of surface tension and gravity, so that the tip 120 of the metal probe 100 is exposed. Then, the metal probe 100 is left to stand to remove most of the solvent of the outer wall of the metal probe 100, so that the remaining coating liquid 300 is coated on the outer wall of the metal probe 100 to form the insulating layer 200. The coated metal probe 100 is placed in an incubator, and the incubator is heated, so that the temperature in the incubator is raised above the glass transition temperature of the coating solution 300, the coating solution 300 is heated, after a period of heating, all solvents are removed, and the insulating layer 200 is transformed into a glassy state, thereby obtaining the insulating layer 200 which is more uniform, smoother and better in adhesion. The coating process is repeatedly performed until the peak current of the voltammetric cycle test of the metal probe 100 is less than a preset current value, which indicates that the metal probe 100 is coated, and the insulating layer 200 is accurately coated on the outer side of the metal probe 100 to form a microelectrode, which can be subjected to an electrochemical experiment.
According to the microelectrode preparation method, the metal probe 100 is used for preparing the microelectrode, the metal probe 100 is provided with the needle tip 120/cone angle, the insulation layer 200 is arranged on the outer wall of the metal probe 100 by adopting a lifting film coating device, the needle tip 120 of the metal probe 100 is exposed, polishing is not needed, the metal probe can be used as the microelectrode, the preparation process is simplified, the problem of breakage caused by polishing is avoided, and the preparation difficulty is reduced. Meanwhile, the metal probe 100 is coated by a lifting coating method, cutting by a focused ion beam scanning electron microscope is not needed, manufacturing cost is reduced, and preparation of microelectrodes is facilitated. The microelectrode preparation method can be used for preparing the metal probe 100 coated by the insulating layer 200 and preparing the electrochemical microelectrode.
Referring to fig. 1 and 2, in an embodiment, the metal probe 100 includes a probe body 110 and the above-mentioned needle tip 120, the needle tip 120 being disposed at a bottom end of the probe body 110. The insulating layer 200 covers an end of the probe body 110 near the tip 120 and partially covers the tip 120. The needle tip 120 is tapered, the bottommost part of the needle tip 120 is pointed, and the probe body 110 is cylindrical. The insulating layer 200 covers a portion of the tapered surface and a portion of the cylindrical surface.
In one embodiment, the probe body 110 has a diameter dimension in the range of greater than 100 microns. Thus, the mechanical strength of the metal probe 100 can be improved, so that the mechanical strength of the metal probe 100 is far higher than that of a platinum wire, and the metal probe 100 is convenient to process.
In one embodiment, the tip 120 of the metallic probe 100 has a diameter dimension of less than 20 microns. In this way, the tip 120 of the metal probe 100 can meet the requirements of an electrochemical experiment.
Alternatively, the diameter of the needle tip 120 is gradually reduced in size from the end connected to the probe body 110 to the end distant from the probe body 110. This can prevent a step structure from being formed at the junction of the probe body 110 and the tip 120, and ensure structural strength of the metal probe 100.
Referring to fig. 3, in an embodiment, before the metal probe 100 is pulled out from the coating solution 300, the method for preparing a microelectrode further includes the steps of:
s7: the metal probe 100 is left standing in the coating liquid 300 for a first preset time.
That is, after the metal probe 100 is inserted into the coating liquid 300 by the pulling coating apparatus, the metal probe 100 needs to stand in the coating liquid 300 for a certain time so that the metal probe 100 is sufficiently contacted with the coating liquid 300, thereby achieving sufficient wetting of the metal probe 100. Thus, when the metal probe 100 is pulled up by the pulling-up coating apparatus, the outer wall of the metal probe 100 can be pulled out by attaching a certain coating liquid 300 thereto. Optionally, the first preset time is 30s to 90s. Preferably, the first preset time is 30s. Of course, in other embodiments of the invention, this process may be omitted. That is, after the metal probe 100 is inserted into the coating liquid 300 by the pulling-up coating apparatus, the metal probe 100 may be directly pulled up so that the metal probe 100 is pulled out from the coating liquid 300, and the insulating layer 200 is formed on the outer wall of the metal probe 100 by repeating the coating operation a plurality of times.
Referring to fig. 3 and 4, in one embodiment, the step of standing the coated metal probe 100 includes:
s51: and placing the coated metal probe 100 in a room temperature environment for standing for a second preset time, or placing the coated metal probe 100 in a heating device for standing for a third preset time, and controlling the heating device to heat at a first preset temperature.
When the metal probe 100 pulled out of the coating liquid 300 is left to stand, the metal probe 100 may be left to stand in a room temperature environment, and the solvent on the outer wall of the metal probe 100 may volatilize in the room temperature environment. After most of the solvent on the outer wall of the metal probe 100 volatilizes, the metal probe 100 is transferred from the room temperature environment to an incubator. Of course, when the metal probe 100 pulled out from the coating liquid 300 is left to stand, the metal probe 100 may be left to stand in a heating device, and the environment in which the metal probe 100 is located may be heated by the heating device, so that the solution on the outer wall of the metal probe 100 volatilizes in the heating device. After most of the solvent on the outer wall of the metal probe 100 volatilizes, the metal probe 100 is transferred from the heating device to the incubator. The heating device is an existing device and will not be described in detail here.
Alternatively, the metal probe 100 is left standing in the room temperature environment for a second preset time, or the metal probe 100 is left standing in the heating device for a third preset time, the second preset time being greater than the third preset time. It will be appreciated that solvents will evaporate rapidly in high temperature environments and slowly in low temperature environments. The temperature of the environment in the heating means is higher than that of the room temperature environment, so that the metal probe 100 is allowed to stand in the room temperature environment for a longer period of time than in the heating means.
It should be noted that, the setting of the second preset time and the third preset time is selected according to the current temperature. For example, if a heating environment of 50 ℃ is provided in the heating device, the third preset time is 3min to 5min. That is, the metal probe 100 is allowed to stand at 50℃for 3 to 5 minutes, thereby achieving the technical effect of removing most of the solvent. The lower the temperature, the longer the metal probe 100 needs to be left to stand, and will not be described in detail herein.
Referring to fig. 3 and 4, in an embodiment, the step of converting the insulating layer 200 into the glassy state in the incubator includes:
s52: placing the metal probe 100 after standing in the incubator;
s53: controlling the temperature of the incubator to rise to a second preset temperature;
s54: and after the coated metal probe 100 is heated in the incubator for a fourth preset time, taking out the metal probe 100.
After the metal probe 100 is placed still, most of the solvent on the outer wall of the metal probe 100 is removed, and the remaining coating solution 300 forms the insulating layer 200 on the outer wall of the metal probe 100, at this time, the insulating layer 200 on the outer wall of the metal probe 100 needs to be converted into a glass state, so that the insulating layer 200 in a glass state is formed, so that the insulating effect and the thickness of the insulating layer 200 are uniform. Specifically, the metal probe 100 after standing is transferred to an incubator, and the incubator is controlled to heat so that the temperature rises above the glass transition temperature of the coating liquid 300. In this way, after the metal probe 100 is heated in the incubator for a period of time, all the solvent can be removed, and the insulating layer 200 is converted into the glassy insulating layer 200 at the temperature, so that a more uniform and smoother insulating layer 200 is obtained, and the insulating effect of the metal probe 100 is ensured.
It can be appreciated that the temperatures at which the different coating solutions 300 are converted into the glassy state are different, that is, the second preset temperature is designed according to the type of the coating solution 300, so long as the second preset temperature is ensured to be equal to or higher than the temperature at which the coating solution 300 is converted into the glassy state. Illustratively, the coating solution 300 is a fluorochemical solution having a second predetermined temperature greater than 135 ℃, i.e., the fluorochemical solution has a corresponding transition temperature of 135 ℃, so long as the temperature in the incubator is greater than this temperature, the glass transition is achieved.
Moreover, the metal probe 100 needs to be heated in an incubator for a fourth preset time to volatilize all solvents while sufficiently converting the insulating layer 200 into a glassy state. It should be noted that the fourth preset time is set according to the heating temperature, i.e. the type of the coating liquid 300, and will not be described herein.
Referring to fig. 3 and 5, in an embodiment, the step of pulling the coating film to pull the metal probe 100 out of the coating solution 300 includes:
s31: the pulling coating apparatus controls the metal probe 100 to be pulled out from the coating liquid 300 in the vertical direction;
s32: the pulling coating equipment controls the pulling speed of the metal probe 100 to be more than 100mm/min.
The metal probe 100 is driven by the lifting coating equipment to be inserted into the coating liquid 300 along the vertical direction, and after the metal probe 100 is fully soaked with the coating liquid 300, the metal probe 100 is lifted by the lifting coating equipment along the vertical direction, so that the metal probe 100 is pulled out of the coating liquid 300 along the vertical direction. In this way, the coating liquid 300 attached to the outer wall of the metal probe 100 can be subjected to gravity in the vertical direction, and thus a droplet is formed at the tip 120 of the metal probe 100 under the action of gravity and surface tension.
Moreover, the lifting coating equipment drives the metal probe 100 to lift at a speed greater than 100mm/min, so that the metal probe 100 is slowly pulled out of the coating liquid 300, and the phenomenon that the coating liquid 300 cannot be adhered to the outer wall of the metal probe 100 or the adhered coating liquid 300 is too small due to too high speed is avoided.
Referring to fig. 3 and 6, in an embodiment, the step of the peak current in the cyclic voltammetry test of the metal probe 100 is less than a preset current value includes:
s61: taking the microelectrode as a working electrode, and setting a counter electrode;
s62: and performing cyclic voltammetry in a range of 0.01V to 4.3V in point position with respect to the working electrode and the counter electrode to obtain peak current of the metal probe 100.
After the metal probe 100 is coated with a layer, the metal probe 100 is subjected to cyclic voltammetry, and if the peak current of the metal probe 100 is greater than the preset current value, it indicates that the thickness of the insulating layer 200 cannot meet the electrochemical requirement, and the coating needs to be performed again. And (3) carrying out cyclic voltammetry test on the metal probe 100 after each coating until the peak current of the metal probe 100 is smaller than a preset current value, and completing the preparation of the microelectrode.
When the metal probe 100 is subjected to the volt-ampere cycle test, the coated metal probe 100 is used as a working electrode, lithium metal or platinum metal is used as a counter electrode, the cyclic volt-ampere test is performed in a range that the point positions of the counter electrode and the counter electrode are 0.01V-4.3V, so that peak current of the metal probe 100 is obtained, and the peak current is compared with a preset current value to judge whether the peak current is smaller than the preset current value. Alternatively, the preset current value is 100pA. That is, the peak current in the cyclic voltammetry test of the metal probe 100 is less than 100pA, and the application of the metal probe 100 can be stopped.
In one embodiment, the metal probe 100 is inserted into the coating solution 300 to a depth of more than 1cm. That is, the depth of the metal probe 100 inserted into the coating solution 300 by the pulling and coating apparatus is greater than 1cm, so that the metal probe 100 can be fully contacted with the coating solution 300 to meet the length requirement of the metal probe 100 for coating the insulating layer 200.
In one embodiment, the coating solution 300 is a fluorochemical liquid. The coating solution 300 employs a chemically stable fluorine-containing compound solution to ensure the insulating effect of forming the insulating layer 200. Alternatively, the coating solution 300 may be a solution of polytetrafluoroethylene, soluble Polytetrafluoroethylene (PFA), amorphous fluororesin, or the like. Alternatively, the coating solution 300 may be a solution of an amorphous fluororesin having a concentration of at most 10% and a fluorinated solution FC-40. In this example, the concentration of the amorphous fluororesin in the coating liquid 300 was 6%.
In one embodiment, the metal probe 100 is made of a hard metal that is easy to process. Optionally, the metal probe 100 is made of tungsten, tungsten steel alloy, beryllium copper alloy, or the like, so as to ensure the strength of the metal probe 100.
Referring to fig. 1 to 3, when the microelectrode is prepared by the microelectrode preparation method, the metal probe 100 is used for preparing the microelectrode, the metal probe 100 is provided with the needle tip 120/cone angle, and after the insulation layer 200 is arranged on the outer wall of the metal probe 100 by adopting the lifting film coating equipment, the needle tip 120 of the metal probe 100 is exposed and can be used as the microelectrode without polishing, so that the preparation process is simplified, the problem of breakage caused by polishing is avoided, and the preparation difficulty is reduced. Meanwhile, the metal probe 100 is coated by a lifting coating method, cutting by a focused ion beam scanning electron microscope is not needed, manufacturing cost is reduced, and preparation of microelectrodes is facilitated. The microelectrode preparation method can be used for preparing the metal probe 100 coated by the insulating layer 200 and preparing the electrochemical microelectrode.
Referring to fig. 1 and 2, the present invention further provides a microelectrode, which includes a metal probe 100 and an insulating layer 200, where the insulating layer 200 is coated on the outer wall of the metal probe 100 by using the microelectrode preparation method according to any of the embodiments described above. According to the microelectrode, the insulating layer 200 is coated on the outer side of the metal probe 100, so that the needle tip 120 of the metal probe 100 is exposed, the microelectrode can be used as the microelectrode without polishing, the preparation process is simplified, the problem of breakage caused by polishing is avoided, and the preparation difficulty is reduced. Meanwhile, the metal probe 100 is coated by a lifting coating method, cutting by a focused ion beam scanning electron microscope is not needed, manufacturing cost is reduced, and preparation of microelectrodes is facilitated.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. A method of preparing a microelectrode comprising:
lifting and drawing the top of the metal probe by the film coating equipment to keep the metal probe in a vertical state;
controlling the lifting film coating equipment to drive the metal probe to be inserted into the coating liquid along the vertical direction;
controlling the lifting coating equipment to drive the metal probe to be pulled out of the coating liquid;
the coating liquid on the outer wall of the metal probe forms liquid drops on the needle tip under the action of gravity and surface tension, the needle tip of the metal probe is exposed, and the coating liquid is coated on the outer wall of the metal probe to form an insulating layer;
standing the coated metal probe, and transferring the metal probe after standing to an incubator to convert the insulating layer into a glassy coating;
repeating the coating steps until the peak current in the cyclic voltammetry test of the metal probe is smaller than a preset current value, and forming a microelectrode by the coated metal probe.
2. The method of manufacturing a microelectrode according to claim 1, further comprising the step of, before extracting the metal probe from the coating liquid:
the metal probe is placed in the coating liquid for a first preset time.
3. The method of manufacturing a microelectrode according to claim 1, wherein the step of leaving the coated metal probe to stand comprises:
and placing the coated metal probe in a room temperature environment for standing for a second preset time, or placing the coated metal probe in a heating device for standing for a third preset time, and controlling the heating device to heat at a first preset temperature.
4. The method according to claim 1, wherein the step of pulling the coating film to pull the metal probe out of the coating liquid comprises:
the lifting coating equipment controls the metal probe to be pulled out of the coating liquid along the vertical direction;
the lifting speed of the metal probe is controlled to be greater than 100mm/min by the lifting film coating equipment.
5. The method of manufacturing a microelectrode according to claim 1, wherein the step of converting the insulating layer into the glassy state in the incubator includes:
placing the metal probe after standing in the incubator;
controlling the temperature of the incubator to rise to a second preset temperature;
and heating the coated metal probe in the incubator for a fourth preset time, and taking out the metal probe.
6. The method of manufacturing a microelectrode according to claim 1, wherein the step of measuring the peak current in the cyclic voltammetry of the metal probe to be smaller than a preset current value comprises:
taking the microelectrode as a working electrode, and setting a counter electrode;
and performing cyclic voltammetry in the range of 0.01V-4.3V relative to the working electrode and the counter electrode to obtain the peak current of the metal probe.
7. The method according to any one of claims 1 to 6, wherein the metal probe is inserted into the coating liquid to a depth of more than 1cm.
8. The method of any one of claims 1 to 6, wherein the diameter of the tip of the metal probe is less than 20 microns.
9. The method of any one of claims 1 to 6, wherein the metal probe is made of tungsten, tungsten steel alloy or beryllium copper alloy.
10. A microelectrode comprising a metal probe and an insulating layer, wherein the insulating layer is coated on the outer wall of the metal probe by the microelectrode preparation method according to any one of claims 1 to 9.
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| CN101813659A (en) * | 2009-02-20 | 2010-08-25 | 厦门大学 | Preparation method of palladium black-hydrogen pH microelectrode |
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| CN113390790A (en) * | 2021-05-24 | 2021-09-14 | 西安交通大学 | Optical fiber nano probe with large length-diameter ratio and preparation method and application thereof |
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| CN101813659A (en) * | 2009-02-20 | 2010-08-25 | 厦门大学 | Preparation method of palladium black-hydrogen pH microelectrode |
| JP2012127869A (en) * | 2010-12-16 | 2012-07-05 | Mitsubishi Cable Ind Ltd | Insulation-coated probe pin and method for manufacturing the same |
| CN104785871A (en) * | 2015-04-17 | 2015-07-22 | 清华大学深圳研究生院 | Probe manufacturing method and device |
| CN113390790A (en) * | 2021-05-24 | 2021-09-14 | 西安交通大学 | Optical fiber nano probe with large length-diameter ratio and preparation method and application thereof |
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