CN113594873B - Electrode with metal micro-column array on surface and preparation method thereof - Google Patents
Electrode with metal micro-column array on surface and preparation method thereof Download PDFInfo
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- CN113594873B CN113594873B CN202110807164.5A CN202110807164A CN113594873B CN 113594873 B CN113594873 B CN 113594873B CN 202110807164 A CN202110807164 A CN 202110807164A CN 113594873 B CN113594873 B CN 113594873B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01T—SPARK GAPS; OVERVOLTAGE ARRESTERS USING SPARK GAPS; SPARKING PLUGS; CORONA DEVICES; GENERATING IONS TO BE INTRODUCED INTO NON-ENCLOSED GASES
- H01T1/00—Details of spark gaps
- H01T1/20—Means for starting arc or facilitating ignition of spark gap
- H01T1/22—Means for starting arc or facilitating ignition of spark gap by the shape or the composition of the electrodes
Abstract
The invention discloses an electrode with a metal micro-column array on the surface and a preparation method thereof. The surface of the electrode is a metal micro-column array structure with the diameter of tens of microns to hundreds of microns. Compared with a planar electrode structure, the electrode structure can enhance an electric field at the top end of each metal microcolumn, and each metal microcolumn can effectively emit electrons under the action of high voltage; the stability of the position of the electron emitted by the electrode is ensured, and the dispersion of the emission voltage is effectively reduced. In order to realize the preparation of the electrode structure, a preparation method combining film covering, laser array etching and space-limited electroplating is provided. Firstly, cleaning the surface of metal, coating an insulating film on the surface, etching array cylindrical holes on the surface of the coating film in a laser etching mode, electroplating metal inside the array cylindrical holes in an electroplating mode, and finally removing redundant insulating film in a high-temperature carbonization mode to obtain the electrode with the metal micro-column array on the surface.
Description
Technical Field
The invention belongs to the field of high-voltage gas discharge switches, and relates to an electrode with a metal micro-column array on the surface and a preparation method thereof.
Background
In the field of pulse power technology, a gas switch is generally selected to conduct a circuit to form pulses, and the performance of the switch determines the output characteristic of pulse power. However, the stability of the general gas switch is poor, and the discharge voltage fluctuation is large, which seriously affects the pulse formation and the working stability of the pulse power device, so the switching technology becomes a big problem of the pulse power technology.
In order to obtain a stable gas switch, researchers in the field have researched various factors such as a gas switch electrode material, an electrode structure, a gas state, a voltage type and the like, and the specific contents are described in a document I [ Guo Lifu, Li, Living friend and the like ], a graphite type high-energy two-electrode gas switch [ J ]. strong laser and particle beam, 2010, 22(12): 3034-.
According to the research of the documents, the influence of the surface structure of the electrode on the discharge process of the switch is great; meanwhile, the surface of the electrode is continuously ablated by discharge, so that the surface structure of the electrode is continuously changed, the gas switch has poor stability due to the changed surface structure of the electrode, and the discharge voltage fluctuation is large.
In order to solve the above problems, a microgroove graphite cathode structure is proposed, which effectively improves the stability of electrode discharge and reduces the fluctuation of discharge voltage, and the specific scheme is described in the documents [ Wanggang, Zhang Happy wave, Wanjunjie, and the like.
However, this structure has the following problems: because the graphite material is brittle, the graphite structure with the surface projection gradually falls off particles under the impact of micro explosion generated by discharge of the microgroove graphite cathode with the thickness of tens of micrometers, is continuously shortened, finally loses the surface structure and loses the effect of stabilizing discharge voltage. Although the service life of the graphite electrode can be theoretically increased by increasing the aspect ratio, the graphite electrode cannot be practically used at present because the graphite structure having a large aspect ratio is more likely to be broken.
Disclosure of Invention
In order to solve the problems that the gas switch stability is poor and the discharge voltage fluctuation is large due to the changed electrode surface structure when the existing electrode is used, the patent provides an electrode with a metal micro-column array on the surface, and meanwhile, the invention also provides a preparation method of the electrode.
The specific technical scheme of the invention is as follows:
an electrode with a metal micro-column array on the surface is provided, which comprises a metal electrode substrate and a plurality of metal micro-columns;
all the metal microcolumns are vertically embedded on the metal electrode substrate and distributed in an array on the metal electrode substrate;
the diameter of the metal microcolumn ranges from 25 micrometers to 200 micrometers, and the length-diameter ratio of the metal microcolumn ranges from 1:1 to 5: 1; the interval between every two adjacent metal microcolumns is 50-1000 mu m.
Furthermore, the metal microcolumn is grown on the metal electrode substrate in an electroplating deposition mode.
Further, the metal electrode substrate is made of stainless steel or copper, and the metal microcolumn is made of copper or nickel.
Meanwhile, the invention also provides a preparation method of the electrode with the metal micro-column array on the surface, which comprises the following steps:
step 1: cleaning the surface of a metal electrode substrate, and coating an insulating film on the surface of the metal electrode substrate;
step 2: etching cylindrical holes in array arrangement on the surface of the metal electrode substrate of the film in a laser etching mode;
and 3, step 3: cleaning the metal electrode substrate with the cylindrical hole again, and removing an oxide film at the bottom of the cylindrical hole due to the laser action through acid liquor;
and 4, step 4: growing a metal microcolumn vertical to the metal electrode substrate in each cylindrical hole in an electroplating deposition mode;
and 5: and finally, removing the redundant insulating film through carbonization treatment to obtain the electrode with the array structure on the surface.
Furthermore, the diameter of the metal microcolumn ranges from 25 μm to 200 μm, and the length-diameter ratio of the metal microcolumn ranges from 1:1 to 5: 1; the interval between every two adjacent metal microcolumns is 50-1000 mu m.
Further, the depth range of the etched cylindrical hole in the step 2 is 10-50 μm; the laser is an ultraviolet laser.
Furthermore, the insulating film is made of transparent adhesive tape or polyimide adhesive and is firmly bonded with the metal electrode substrate through adhesion.
Further, the acid solution in the step 3 is selected from dilute sulfuric acid, dilute nitric acid, hydrochloric acid or mixed acid solution.
Further, the carbonization temperature in the step 5 is 400-800 ℃, and the carbonization process is performed in argon, nitrogen, reducing atmosphere or vacuum environment.
Further, the metal electrode substrate is made of stainless steel or copper, and the metal microcolumn is made of copper or nickel.
The invention has the following beneficial effects:
1. when the metal micro-column array electrode structure provided by the invention is applied to a gas switch, as the discharge positions are all at the top ends of the metal micro-columns, and the discharge process basically has no influence on the surface appearance of the metal electrode (the metal micro-column array structure is adopted before and after discharge), the discharge voltage is stable, and the discharge fluctuation is small.
2. The metal microcolumns are obtained by electroplating, no special requirements are imposed on the material of the metal electrode substrate, and the metal microcolumn arrays can be prepared on the surface of a material which can generally conduct electricity; meanwhile, a cylindrical hole with a certain depth is etched on the metal electrode substrate by laser, the metal microcolumn is deposited and formed from the inside of the cylindrical hole and embedded into the metal electrode substrate, the combination is good, and the stability is high in the using process.
3. The film is coated by the common transparent adhesive tape or the polyimide insulating adhesive tape, so that the film is easy to obtain, the method is simple, and the technical threshold is low; the method for removing the insulating film through atmosphere carbonization does not damage the structure of the metal micro-column array, and meanwhile, the metal micro-column array is subjected to heat treatment in a high-temperature carbonization environment, so that the stability is further improved.
4. The metal microcolumn array on the surface of the electrode is made of metal, so that the electrode is high in toughness, free of crack in the discharging process, small in mass loss and long in service life.
Drawings
FIG. 1 is a schematic view of an electrode structure according to the present invention;
FIG. 2 is a schematic diagram of the discharge process of the electrode structure of the present invention;
FIG. 3 is a flow chart of the preparation of the electrode of the present invention;
FIG. 4 is an electron micrograph of surface structure change during electrode preparation.
The reference numbers are as follows:
1-metal electrode substrate, 2-metal microcolumn.
Detailed Description
The invention provides an electrode with a surface array structure, which comprises a metal electrode substrate 1 and a plurality of metal microcolumns 2 as shown in figure 1; all the metal microcolumns 2 are vertically embedded on the metal electrode substrate 1 and distributed on the metal electrode substrate 1 in an array; the diameter of the metal microcolumns 2 is 25-200 μm, the length-diameter ratio of the metal microcolumns 2 is 1: 1-5: 1, and the interval between every two adjacent metal microcolumns is 50-1000 μm.
As shown in fig. 2, under the action of high voltage, the electrode structure can enhance the electric field at the top end of each metal microcolumn, and each metal microcolumn can effectively emit electrons after a certain voltage threshold is reached. The position of the emitted electrons is stabilized at the top end of each metal microcolumn, and the metal microcolumn structures distributed in an array on the surface of the metal electrode substrate basically do not change along with the emission, so that the stability of the emission voltage can be maintained, the dispersity of the emission voltage is reduced, and meanwhile, the stable structure can be maintained in the discharge process due to the higher metal toughness, and the service life of the electrode is longer.
In order to realize the preparation of the electrode structure, the invention also provides a preparation method combining film coating, laser array etching and space-limited electroplating. As shown in fig. 2, the preparation process is as follows:
step 1: cleaning the surface of the metal electrode substrate, and coating an insulating film on the surface of the metal electrode substrate;
while this step is being performed: the metal electrode substrate material can be common metal electrode materials such as stainless steel, copper and the like; the insulating film can be non-conductive adhesive tapes such as a transparent adhesive tape, a polyimide adhesive tape and the like, and is firmly bonded with the metal electrode substrate through the bonding of glue solution;
step 2: etching cylindrical holes arranged in an array on the surface of the metal electrode substrate of the film in a laser etching mode;
while this step is being performed: the depth of the laser etched cylindrical hole is 10-50 μm higher than the thickness of the insulating film, so that the insulating film is ensured to be etched through, a plating solution is ensured to be capable of contacting the surface of the metal electrode substrate, and the metal microcolumn generated by electroplating is ensured to be firmly combined with the metal substrate;
and step 3: cleaning the metal electrode substrate with the cylindrical hole, and removing an oxide film at the bottom of the cylindrical hole due to the laser action by acid liquor;
when the oxide film generated by the laser action is removed by using the acid liquor in the step, dilute sulfuric acid, dilute nitric acid, hydrochloric acid or mixed acid liquor can be selected according to the type of the metal to expose the base metal, so that favorable implementation conditions are provided for the next electroplating process;
and 4, step 4: growing a metal microcolumn vertical to the metal electrode substrate in each cylindrical hole in an electroplating deposition mode; the metal microcolumn is made of metal materials such as copper, nickel and the like which are easy to electroplate;
and 5: and finally, removing the redundant insulating film through carbonization treatment to obtain the electrode with the array structure on the surface.
In this step, the temperature of the carbonization treatment is selected from 400 ℃ to 800 ℃ according to the material of the insulating film, and the carbonization is performed under argon, nitrogen, a reducing atmosphere or vacuum, so as to prevent the metal prepared by electroplating from being oxidized.
To further demonstrate the performance of the electrode structure of the present invention, a more detailed description is provided below by comparing two specific sets of examples.
Example 1
1. Selecting copper as a metal electrode substrate material, processing the copper into a Bruce-shaped electrode with the diameter of 25mm and the thickness of 8mm, respectively cleaning the Bruce-shaped electrode in acetone, ethanol and deionized water, and drying the Bruce-shaped electrode in an oven at 80 ℃ for 2 hours;
2. sticking a polyethylene transparent insulating tape with the thickness of 100 mu m on the surface of the cleaned metal electrode substrate, and enabling the insulating tape to be tightly attached to the metal electrode substrate;
3. etching a cylindrical hole array with the diameter of 160 microns, the depth of 120 microns and the period of 400 microns on the surface of the insulating tape by using an ultraviolet laser with the wavelength of 355nm (the period is the interval between two adjacent cylindrical holes), wherein each cylindrical hole in the cylindrical hole array penetrates through the insulating tape, and the depth of the cylindrical hole in the metal electrode substrate is 20 microns;
4. ultrasonically soaking the film-coated electrode subjected to laser etching in a dilute nitric acid solution with the mass fraction of 5% for 5mins, and removing an oxide film at the bottom of each cylindrical hole, which is generated due to the action of laser;
5. in an acidic copper plating bath (CuSO) 4 180g/L，NaCl 0.1g/L,H 2 SO 4 60g/L), the metal copper is used as an anode, the film-coated copper electrode is used as a cathode, and the current density is 3A/dm 2 Electroplating for 3h at room temperature of 25 ℃ to obtain a plurality of metal micro-columns arranged in an array;
6. cleaning the electroplated electrode with the array metal micro-column structure by using deionized water, and pyrolyzing the electrode for 3 hours at 500 ℃ in an atmosphere furnace under the protection of argon to remove residual insulating adhesive tapes on the surface;
7. and cleaning the electrode of the array metal micro-column structure after pyrolysis treatment by using acetone and deionized water, drying for 2h at 80 ℃ to obtain an electrode shown in figure 4, wherein the diameter of each metal micro-column is 160 micrometers, the length of each metal micro-column is 100 micrometers, and the interval between every two adjacent metal micro-columns is 400 micrometers, and the electrode is marked as an array electrode A.
Example 2
1. Selecting 304 stainless steel as a metal electrode substrate material, processing the metal electrode substrate material into a Bruce-shaped electrode with the diameter of 25mm and the thickness of 8mm, respectively cleaning the Bruce-shaped electrode in acetone, ethanol and deionized water, and drying the Bruce-shaped electrode in an oven at 80 ℃ for 2 hours;
2. adhering a polyimide insulating tape with the thickness of 200 mu m on the surface of the cleaned metal electrode substrate, and enabling the insulating tape to be tightly attached to the metal electrode substrate;
3. etching a cylindrical hole array with the diameter of 100 micrometers, the depth of 240 micrometers and the period of 300 micrometers on the surface of the polyimide adhesive tape by using an ultraviolet laser with the wavelength of 355nm, wherein each cylindrical hole in the cylindrical hole array penetrates through the insulating adhesive tape, and the depth of the cylindrical hole in the metal electrode substrate is 40 micrometers;
4. ultrasonically soaking the film-coated electrode subjected to laser etching in a dilute sulfuric acid solution with the mass fraction of 10% for 5mins, and removing an oxide film generated due to the action of laser at the bottom of each cylindrical hole;
5. plating nickel on WattsLiquid (NiSO) 4 250g/L，NiCl 2 40g/L, 35g/L boric acid, 0.05g/L sodium dodecyl sulfate and pH of 3.8-4.4), using metallic nickel as an anode, using a film-coated stainless steel electrode as a cathode, and having a current density of 1.5A/dm 2 Electroplating for 6 hours at the temperature of 60 ℃ to obtain a plurality of metal microcolumns arranged in an array;
6. cleaning the electroplated electrode with the array metal micro-column structure by using deionized water, and performing pyrolysis heat removal for 5 hours at 700 ℃ in an atmosphere furnace under the protection of argon to remove residual insulating adhesive tapes on the surface;
7. and cleaning the electrodes of the array metal micro-column structure after pyrolysis treatment by using acetone and deionized water, drying for 2h at 80 ℃ to obtain electrodes of which the surface metal micro-columns have the diameter of 100 micrometers and the length of 200 micrometers, and the interval between every two adjacent metal micro-columns is 300 micrometers, and marking as an array electrode B.
And respectively carrying out discharge voltage stability test on the two electrodes in an electrode test system, wherein under the conditions of the same switch form, loading voltage and 0.6MPa of high-purity nitrogen, stainless steel is used as an anode, and a copper electrode or the array electrode A or the stainless steel electrode in the embodiment 1 or the array electrode B in the embodiment 2 is used as a cathode. The obtained breakdown voltage and the relative standard deviation of the voltage are shown in table 1, and it can be seen that the electrode breakdown voltage dispersity with an array structure is obviously reduced, and the operation stability of the pulse power device can be greatly improved by adopting the electrode as a gas switch cathode.
Table 1: electrode breakdown voltage and relative standard deviation test results
| Electrode type | Breakdown voltage (kV) | Relative Standard Deviation (SD) |
| Copper electrode | 100 | 4％ |
| Array electrode A | 80 | 0.6％ |
| Stainless steel electrode | 95 | 6％ |
| Array electrode B | 76 | 0.8％ |
。
Claims (10)
1. An electrode with a metal micro-column array on the surface, which is characterized in that: comprises a metal electrode substrate and a plurality of metal microcolumns;
all the metal microcolumns are vertically embedded on the metal electrode substrate and distributed in an array on the metal electrode substrate; the diameter of the metal microcolumn ranges from 25 micrometers to 200 micrometers, the length-diameter ratio of the metal microcolumn ranges from 1:1 to 5:1, and the metal microcolumn extends into the metal electrode substrate by 10 micrometers to 50 micrometers; the interval between every two adjacent metal microcolumns is 50-1000 mu m.
2. The electrode with the surface provided with the metal micro-column array according to claim 1, characterized in that: the metal microcolumn is grown on the metal electrode substrate in an electroplating deposition mode.
3. The electrode having a surface with an array of metal micropillars according to claim 1 or 2, wherein: the metal electrode substrate is made of stainless steel or copper, and the metal microcolumn is made of copper or nickel.
4. A method for preparing an electrode with a metal micropillar array on the surface, which is used for preparing the electrode with the metal micropillar array on the surface of claim 1, and comprises the following steps:
step 1: cleaning the surface of the metal electrode substrate, and coating an insulating film on the surface of the metal electrode substrate;
step 2: etching cylindrical holes in array arrangement on the surface of the metal electrode substrate of the film in a laser etching mode;
and step 3: cleaning the metal electrode substrate with the cylindrical hole again, and removing an oxide film at the bottom of the cylindrical hole due to the laser action through acid liquor;
and 4, step 4: growing a metal microcolumn vertical to the metal electrode substrate in each cylindrical hole in an electroplating deposition mode;
and 5: and finally, removing the redundant insulating film through carbonization treatment to obtain the electrode with the array structure on the surface.
5. The method for preparing an electrode having a metal micropillar array on the surface thereof according to claim 4, wherein: the diameter of the metal microcolumn ranges from 25 micrometers to 200 micrometers, and the length-diameter ratio of the metal microcolumn ranges from 1:1 to 5: 1; the interval between every two adjacent metal microcolumns is 50-1000 mu m.
6. The method for preparing an electrode having a metal micropillar array on the surface thereof according to claim 4, wherein: the depth range of the etched cylindrical hole in the step 2 is 10-50 mu m; the laser is an ultraviolet laser.
7. The method for preparing an electrode having a metal micropillar array on its surface as claimed in claim 4, wherein: the insulating film is made of transparent adhesive tape or polyimide glue and is firmly combined with the metal electrode substrate through bonding.
8. The method for preparing an electrode having a metal micropillar array on the surface thereof according to claim 4, wherein: and 3, selecting dilute sulfuric acid, dilute nitric acid, hydrochloric acid or mixed acid solution as the acid solution.
9. The method for preparing an electrode having a metal micropillar array on the surface thereof according to claim 4, wherein: the temperature range of the carbonization treatment in the step 5 is 400-800 ℃, and the carbonization treatment process is carried out in argon, nitrogen, reducing atmosphere or vacuum environment.
10. The method for preparing an electrode having a metal micropillar array on the surface thereof according to claim 4, wherein: the metal electrode substrate is made of stainless steel or copper, and the metal microcolumn is made of copper or nickel.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3812559A (en) * | 1970-07-13 | 1974-05-28 | Stanford Research Inst | Methods of producing field ionizer and field emission cathode structures |
| CN101950686A (en) * | 2010-08-23 | 2011-01-19 | 清华大学 | Three-dimensional structure microelectrode applied to mini-super capacitor and manufacturing method thereof |
| CN104269744A (en) * | 2014-10-10 | 2015-01-07 | 广州市汇研微电子技术有限公司 | High-concentration small-granule anion generator system |
| CN108336645A (en) * | 2017-12-28 | 2018-07-27 | 青岛海尔智能技术研发有限公司 | Ion air-supply arrangement and its method for maintaining |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3812559A (en) * | 1970-07-13 | 1974-05-28 | Stanford Research Inst | Methods of producing field ionizer and field emission cathode structures |
| CN101950686A (en) * | 2010-08-23 | 2011-01-19 | 清华大学 | Three-dimensional structure microelectrode applied to mini-super capacitor and manufacturing method thereof |
| CN104269744A (en) * | 2014-10-10 | 2015-01-07 | 广州市汇研微电子技术有限公司 | High-concentration small-granule anion generator system |
| CN108336645A (en) * | 2017-12-28 | 2018-07-27 | 青岛海尔智能技术研发有限公司 | Ion air-supply arrangement and its method for maintaining |
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