CN114289854B - Method for preparing copper-silver alloy hydrogen evolution catalyst by friction stir processing - Google Patents
Method for preparing copper-silver alloy hydrogen evolution catalyst by friction stir processing Download PDFInfo
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Abstract
The invention relates to a method for preparing a copper-silver alloy hydrogen evolution catalyst by friction stir processing; taking a block-shaped metal copper plate, a copper sheet and a silver sheet as raw materials; fixing the metal copper plates and the staggered copper silver plates on a workbench of a friction stir welding machine by using a clamp, and clamping the silver plates and the copper plates between the two copper plates in a staggered manner, wherein the superposition width of the copper silver plates is smaller than the diameter of a stirring head; using a stirring head with a shaft shoulder; the stirring head is aligned with the copper silver sheet when processing is started, the stirring head is adjusted to be pressed down until the stirring pin is completely immersed into processed metal, and the stirring head automatically rotates along one end of the copper silver sheet to advance to the other end for mixing once; until the copper-silver boundary on the surface disappears; the metal strips extruded by the stirring head are cut off to be directly used as the catalyst. The invention solves the problem that the prior non-solid solution metal alloying method is not suitable for block materials. The friction stir processing is applied to the field of electrocatalysis for the first time, the process is simple, the operation is convenient, toxic reaction raw materials are not used, and the method is an environment-friendly green synthesis process.
Description
Technical Field
The invention relates to the technical field of welding and the field of electrocatalysis, in particular to a friction stir processing technology and hydrogen evolution performance of a self-supporting material.
Background
The alloying of the non-solid solution metal can adjust the electronic state of the whole metal, and the non-solid solution alloy has very good application prospect in the field of electrocatalysis. Copper is used for catalytic hydrogen evolution reactions due to its excellent electrical conductivity and abundant reserves, which mainly comprise two processes, adsorption and desorption, and if the adsorption is strong, the desorption process is difficult to occur, and all available surface sites are occupied, making it difficult for the reaction to proceed; when the catalyst is easy to desorb, the adsorption is too weak, so that the equilibrium point of the adsorption and the desorption is found, and the adsorption of hydrogen atoms cannot be too strong or weak on the surface of an ideal catalyst; the d layer of electrons of copper are completely filled, the reverse bonding state is lower than the fermi level, the bonding strength is small, the bonding with the adsorbate is weak, the adsorption process of hydrogen evolution reaction is difficult, and a large overpotential is required to be applied to enable the reaction to occur; if the catalytic performance of copper is to be improved, a second metal, such as silver, is introduced to form copper-silver non-solid solution alloy, the electronic state of copper is adjusted, the position of the d-band center of copper is adjusted, the adsorption of hydrogen on the surface of copper is enhanced, the adsorption process is easier to occur, the overpotential required by the reaction is smaller, and thus the efficient hydrogen evolution catalyst is obtained, see Ruban A, hammer B, stoltze P, et al surface electronic structure and reactivity of transition and noble metals [ J ]. Journal of Molecular Catalysis A:chemical,1997,115 (3): 421-429.
The constituent elements of the non-solid solution metal system are lack of thermodynamic driving force and cannot be alloyed at normal temperature and pressure, for example, copper and silver have only small solid solubility, direct alloying is difficult to realize by using a conventional method, an alloying method becomes a research focus, various non-solid solution metal alloying methods such as ball milling, physical vapor deposition, ion beam mixing and the like are sequentially appeared in recent years, see Huang Yuan, du Jinlong and Wang Zumin.
The friction stir processing is a solid phase connection process, and the metal materials are plasticized by the heat generated by friction between a high-speed rotary stirring head and a welded workpiece, so that the welding of two metals is realized under the combined action of stirring and shaft shoulder pressure. At present, the method is only used as an effective welding mode of bulk materials, not aiming at metal mixing, but changing the process method and parameters of conventional welding or realizing good dispersion of second phase metals.
Disclosure of Invention
Aiming at the problem that the existing preparation process can not obtain a stable and efficient copper-silver alloy catalyst, the copper-silver alloy self-supporting material is prepared by using a friction stir processing copper plate, a copper sheet and a silver sheet, and the catalyst with lower hydrogen evolution overpotential is obtained by the advantage of non-solid solution alloy, and the excellent performance of the catalyst is not attenuated for a long time. The stirring friction welder uses a stirring head with a shaft shoulder, the stirring head consists of the shaft shoulder and a stirring needle, the stirring needle is a conical part with one end protruding out, and the cylindrical part is the shaft shoulder. The stirring head is used as a stirring tool for copper-silver mixing by utilizing the characteristics that a stirring pin rotates to drive metal to flow and a shaft shoulder is pressed down; copper silver flake realizes the preliminary dispersion of copper silver through crisscross superimposed mode, increases copper silver's contact surface and is convenient for realize more even mixing, receives the shearing force and the downforce of shaft shoulder that the stirring head rotation brought again, and two metals undergo strong plastic deformation and flow mixing in solid state, forms copper silver alloy block. The invention has simple process, ingenious design, safety, controllability and low cost.
The technical scheme of the invention is as follows:
the method for preparing the copper-silver alloy hydrogen evolution catalyst by using friction stir processing comprises the following steps:
(1) Taking a block-shaped metal copper plate, a copper sheet and a silver sheet as raw materials; cleaning the surface of the raw material;
(2) Fixing the metal copper plates and the staggered copper silver plates on a workbench of a friction stir welding machine by using a clamp, and clamping the silver plates and the copper plates between the two copper plates in a staggered manner, wherein the superposition width of the copper silver plates is smaller than the diameter of a stirring head;
(3) Using a stirring head with a shaft shoulder; when the processing is started, the stirring head is aligned with the copper silver flake, the stirring head is adjusted to be pressed down until the stirring pin is completely immersed into the processed metal, the distance between the shaft shoulder and the surface of the copper plate is less than 2mm, and the stirring head automatically rotates along one end of the copper silver flake to advance to the other end for mixing once; if clear copper-silver boundary parallel to the processing direction can still be observed on the surface of the processing area, the copper-silver boundary needs to be mixed again until the copper-silver boundary on the surface disappears;
(4) Sampling: the stirring head starts to process from the last processing starting position, the stirring head automatically rotates along one end of the copper silver sheet to the other end, and the stirring head is adjusted to be pressed down until the metal below the stirring head is extruded from the two sides of the stirring head; the metal strips extruded by the stirring head are cut off to be directly used as the catalyst.
The method for cleaning the surface of the raw material comprises the following steps: polishing the surface of the raw material by sand paper and then ultrasonically cleaning the surface by dilute hydrochloric acid to remove an oxide layer; and then cleaning the surface of the raw material with deionized water for several times to remove residual dilute hydrochloric acid, and then drying the surface of the raw material for later use.
The rotating speed of the friction stir welding machine is preferably 600-1800 rpm, and the welding speed is preferably 30-200 mm/min. We usually combine the two conditions abbreviated rpm-mm/min.
The metal strip is directly used as a cathode for producing hydrogen by water electrolysis.
The number of the silver sheets is more than 1, the copper sheets are used for separating the silver sheets, and the arrangement sequence of the metal copper plate and the copper silver sheets is [ copper plate+silver sheet+ (copper sheet+silver sheet) n +copper plate]，n>0。
The heights of the copper plates and the copper silver plates are equal, and the heights of the copper plates and the copper silver plates are larger than the length of the stirring pin; among them, preferred is:
copper plate: the length is more than or equal to 10mm, the width is more than or equal to 10mm, and the height is more than or equal to 3mm;
copper sheet: the length is more than or equal to 10mm, the width is more than or equal to 0.01mm, and the height is more than or equal to 3mm;
silver flake: the length is more than or equal to 10mm, the width is more than or equal to 0.01mm, and the height is more than or equal to 3mm.
The metal strip preferably has a silver content of greater than 3%.
The preferable surface of the metal strip is provided with regular arc lines, and the thickness is 2+/-1 mm.
The stirring head is preferably a conical stirring head, the material is steel, tungsten-based alloy or nickel-based alloy, and the length of the stirring pin is smaller than the thickness of the copper plate.
The concrete explanation is as follows:
to avoid reoxidation, the raw materials should be processed immediately after washing and drying.
The purity of the copper plate and the copper silver sheet is more than 99%, and if the copper silver alloy with higher purity is required to be obtained, the higher the purity of the raw material is, the better the raw material is.
The influence of the rotating speed of the stirring head on metal mixing is larger than the welding speed, and the faster rotating speed is beneficial to metal mixing.
The stirring head used for processing is a conical stirring head, the material is tungsten steel, and the length of the stirring pin is 3mm. The material of the stirring head can be replaced, and only the hardness and the melting point are higher than those of copper and silver, such as nickel-based alloy, steel and the like; the stirring pin is conical, the length of the stirring pin is matched with the thickness of the copper plate, and the length of the stirring pin is smaller than the thickness of the copper plate.
Electrochemical testing of the catalyst Using 0.5mol/L H 2 SO 4 The method is characterized in that the method comprises the steps of immersing the metal strip serving as a cathode (working electrode) for producing hydrogen by electrolyzing water in the electrolyte for at least 2 minutes before testing, and connecting the metal strip to a three-electrode (working electrode, reference electrode and counter electrode) system for testing, wherein bubbles continuously emerge from the surface of the catalyst in the testing process, so that the hydrogen evolution reaction is performed.
The copper-silver alloy with excellent hydrogen evolution performance has the advantages that the silver content is at least more than 3%, and the higher the silver content is, the more uniform the distribution is, the better the performance is; in order to facilitate sampling the thickness of the catalyst to be (2+/-1) mm, the surface is provided with regular arc lines, so that the catalyst and the electrolyte are ensured to have a larger contact area.
The invention has the following advantages: the invention utilizes friction stir processing to prepare the copper-silver alloy, and solves the problem that the existing non-solid solution metal alloying method is not suitable for block materials. The friction stir processing is applied to the field of electrocatalysis for the first time, so that the simple green synthesis of the copper-silver alloy self-supported catalyst is realized under the ordinary external environment at normal temperature and normal pressure, and the coating process of the catalyst is omitted. The catalyst was used at 10mA/cm 2 The overpotential at the position is half of that of a unprocessed copper plate, and the huge effect of non-solid solution metal alloying on improving the hydrogen evolution performance of the catalyst is proved for the first time; the equivalent current is not attenuated after 180 hours of continuous reaction, and the excellent stability of the copper-silver alloy self-supporting catalyst is proved. In addition, the synthesis method adopted by the invention has simple process, convenient operation and easy control, belongs to normal-temperature and normal-pressure synthesis, does not use toxic reaction raw materials, and is an environment-friendly green synthesis process.
Drawings
Fig. 1 is a diagram of a process apparatus for preparing copper-silver alloy by friction stir processing.
FIG. 2 is an LSV curve of a copper-silver alloy obtained by friction stir processing, wherein the width of one silver sheet is 1mm, and the parameters are 1800 rpm-100 mm/min;
FIG. 3 is a LSV curve of a copper-silver alloy obtained by friction stir processing, wherein the width of one silver sheet is 1mm, and the parameters are 1200 rpm-30 mm/min;
FIG. 4 is a LSV curve of a copper-silver alloy obtained by friction stir processing, wherein the width of one silver sheet is 1mm, and the parameters are 1200 rpm-200 mm/min;
FIG. 5 is a LSV curve of a copper-silver alloy obtained by friction stir processing, wherein the width of two silver sheets is 0.5mm, and the parameters are 1200 rpm-100 mm/min;
FIG. 6 is a LSV curve of a copper-silver alloy obtained by friction stir processing, wherein the widths of three silver sheets are 0.5mm, and the parameters are 1200 rpm-100 mm/min;
FIG. 7 is a LSV curve of a copper-silver alloy obtained by friction stir processing, wherein the width of four silver sheets is 0.5mm, and the parameters are 600 rpm-100 mm/min;
FIG. 8 is a graph of (a) LSV of a copper silver alloy obtained by friction stir processing; (b) an i-t curve; (c) XRD, the width of the four silver sheets is 0.5mm, and the parameters are 1200 rpm-100 mm/min.
Detailed Description
As shown in the process device diagram of FIG. 1, copper plates on two sides are fixed on a workbench under the pressure of a clamp in the vertical direction and the horizontal direction, copper-silver sheet overlapping is needed to be fixed by extrusion of copper plates on two sides, and the fixing mode can be implemented according to specific conditions, and the whole processing process is not loosened as a standard. The stirring head automatically rotates along one end of the copper silver sheet to the other end, when the stirring head rotates, metal below the stirring head is extruded from two sides of the stirring head, metal strips are formed to be left on the upper surface of the copper plate, and regular arc lines are left on the surface of the area processed by the stirring head.
The friction stir welding machine is FSW-3LM-020 type equipment manufactured by Beijing Saifusi technology Co., ltd, and the flash is about one millimeter thick and is easy to cut from a copper plate.
Controlling the area immersed in the electrolyte to be at least 0.2cm during electrochemical testing of flash 2 Too small an area is inconvenient for testing.
Example 1:
(1) Taking a block-shaped metal copper plate, a copper sheet and a silver sheet as raw materials; cleaning the surface of the raw material;
(2) Fixing a metal copper plate and a silver sheet on a workbench of a friction stir welding machine by using a clamp, and clamping a silver sheet (length is 20mm multiplied by width is 1mm multiplied by height is 5 mm) between the two copper plates;
(3) Using a stirring head with a shaft shoulder; the stirring head is aligned with the copper silver flake when processing is started, the stirring head is adjusted to be pressed down until the stirring pin is completely immersed into the processed metal, the distance between the shaft shoulder and the surface of the copper plate is less than 2mm, and the stirring head is automatically rotated along one end of the copper silver flake to advance to the other end for mixing once under the condition that the processing parameters are set to 1800 rpm-100 mm/min;
(4) Sampling: the stirring head starts to process from the last processing starting position, the stirring head automatically rotates along one end of the copper silver sheet to the other end, and the stirring head is adjusted to be pressed down until the metal below the stirring head is extruded from the two sides of the stirring head; the metal strips extruded by the stirring head are cut off to be directly used as the catalyst.
The hydrogen evolution performance test is carried out on the copper-silver alloy obtained by friction stir processing, and the linear sweep voltammetry curve of the test is shown as figure 2, 10mA/cm 2 The overpotential at this point was 384mV and the silver content was 6.8%.
Example 2:
(1) Taking a block-shaped metal copper plate, a copper sheet and a silver sheet as raw materials; cleaning the surface of the raw material;
(2) Fixing a metal copper plate and a silver sheet on a workbench of a friction stir welding machine by using a clamp, and clamping a silver sheet (length is 20mm multiplied by width is 1mm multiplied by height is 5 mm) between the two copper plates;
(3) Using a stirring head with a shaft shoulder; the stirring head is aligned with the copper silver flake when processing is started, the stirring head is adjusted to be pressed down until the stirring pin is completely immersed into the processed metal, the distance between the shaft shoulder and the surface of the copper plate is less than 2mm, and the stirring head is automatically rotated along one end of the copper silver flake to advance to the other end for mixing once under the condition that the processing parameters are set to be 1200 rpm-30 mm/min;
(4) Sampling: the stirring head starts to process from the last processing starting position, the stirring head automatically rotates along one end of the copper silver sheet to the other end, and the stirring head is adjusted to be pressed down until the metal below the stirring head is extruded from the two sides of the stirring head; the metal strips extruded by the stirring head are cut off to be directly used as the catalyst.
The hydrogen evolution performance test is carried out on the copper-silver alloy obtained by friction stir processing, and the linear sweep voltammetry curve of the test is shown as figure 3, 10mA/cm 2 The overpotential at this point was 390mV and the silver content was 6.8%.
Example 3:
(1) Taking a block-shaped metal copper plate, a copper sheet and a silver sheet as raw materials; cleaning the surface of the raw material;
(2) Fixing a metal copper plate and a silver sheet on a workbench of a friction stir welding machine by using a clamp, and clamping a silver sheet (length is 20mm multiplied by width is 1mm multiplied by height is 5 mm) between the two copper plates;
(3) Using a stirring head with a shaft shoulder; the stirring head is aligned with the copper silver flake when processing is started, the stirring head is adjusted to be pressed down until the stirring pin is completely immersed into the processed metal, the distance between the shaft shoulder and the surface of the copper plate is less than 2mm, and the stirring head is automatically rotated along one end of the copper silver flake to advance to the other end for mixing once under the condition that the processing parameters are set to be 1200 rpm-200 mm/min;
(4) Sampling: the stirring head starts to process from the last processing starting position, the stirring head automatically rotates along one end of the copper silver sheet to the other end, and the stirring head is adjusted to be pressed down until the metal below the stirring head is extruded from the two sides of the stirring head; the metal strips extruded by the stirring head are cut off to be directly used as the catalyst.
The hydrogen evolution performance test is carried out on the copper-silver alloy obtained by friction stir processing, and the linear sweep voltammetry curve of the test is shown as figure 4, 10mA/cm 2 The overpotential at this point was 485mV and the silver content was 6.8%.
Example 4:
(1) Taking a block-shaped metal copper plate, a copper sheet and a silver sheet as raw materials; cleaning the surface of the raw material;
(2) Fixing a metal copper plate and copper silver sheets on a workbench of a friction stir welding machine by using a clamp, separating two silver sheets (20 mm long by 0.5mm wide by 5mm high) by using a copper sheet (20 mm long by 0.05mm wide by 5mm high), and then clamping the copper sheets between the two copper plates;
(3) Using a stirring head with a shaft shoulder; the stirring head is aligned with the copper silver flake when processing is started, the stirring head is adjusted to be pressed down until the stirring pin is completely immersed into the processed metal, the distance between the shaft shoulder and the surface of the copper plate is less than 2mm, and the stirring head is automatically rotated along one end of the copper silver flake to advance to the other end for mixing once under the condition that the processing parameters are set to be 1200 rpm-100 mm/min;
(4) Sampling: the stirring head starts to process from the last processing starting position, the stirring head automatically rotates along one end of the copper silver sheet to the other end, and the stirring head is adjusted to be pressed down until the metal below the stirring head is extruded from the two sides of the stirring head; the metal strips extruded by the stirring head are cut off to be directly used as the catalyst.
The hydrogen evolution performance test is carried out on the copper-silver alloy obtained by friction stir processing, and the linear sweep voltammetry curve of the test is shown as figure 5, 10mA/cm 2 The overpotential at this point was 318mV and the silver content was 9.8%.
Example 5:
(1) Taking a block-shaped metal copper plate, a copper sheet and a silver sheet as raw materials; cleaning the surface of the raw material;
(2) Fixing a metal copper plate and copper silver sheets on a workbench of a friction stir welding machine by using a clamp, separating three silver sheets (20 mm long by 0.5mm wide by 5mm high) by using two copper sheets (20 mm long by 0.05mm wide by 5mm high), and then clamping the copper sheets between the two copper plates;
(3) Using a stirring head with a shaft shoulder; the stirring head is aligned with the copper silver flake when processing is started, the stirring head is adjusted to be pressed down until the stirring pin is completely immersed into the processed metal, the distance between the shaft shoulder and the surface of the copper plate is less than 2mm, and the stirring head is automatically rotated along one end of the copper silver flake to advance to the other end for mixing once under the condition that the processing parameters are set to be 1200 rpm-100 mm/min;
(4) Sampling: the stirring head starts to process from the last processing starting position, the stirring head automatically rotates along one end of the copper silver sheet to the other end, and the stirring head is adjusted to be pressed down until the metal below the stirring head is extruded from the two sides of the stirring head; the metal strips extruded by the stirring head are cut off to be directly used as the catalyst.
The hydrogen evolution performance test is carried out on the copper-silver alloy obtained by friction stir processing, and the linear sweep voltammetry curve of the test is shown as figure 6, 10mA/cm 2 The overpotential at this point was 295mV and the silver content was 13.4%.
Example 6:
(1) Taking a block-shaped metal copper plate, a copper sheet and a silver sheet as raw materials; cleaning the surface of the raw material;
(2) Fixing the metal copper plate and the copper silver sheet on a workbench of a friction stir welding machine by using a clamp, separating four silver sheets (20 mm long by 0.5mm wide by 5mm high) by using three copper sheets (20 mm long by 0.05mm wide by 5mm high), and then clamping the copper sheets between the two copper plates;
(3) Using a stirring head with a shaft shoulder; the stirring head is aligned with the copper silver flake when processing is started, the stirring head is adjusted to be pressed down until the stirring pin is completely immersed into the processed metal, the distance between the shaft shoulder and the surface of the copper plate is less than 2mm, and the stirring head is automatically rotated along one end of the copper silver flake to advance to the other end for mixing once under the condition that the processing parameters are set to be 600 rpm-100 mm/min;
(4) Sampling: the stirring head starts to process from the last processing starting position, the stirring head automatically rotates along one end of the copper silver sheet to the other end, and the stirring head is adjusted to be pressed down until the metal below the stirring head is extruded from the two sides of the stirring head; the metal strips extruded by the stirring head are cut off to be directly used as the catalyst.
The hydrogen evolution performance test is carried out on the copper-silver alloy obtained by friction stir processing, and the linear sweep voltammetry curve of the test is shown as figure 7, 10mA/cm 2 The overpotential at this point was 366mV and the silver content was 17%.
Example 7:
(1) Taking a block-shaped metal copper plate, a copper sheet and a silver sheet as raw materials; cleaning the surface of the raw material;
(2) Fixing the metal copper plate and the copper silver sheet on a workbench of a friction stir welding machine by using a clamp, separating four silver sheets (20 mm long by 0.5mm wide by 5mm high) by using three copper sheets (20 mm long by 0.05mm wide by 5mm high), and then clamping the copper sheets between the two copper plates;
(3) Using a stirring head with a shaft shoulder; the stirring head is aligned with the copper silver flake when processing is started, the stirring head is adjusted to be pressed down until the stirring pin is completely immersed into the processed metal, the distance between the shaft shoulder and the surface of the copper plate is less than 2mm, and the stirring head is automatically rotated along one end of the copper silver flake to advance to the other end for mixing once under the condition that the processing parameters are set to be 1200 rpm-100 mm/min;
(4) Sampling: the stirring head starts to process from the last processing starting position, the stirring head automatically rotates along one end of the copper silver sheet to the other end, and the stirring head is adjusted to be pressed down until the metal below the stirring head is extruded from the two sides of the stirring head; the metal strips extruded by the stirring head are cut off to be directly used as the catalyst.
The hydrogen evolution performance test of the copper-silver alloy obtained by friction stir processing is shown in fig. 8. FIG. 8a is a linear sweep voltammogram of 10mA/cm 2 The overpotential at this point was 256mV and the silver content was 17%. FIG. 8b is a stability test result showing that the copper-silver alloy 180h under a certain voltage maintains a current of 0.5A/cm 2 Stable and unchanged, and good stability. As shown in fig. 8c, the phase analysis was performed on the copper-silver alloy obtained by friction stir processing, and the presence of copper and silver was detected, and the occurrence of peak shift proved to form an alloy.
The technical scheme disclosed and proposed by the invention can be realized by a person skilled in the art by appropriately changing the condition route and other links in consideration of the content of the present invention, although the method and the preparation technology of the invention have been described by the preferred embodiment examples, the related person can obviously modify or recombine the method and the technical route described herein to realize the final preparation technology without departing from the content, spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be included within the spirit, scope and content of the invention. The invention belongs to the known technology.
Claims (9)
1. The method for preparing the copper-silver alloy hydrogen evolution catalyst by using friction stir processing is characterized by comprising the following steps of:
(1) Copper plates, copper sheets and silver sheets are used as raw materials; cleaning the surface of the raw material;
(2) Fixing the copper plates, the copper sheets and the silver sheets on a workbench of a friction stir welding machine by using a clamp, and alternately arranging the silver sheets and the copper sheets between the two copper plates, wherein the width formed by overlapping the copper sheets and the silver sheets is smaller than the diameter of a stirring head;
(3) Using a stirring head with a shaft shoulder; when the processing is started, the stirring head is aligned with the copper silver sheet, the stirring head is adjusted to be pressed down until the stirring pin is completely immersed into the processed metal, the distance between the shaft shoulder and the surface of the copper plate is less than 2mm, and the stirring head automatically rotates along one end of the copper silver sheet to advance to the other end for mixing once; if clear copper-silver boundary parallel to the processing direction can still be observed on the surface of the processing area, the copper-silver boundary needs to be mixed again until the copper-silver boundary on the surface disappears;
(4) Sampling: the stirring head starts to process from the last processing starting position, the stirring head automatically rotates along one end of the copper silver sheet to the other end, and the stirring head is adjusted to be pressed down until the metal below the stirring head is extruded from the two sides of the stirring head; the metal strips extruded by the stirring head are cut off to be directly used as the catalyst.
2. The method of claim 1, wherein the raw material surface cleaning method comprises the steps of: polishing the surface of the raw material by sand paper and then ultrasonically cleaning the surface by dilute hydrochloric acid to remove an oxide layer; and then cleaning the surface of the raw material with deionized water for several times to remove residual dilute hydrochloric acid, and then drying the surface of the raw material for later use.
3. The method of claim 1, wherein the friction stir welding machine has a rotational speed of 600 to 1800rpm and a welding speed of 30 to 200mm/min.
4. The method of claim 1, wherein the metal strip directly acts as a cathode for producing hydrogen by electrolysis of water.
5. The method of claim 1, wherein the number of silver flakes is greater than 1, the copper flakes are used to separate the silver flakes, and the copper, copper and silver flakes are arranged in the order copper + silver + (copper + silver flakes) n +copper plate, n>0。
6. The method of claim 1, wherein the copper plate, copper sheet, and silver sheet are equal in height and greater than the length of the pin;
wherein: copper plate: the length is more than or equal to 10mm, the width is more than or equal to 10mm, and the height is more than or equal to 3mm;
copper sheet: the length is more than or equal to 10mm, the width is more than or equal to 0.01mm, and the height is more than or equal to 3mm;
silver flake: the length is more than or equal to 10mm, the width is more than or equal to 0.01mm, and the height is more than or equal to 3mm.
7. The method of claim 1, wherein the silver content of the metal strip is greater than 3%.
8. The method of claim 1, wherein the metal strip has regular arcuate patterns on its surface and a thickness of 2±1mm.
9. The method of claim 1, wherein the stirring head is a conical stirring head, the material is steel, tungsten-based alloy or nickel-based alloy, and the length of the stirring pin is less than the thickness of the copper plate.
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| CN104227225B (en) * | 2014-09-01 | 2017-02-01 | 西安交通大学 | Agitation friction point braze welding method for metal plate overlap joint combination |
| CN106181017A (en) * | 2016-07-11 | 2016-12-07 | 中国船舶重工集团公司第七二五研究所 | A kind of friction stir welding method of corronil |
| JP6875212B2 (en) * | 2017-06-23 | 2021-05-19 | トヨタ自動車株式会社 | Manufacturing method of terminal plate |
| CN107598359A (en) * | 2017-11-01 | 2018-01-19 | 广东柳泰焊接科技有限公司 | A kind of preparation method of heat sink |
| CN112605522A (en) * | 2020-12-16 | 2021-04-06 | 厦门理工学院 | Welding method of Pb-Ag-RE alloy anode plate |
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2022
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