CN114965615A - Mechanical stirring preparation of copper electrode with high-density dislocation and application of copper electrode in electrochemical hydrogen evolution reaction - Google Patents
Mechanical stirring preparation of copper electrode with high-density dislocation and application of copper electrode in electrochemical hydrogen evolution reaction Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 75
- 239000010949 copper Substances 0.000 title claims abstract description 75
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 38
- 239000001257 hydrogen Substances 0.000 title claims abstract description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000010907 mechanical stirring Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000003466 welding Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003754 machining Methods 0.000 claims abstract description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000011089 carbon dioxide Nutrition 0.000 claims abstract description 5
- 229910000691 Re alloy Inorganic materials 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- DECCZIUVGMLHKQ-UHFFFAOYSA-N rhenium tungsten Chemical compound [W].[Re] DECCZIUVGMLHKQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 244000137852 Petrea volubilis Species 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052697 platinum Inorganic materials 0.000 abstract description 6
- 238000012545 processing Methods 0.000 description 13
- 238000009826 distribution Methods 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000003775 Density Functional Theory Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000007806 chemical reaction intermediate Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 241000784732 Lycaena phlaeas Species 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to a method for preparing a copper electrode with high-density dislocation by mechanical stirring and an electrochemical hydrogen evolution reaction. Using a block-shaped metal copper plate as a raw material; removing the oxide layer on the surface of the raw material; then, washing the surface of the raw material with deionized water and ethanol for several times to remove residual dilute hydrochloric acid, and then drying the surface of the raw material; fixing the dried metal copper plate on a workbench of a friction stir welding machine by using a clamp, and adopting a tungsten-rhenium alloy stirring head with a stirring pin; starting the friction stir welding machine, setting the rotating speed of 100-; meanwhile, in the whole process of mechanical stirring, the copper plate is cooled by dry ice; and after the machining is finished, cutting the arc-shaped grain area to obtain the copper block electrode. The copper electrode has excellent electrochemical hydrogen evolution reaction activity, and specifically reaches 1A/cm under the over potential of-1.2V 2 Current density, and can work stably for 50 hours, and the activity and stability at the potential exceed those of metal platinum.
Description
Technical Field
The invention relates to the field of metal electrode preparation, and relates to a copper metal electrochemical hydrogen evolution reaction electrode with high-density dislocation. In particular to a mechanical stirring preparation method of a copper electrode with high density dislocation for electrochemical hydrogen evolution reaction.
Background
The electrochemical hydrogen evolution reaction is used as a means for preparing hydrogen, and meets the clean and efficient requirements of energy and environmental development in the current society. The efficiency of hydrogen evolution reactions driven by renewable electricity depends to a large extent on the catalytic activity of the electrodes. The activity of the metal catalyst electrode depends on the adsorption strength of the catalyst to reaction intermediates, and the reduction of the catalytic activity can be caused by the over-strong or over-weak adsorption. Among various metal materials researched at present, metal platinum has higher catalytic activity, so that the metal platinum has more applications in electrochemical hydrogen evolution reaction. However, the expensive price of platinum as a noble metal limits its further large-scale use.
The metallic copper has rich reserves and low price, is a high-conductivity metallic material, and has the potential of being applied to the field of electrocatalysis. However, the d-electron orbitals of metallic copper are completely filled, and the adsorption to catalytic reaction intermediates is weak, so the activity to electrochemical hydrogen evolution reaction is poor. Defects (such as stacking faults) can improve the adsorption energy of catalytic reaction intermediates by adjusting surface atom coordination and introducing lattice distortion, however, in nanoparticles, defects are difficult to stably exist in nanomaterials due to large specific surface area brought by small size and self-purification effect thereof. Meanwhile, the nanoparticles need to be coated on the surface of the electrode, and have problems of agglomeration or falling off. Compared with the prior art, the bulk material has the advantages that the relatively stable defect can be observed more, meanwhile, the bulk metal can be used for directly preparing the electrode with the self-supporting structure, the preparation is convenient, the performance is stable, and the industrial application is facilitated.
In summary, the field of electrochemical hydrogen evolution still lacks of metal catalysts which have high activity, low price and are easy to be applied in large scale. Meanwhile, the existing nanoparticles with relatively high activity have unstable phenomenon, so that the metal catalyst electrode with a self-supporting structure has certain advantages.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a metal copper electrode which is prepared by machining and has activity and low price. The strong deformation effect of the mechanical stirring processing technology and the quick cooling effect of the dry ice are utilized to introduce high-density dislocation into the bulk metal copper, and the high-density dislocation promotes the activity of the electrochemical hydrogen evolution reaction, so that the self-supporting metal electrode material with the structure function integration is prepared. The machining process is connected with the functional material, the inactive metal copper is modified into the self-supporting electrode with high activity and durability, and the method has the advantages of interdisciplinary design, simple process, low cost and easy large-scale application.
The invention provides a method for preparing a stable and efficient copper electrode by mechanical stirring processing, which comprises the following steps:
step 1: using a block-shaped metal copper plate as a raw material; polishing the surface of the raw material by using sand paper, and then ultrasonically cleaning the raw material by using dilute hydrochloric acid to remove an oxide layer of the raw material; then, washing the surface of the raw material with deionized water and ethanol for several times to remove residual dilute hydrochloric acid, and then drying the surface of the raw material;
and 2, step: fixing the dried metal copper plate on a workbench of a friction stir welding machine by using a clamp, and adopting a tungsten-rhenium alloy stirring head with a stirring pin; starting the friction stir welding machine, setting the rotation speed of 100-400rpm and the running speed of 30 mm/min; meanwhile, in the whole process of mechanical stirring, the copper plate is cooled by dry ice;
and step 3: and after the machining is finished, the shaft shoulder of the stirring friction welding head leaves an arc-shaped pattern on the copper plate, and the arc-shaped pattern area is cut to obtain the copper block electrode.
The mechanical stirring of the invention is adopted to prepare the copper electrode with high density dislocation for electrochemical hydrogen evolution reaction.
And observing the microstructure of the mechanically stirred and processed copper electrode by adopting an electron microscope technology. By observation in the diffraction contrast imaging mode of a transmission electron microscope, a large number of dislocation lines can be observed. Further, a high-resolution transmission electron microscope image was observed, and distortion of the crystal lattice was observed by inverse fourier transform, and a large amount of edge dislocations were observed. The grain boundary distribution and the intra-grain local misorientation distribution were tested by the electron back-scattering diffraction technique, with a higher proportion of small-angle grain boundaries and a larger distribution of local misorientation compared to the unprocessed copper. The above tests of the micro-topography demonstrate that a large number of dislocations are introduced in the metallic copper by the mechanical stirring process.
The influence of dislocation on the electrochemical hydrogen evolution performance is calculated by adopting a density functional theory analysis. Edge dislocation is embodied as redundant half atomic plane in the crystal, due to the influence of the half atomic plane, the charge density distribution in the crystal is uneven, the charge density of the part with missing half atomic plane is lower, and the lower charge density distribution can cause the enhancement of H adsorption, thereby improving the electrochemical hydrogen evolution performance.
The electrochemical hydrogen evolution activity test is carried out on the copper electrode obtained by mechanical stirring processing, the electrochemical hydrogen evolution reaction activity is excellent, and the electrochemical hydrogen evolution activity reaches 1A/cm under-1.2V overpotential 2 Current density, and can work stably for 50 hours, and the activity and stability at the potential exceed those of metal platinum.
The invention has the following advantages: the metal copper electrode is prepared by a mechanical stirring process, and a large amount of dislocation is introduced through deformation, so that low-activity metal is modified into a hydrogen evolution reaction metal electrode with higher activity. The self-supporting metal electrode structure overcomes the defects that the nano-particle catalyst is easy to agglomerate and fall off, and realizes more durable durability. The mechanical stirring processing technology is simple, convenient and quick, and can be used for quickly preparing and producing metal electrode materials; the used metal copper material has low price. The mechanical processing technology does not use any toxic raw materials and reagents, and is green and environment-friendly.
Drawings
FIG. 1 is a diagram of a process unit for preparing a copper self-supporting electrode by mechanical stirring processing.
FIG. 2 is a microscopic topography of a copper free-standing electrode obtained by mechanical stirring processing.
(1) Diffraction contrast transmission electron microscope images; (2-1) high-resolution transmission electron microscopy images; (2-2) a Fourier transform map corresponding to 2-1; (2-3)2-1, wherein "vertisement" represents a dislocation.
FIG. 3 is a grain boundary orientation difference plot obtained by electron back scattering diffraction technique.
(1) Mechanically stirring the obtained copper; (2) raw copper
FIG. 4 is a plot of the differential local orientation within a grain obtained by electron back-scattered diffraction techniques.
(1) Mechanically stirring the obtained copper; (2) raw copper
FIG. 5 shows the dislocation structure calculated by the density functional theory and the effect thereof on the electrochemical hydrogen evolution performance.
(1) A schematic view of edge dislocations; (2) edge dislocation atom model diagram; (3) atomic charge density profile of edge dislocations; (4) dislocation-free atomic charge density profiles; (5) dislocation-free (raw copper), and H adsorption gibbs free energy of dislocation points 1, 2.
FIG. 6 is a polarization diagram of electrochemical hydrogen evolution reaction of a copper self-supporting electrode obtained by mechanical stirring processing.
FIG. 7 is a graph showing the stability of electrochemical hydrogen evolution reaction of a copper self-supporting electrode obtained by mechanical stirring.
FIG. 8 is a graph comparing the electrochemical hydrogen evolution performance of copper electrodes obtained by mechanical stirring at different rotation speeds with the small-angle grain boundary density.
Detailed Description
Example 1:
step 1: using a block-shaped metal copper plate as a raw material; polishing the surface of the raw material by using sand paper, and then ultrasonically cleaning the raw material by using dilute hydrochloric acid to remove an oxide layer of the raw material; then, washing the surface of the raw material with deionized water and ethanol for several times to remove residual dilute hydrochloric acid, and then drying the surface of the raw material;
step 2: fixing the dried metal copper plate on a workbench of a friction stir welding machine by using a clamp, and adopting a tungsten-rhenium alloy stirring head with a stirring pin; starting a stirring friction welding machine, setting the rotating speed to be 200rpm, and setting the running speed to be 30 mm/min; meanwhile, in the whole process of mechanical stirring, the copper plate is cooled by dry ice;
and step 3: after the machining is finished, the shaft shoulder of the stirring and rubbing welding head leaves an arc-shaped line on the copper plate, and the arc-shaped line area is cut to obtain a copper block electrode which is directly used as a reaction electrode for subsequent electrochemical hydrogen evolution, as shown in figure 1.
The microstructure morphology of the copper electrode was observed using a transmission electron microscope, as shown in FIG. 2. Dislocation lines were observed in the diffraction contrast mode (FIG. 2-1), and dislocation line plugs formed dislocation bands, indicating that a large number of dislocations were formed in the copper. As shown in figure 2-2-1, the lattice information of the copper electrode is observed by the image of the high-resolution transmission electron microscope, and a large amount of edge dislocations can be observed by the inverse Fourier transform (such as figure 2-2-2,2-2-3) and are marked by +/-.
And (3) qualitatively analyzing the dislocation in the copper electrode by adopting an electron back scattering diffraction technology. As shown in the grain boundary misorientation distribution of FIG. 3, the proportion of the small-angle grain boundaries of the copper electrode obtained by mechanical stirring was higher, particularly, the small-angle grain boundaries of 2 to 5 degrees, as high as 42.7% compared with the unprocessed copper, and the density of the small-angle grain boundaries of 2 to 5 degrees was 1.21. mu.m -1 The large number of small-angle grain boundaries indicates that a large number of dislocations exist in the processed copper. Meanwhile, the local orientation difference distribution pattern (figure 4) in the crystal grains also shows that the local orientation difference distribution of the processed copper electrode is larger, and the dislocation density of the processed copper electrode is up to 8.0 multiplied by 10 through analysis 16 m -2 Whereas the dislocation density of the raw copper is only 6.4X 10 15 m -2 。
The above microstructure tests show that mechanical agitation processing can introduce a large number of dislocations in the copper, thereby improving hydrogen evolution electrochemical activity.
And then analyzing the influence of dislocation on the electrochemical hydrogen evolution performance through density functional theory calculation. The atomic structure model of the edge dislocations is first constructed as shown in FIGS. 5-1 and 5-2. The influence of redundant half-atom planes in the edge dislocation is analyzed through charge density distribution, the half-atom planes can cause uneven charge density distribution, and the charge density changes from high to low around the center of the dislocation. As shown in fig. 5-3, the charge density of the missing half atomic plane part is lower, and is obviously lower than that of a perfect crystal lattice (fig. 5-4, i.e. unprocessed copper), the low charge density can enhance the adsorption of the intermediate H by the metal copper, and as shown in fig. 5-5, compared with 0.58eV of the common copper, the adsorption energy of the processed copper electrode is reduced to 0.39eV, which indicates that the dislocation structure can cause charge density redistribution, enhance the adsorption of the intermediate H by the copper, and thus improve the electrochemical hydrogen evolution activity.
And testing the electrochemical hydrogen evolution performance of the mechanical stirring copper electrode under a three-electrode system. Prepare 0.5M H 2 SO 4 The aqueous solution was used as an electrolyte, a platinum electrode was used as a counter electrode, the copper electrode obtained by the above processing was used as a working electrode, and the electrochemical hydrogen evolution reaction was tested using an electrochemical workstation. The polarization curve reaches 1A/cm in the test 2 Required current densityThe stability of hydrogen evolution of the copper electrode was tested by the i-t curve. The copper electrode is 10mA/cm 2 The over-potential of (a) is 323mV, which reaches 1A/cm at an over-potential of-1.2V 2 Current density (fig. 6), and can be stably operated for 50 hours (fig. 7). The copper electrode prepared by the method has excellent electrochemical hydrogen evolution activity and stability.
Example 2:
the other steps are the same as those of example 1 except that the rotation speed in step 2 is changed to 100 rpm.
Example 3:
the other steps are the same as those of the example 1 except that the rotation speed in the step 2 is changed to 300 rpm.
Example 4:
the other steps are the same as those of the example 1 except that the rotation speed in the step 2 is changed to 400 rpm.
The test result shows that when the processing rotating speed is changed to 100rpm, the dislocation density in the copper electrode is slightly reduced, and the grain boundary density of small angles of 2-5 degrees is 0.99 mu m -1 Meanwhile, the electrochemical hydrogen evolution performance is slightly reduced, 10mA/cm 2 The overpotential of (a) is 356 mV; when the processing rotating speed is changed to 400rpm, the dislocation density in the copper electrode is reduced, and the density of 2-5 degrees small-angle grain boundary is 0.41 mu m -1 And simultaneously the electrochemical hydrogen evolution performance is reduced, 10mA/cm 2 The overpotential of (a) is 476 mV. As shown in fig. 8, when the processing rotation speed is gradually increased from 100rpm, the dislocation density in the copper electrode is increased from low to high, and the electrochemical hydrogen evolution performance is also improved from poor; when the rotating speed is increased to 200rpm, the dislocation density is highest, and the electrochemical hydrogen evolution performance is optimal; when the rotation speed continues to increase, the dislocation density decreases, and the electrochemical hydrogen evolution performance also decreases.
Claims (2)
1. Mechanical agitation to produce copper electrodes with high density dislocations is challenging including the following steps:
(1) using a block-shaped metal copper plate as a raw material; polishing the surface of the raw material by using sand paper, and then ultrasonically cleaning the raw material by using dilute hydrochloric acid to remove an oxide layer of the raw material; then, washing the surface of the raw material with deionized water and ethanol for several times to remove residual dilute hydrochloric acid, and then drying the surface of the raw material;
(2) fixing the dried metal copper plate on a workbench of a friction stir welding machine by using a clamp, and adopting a tungsten-rhenium alloy stirring head with a stirring pin; starting the friction stir welding machine, setting the rotating speed of 100-; meanwhile, in the whole process of mechanical stirring, the copper plate is cooled by dry ice;
(3) and after the machining is finished, the shaft shoulder of the stirring friction welding head leaves an arc-shaped pattern on the copper plate, and the arc-shaped pattern area is cut to obtain the copper block electrode.
2. The mechanical stirring of claim 1 produces copper electrodes with high density dislocations for electrochemical hydrogen evolution reactions.
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