Claim of Priority

[0001] This application claims priority to U.S. Patent Application No. 17/118,115, filed on 10 December 2020, the entire contents of which are hereby incorporated by reference.

Technical Field

[0002] The present disclosure is directed to smoothing a surface of a metal electrode. More specifically, the disclosure is directed to the electropolishing of a copper electrode to form an atomically smooth surface.

Background

[0003] The rising concentration of CO2 in the atmosphere and its contributions to atmospheric instability have prompted numerous projects into the use or sequestration of the gas. For example, research has continued on the catalytic production of fuels or chemicals from CO2, such as from power plant exhausts and other waste streams including high concentrations of CO2. One technique for generating fuels and chemicals from CO2 is the use of electrochemical reduction. Electrochemical reduction has numerous advantages, including simplicity, low cost, and the ability to use electrical power from renewable resources, such as solar or wind power.

Summary

[0004] An embodiment described in examples herein provides a method for forming an atomically smooth surface by electropolishing. The method includes placing a copper foil in an electrolyte solution including ethylene glycol and phosphoric acid. The copper foil is coupled to a current source. Current is applied to the copper foil to electropolish the copper foil. The electropolishing is stopped when the electropolishing is completed.

[0005] Another embodiment described in examples herein provides a copper catalyst. The copper catalyst includes a surface smoothed by electropolishing. The electropolishing is performed by placing a surface of the copper catalyst in contact with an electrolyte solution including phosphoric acid and ethylene glycol. The copper catalyst is coupled to a current source. Current is applied to the copper catalyst to electropolish the surface of the copper catalyst. The electropolishing is stopped when the electropolishing is complete.

Brief Description of Drawings

[0006] Figure 1 is a drawing of an electrochemical cell used for the electropolishing of a surface of copper foil.

[0007] Figure 2 is a process flow diagram of a method for electropolishing a surface of copper foil.

[0008] Figures 3A and 3B are images of a copper foil surface before and after electropolishing.

[0009] Figures 4A, 4B, and 4C are micrographs collected using a field emission scanning electron microscope (FESEM).

[0010] Figures 5 A and 5B are topology results obtained from an atomic force microscope (AFM) after the electropolishing of the copper foil is completed.

Detailed Description

[0011] The product of the electrochemical reduction of CO2 largely depends on the metallic material selected as the electrode and the degree of smoothness achieved from the electropolishing step. Therefore, to increase the yield from the electrochemical reduction of CO2, the electrode is smoothed prior to the use. An atomically smooth surface enhances the electrodeposition of a catalyst layer and the yield of the electrochemical reduction of CO2.

[0012] Techniques are provided herein for electropolishing copper surfaces to form atomically smooth surfaces for electrodeposition of electrochemical catalysts. The surface morphology and, thus, the surface smoothing resulting from the electropolishing is largely influenced by the adsorption of electrolyte ions.

Accordingly, the electrolyte used for the electropolishing is a solution of ethylene glycol and phosphoric acid.

[0013] In some embodiments, the electropolished copper surface is used to enhance the controlled deposition of C O, for example, as an electrochemical catalyst for the reduction of CO2. The electrochemical reduction of CO2 utilizes a low-cost waste feedstock for the generation of petrochemicals, such as methanol. The methanol may be used to generate other chemicals such as ethanol, hydrocarbons, propanol, and formic acid. The capture of the CO2 may assist in sequestration, and widespread adoption of the techniques may help to reduce the total amount of atmospheric CO2. The methanol generated in the techniques may be used as a fuel, for example, in fuel cells, combustion engines, and the like.

[0014] Figure 1 is a drawing 100 of an electrochemical cell 102 used for the electropolishing of a surface of copper foil. A potentiostat 104 is coupled to electrodes in the electrochemical cell 102, such as a reference electrode 106, a counter electrode 108, and a working electrode 110. The potentiostat 104 provides current to the electrodes 106-110 to complete the electropolishing. In this embodiment, the working electrode 110 has a sense line 112 coupled between the working electrode 110 and the potentiostat 104 to measure the voltage potential between the reference electrode 106 and the working electrode 110.

[0015] In some embodiments, a second working electrode 114 is coupled to the potentiostat 104 to allow two copper foils to be electropolished at the same time. In the embodiment shown, a second sense line 116 is coupled between the second working electrode 114 and the potentiostat 104 to measure the voltage potential between the second working electrode 114 and the reference electrode 106.

[0016] The sense lines 112 and 116 allow the voltage 118 between the working electrodes 110 and 114 and the reference electrode 106 to be measured and controlled by the potentiostat 104. In some embodiments, the current 120 flowing through the electrochemical cell 102 is measured on the line to the counter electrode 108 and controlled by the potentiostat. In some embodiments, the counter electrode 108 is another copper foil.

[0017] In some embodiments, the electrochemical cell 102 has a water jacket 122 to control the temperature of the electrochemical reaction in the electrochemical cell 102. In the embodiment shown, the water jacket 122 is coupled to a water bath 124 for temperature control. In other embodiments, the electrochemical cell 102 is partially submerged in the water bath 124.

[0018] For larger applications, an electrochemical cell with up to three electrodes, the working and the reference electrodes, may be placed inside a cathodic chamber. In this embodiment, the counter electrode is located in an anodic chamber, which is open to the atmosphere. An ion-exchange membrane is placed between the separated chambers to prevent the transportation of the oxygen gas evolved at the anodic cathode from reaching the cathodic chamber and oxidizing the products during electrolysis. [0019] CO2 is introduced into the cathodic chamber through a glass frit to remove oxygen. The dissolved CO2 travels to the surface of the cathode to complete the electrocatalytic carbon dioxide reduction.

[0020] Figure 2 is a process flow diagram of a method 200 for electropolishing a surface of copper foil. The method begins at block 202 when a copper foil is placed in an electrolyte solution. As described herein, the electrolyte solution includes ethylene glycol and phosphoric acid, prepared as described with respect to the examples.

[0021] At block 204, the copper foil is coupled to a current source, such as a potentiostat. The coupled copper foil is placed electrochemical cell, for example, using a Ag/AgCl reference electrode to measure voltage in the cell, and a copper foil counter electrode. In some embodiments, two copper foils are coupled to the current source for simultaneous electropolishing of both copper foils.

[0022] At block 206, current is applied to the copper foil to electropolish the copper foil. The current oxidizes the surface of the copper foil, removing copper ions. Higher and rougher features are preferentially removed, smoothing the surface. As described herein, in some embodiments, the electropolishing is performed at a current of between about 300 mA/ 2 cm ² and 450 mA/ 2 cm ² , at a current of between about 350 mA/ 2 cm ² and 410 mA/ 2 cm ² , or at a current of 380 mA/ 2 cm ² . In some embodiments, the temperature is controlled at between about 50 °C and about 80 °C, or between about 60 °C and about 70 °C, or at about 65 °C.

[0023] At block 208, the electropolishing is stopped at completion, for example, when the surface has reached a satisfactory degree of smoothness. In some embodiments, the electropolishing is continued for between about 9 minutes and about 14 minutes, or for between about 10 min and about 13 minutes, or for about 11.5 minutes. In some embodiments, the completion of the electropolishing process is determined by the color of the electrolyte solution. When the electrolyte solution turns light blue, in about 11.5 minutes, the electropolishing process is stopped.

[0024] Examples

[0025] Materials and equipment

[0026] Phosphoric acid was purchased as an 85% solution (con), e.g., pure orthophosphoric acid, from Sigma-Aldrich of St. Louis, MO, USA, and used without further purification. Ethylene glycol was purchased as a neat liquid from Sigma- Aldrich and used without further purification. [0027] An electrolyte solution of 3 M phosphoric acid and 0.2 M ethylene glycol was prepared in DI water. The electrolyte solution was prepared by adding 174.47 milliliters (mL) of the con phosphoric acid and 11.18 mL of the ethylene glycol to 814.35 mL of DI water.

[0028] Copper foil was purchased as a roll from Sigma- Aldrich. Flags were cut from the copper foil, wherein the flags had a 2 cm ² square lower section, and a narrow section extending upward for coupling to wires from the potentiostat. The reference electrode used for the electropolishing was an Ag/AgCl electrode purchased from Sigma-Aldrich.

[0029] The potentiostat was a Reference 3000 model from Gamry Instruments Company of Warminster, PA, USA. The field emission scanning electron microscope (FESEM) was a LYRA 3, Dual Beam, from Tescan, of Bmo, CZ. The FESEM was coupled with an energy dispersive X-ray spectrometer (EDX) from Oxford Instruments of Abingdon, UK. The FESEM was run at an SEM HV of 15 kV, with a view field of 3.00 pm, and an SEM Magnification of 63.6 kx. The AFM was an Innova AFM from Bruker of Billerica, MA, USA.

[0030] Procedures

[0031] Electropolishing

[0032] Copper foil of about 2 cm ² of area was galvanically polished in an electrolyte solution comprising ethylene glycol and phosphoric acid (3M Phosphoric Acid + 0.2M Ethylene Glycol) at a temperature of 65°C using water circulator. The counter electrode used was a second flag-shaped copper foil and the reference electrode was an Ag/AgCl electrode. The electropolishing was performed using the potentiostat at a set current of 190 mA/cm ² (380 mA/2 cm ² ) for 11.5 minutes. More than one working electrode was electropolished at a time until the electrolyte solution changed color to light blue, indicating completion of the electropolishing.

[0033] Surface Analysis

[0034] The electropolished copper foil working electrode was examined to ascertain the level of smoothness achieved. Micrographs of the surface of the electropolished copper foil were collected using FESEM and AFM.

[0035] Figures 3A and 3B are images of an electropolished copper foil surface and a non-electropolished surface. The electropolished copper, shown in Figure 3A, is smoother than that of the unpolished copper foil, shown in Figure 3B, as indicated by the higher surface reflectance. [0036] Figures 4A, 4B, and 4C are micrographs collected using a field emission scanning electron microscope (FESEM). Figure 4A is a micrograph of the surface of the copper foil as received. In Figure 4A, copper crystals 402 are visible. The copper crystals 402 may be polished to form a smoother surface. Figure 4B shows the copper foil after polishing with 10 pm alumina particles. However, this leaves larger scratches 404 on the surface. Figure 4C shows the surface of the copper foil after electropolishing for 5 min at 190 mA/cm ² in an electrolyte solution of 3 M phosphoric Acid and 0.2 M ethylene glycol. As shown in Figure 4C, the surface is smoother and suitable for forming catalyst for the electrochemical reduction of CO2.

[0037] Figures 5 A and 5B are topography results obtained with an atomic force microscope (AFM) after the electropolishing of the copper foil. In this example, the electropolishing was conducted for 11.5 minutes in the electrolyte solution of 3 M phosphoric acid and 0.2 M ethylene glycol. Figure 5A shows the topography smooth surface in the AFM micrograph. Figure 5B is a topography plot of an ensemble of the surface. As can be seen in the plot, the surface roughness across this cross-section varies by about 3 nm.

[0038] An embodiment described in examples herein provides a method for forming an atomically smooth surface by electropolishing. The method includes placing a copper foil in an electrolyte solution including ethylene glycol and phosphoric acid. The copper foil is coupled to a current source. Current is applied to the copper foil to electropolish the copper foil. The electropolishing is stopped when the electropolishing is completed.

[0039] In an aspect, the method includes forming the electrolyte solution by mixing an 85 % phosphoric acid solution into water and then adding the ethylene glycol to the electrolyte solution. In an aspect, the method includes forming the electrolyte solution at about a 3 molar (M) concentration of phosphoric acid and about a 0.2 M concentration of ethylene glycol.

[0040] In an aspect, the method includes applying the current at about 380 mA per 2 cm ² to the copper foil. In an aspect, the method includes determining that the electropolishing is completed when the electrolyte solution changes color to blue. In an aspect, the method includes determining that the electropolishing is completed after about 11.5 minutes. [0041] In an aspect, the method includes using a counter electrode including a second copper foil. In an aspect, the method includes controlling a temperature during the electropolishing at about 65 °C.

[0042] In an aspect, the method includes using the copper foil as a working electrode in an electrochemical cell. In an aspect, the method includes coupling two copper foils to the current source as working electrodes.

[0043] In an aspect, the method includes using a sense lead to monitor the current of a working electrode. In an aspect, the method includes using a Ag/AgCl electrode as a reference electrode.

[0044] Another embodiment described in examples herein provides a copper catalyst. The copper catalyst includes a surface smoothed by electropolishing. The electropolishing is performed by placing a surface of the copper catalyst in contact with an electrolyte solution including phosphoric acid and ethylene glycol. The copper catalyst is coupled to a current source. Current is applied to the copper catalyst to electropolish the surface of the copper catalyst. The electropolishing is stopped when the electropolishing is complete.

[0045] In an aspect, the electropolishing is complete when the electrolyte solution changes color to blue. In an aspect, the electropolishing is stopped after 11.5 minutes.

[0046] In an aspect, the copper catalyst includes an atomically smooth surface formed by the electropolishing. In an aspect, the electrolyte solution includes about 3 molar (M) phosphoric acid and about 0.2 M ethylene glycol. In an aspect, the current source includes a potentiostat. In an aspect, the current is at about 380 mA/ 2 cm ² . In an aspect, a temperature of the copper catalyst during application of the current is controlled at about 65 °C.

[0047] Other implementations are also within the scope of the following claims.