Methods for electrochemical additive manufacturing while modifying electrolyte solutions
Described herein are electrochemical additive manufacturing systems and methods of using such systems. In some examples, a method comprises flowing an electrolyte solution into the gap formed by an electrode array and a deposition electrode and depositing (electroplating) a target material onto the deposition electrode. The method also comprises changing one or more characteristics of the electrolyte solution within the system, e.g., to remove deposition byproducts, replenish consumed components, and/or change the solution composition to modify various properties of the deposited target material (e.g., composition, morphology) without major changeovers within the system. These electrolyte changes can be performed dynamically while the system continues to operate. The changed characteristics can be acid concentration, feedstock ion concentration, additive concentration, temperature, and flow rate. In some examples, the solution is flowed into the gap from a supply reservoir and recirculated back into the supply reservoir after exiting the gap.
1. A method of electrochemical additive manufacturing using an electrochemical additive manufacturing system comprising an electrodeposition cell formed by an electrode array and a deposition electrode, the method comprising:
flowing an electrolyte solution into and through a gap formed by the electrode array, comprising individually-addressable electrode portions, and the deposition electrode, wherein:
the individually-addressable electrode portions are arranged in a two-dimensional grid defined by an electrode array plane,
the electrolyte solution enters the gap through an inlet and exits the gap through an outlet, and
the inlet is separated from the outlet by the two-dimensional grid such that the electrolyte solution flows through the gap in a direction substantially parallel to the electrode array plane while contacting the individually-addressable electrode portions;
depositing a target material onto the deposition electrode from the electrolyte solution by flowing a current between a subset of the individually-addressable electrode portions of the electrode array in a direction substantially perpendicular to the electrolyte solution flow onto the deposition electrode, operating as a cathode, wherein the subset of the individually-addressable electrode portions is selected based on a desired location of the target material on the deposition electrode,
measuring one or more characteristics of the electrolyte solution thereby producing one or more measured values, wherein the one or more characteristics comprise a current through the electrolyte solution; and
changing the one or more characteristics of the electrolyte solution within the electrochemical additive manufacturing system using one or more electrolyte-altering devices, wherein:
the one or more characteristics of the electrolyte solution, which are changed, comprise one or more of an acid concentration, a feedstock ion concentration, and a plating additive concentration, and
the one or more characteristics of the electrolyte solution are changed based on the one or more measured values.
2. The method of claim 1 , wherein flowing the current between the electrode array and the deposition electrode is caused by selectively applying an individual voltage between the deposition electrode and each electrode portion in the subset of the individually-addressable electrode portions.
3. The method of claim 1 , wherein:
the electrolyte solution is flowed into the gap from a supply reservoir; and
the electrolyte solution is recirculated back into the supply reservoir after exiting the gap.
4. The method of claim 3 , further comprising flowing a second electrolyte solution from a second supply reservoir into the gap, wherein the target material is deposited out of the second electrolyte solution onto the deposition electrode.
5. The method of claim 4 , further comprising changing one or more characteristics of the second electrolyte solution, wherein the one or more characteristics of the second electrolyte solution, which are changed, comprise one or more of the acid concentration, the feedstock ion concentration, and the plating additive concentration.
6. The method of claim 1 , wherein the one or more characteristics of the electrolyte solution are changed before flowing the electrolyte solution into the gap or while the electrolyte solution is in the gap.
7. The method of claim 1 , wherein the one or more characteristics of the electrolyte solution, which are changed, comprise two or more of the acid concentration, the feedstock ion concentration, and the plating additive concentration.
8. The method of claim 1 , wherein:
the electrodeposition cell has a volume filled with the electrolyte solution,
the electrolyte solution is flowed at a volumetric flow rate through the electrodeposition cell, and
a ratio of the volume to the volumetric flow rate is less than 1 second.
9. The method of claim 1 , wherein:
the electrochemical additive manufacturing system further comprises a collection reservoir; and
the electrolyte solution flows from the gap into the collection reservoir.
10. The method of claim 1 , wherein the one more electrolyte-altering devices comprise one or more of a material injector, a thermal unit, and a filter.
11. The method of claim 10 , wherein:
the one more electrolyte-altering devices comprise the material injector; and
the material injector changes the one or more characteristics of the electrolyte solution by injecting one or more of a solvent, an acid, a feedstock ion source, and a plating additive into the electrolyte solution.
12. The method of claim 11 , wherein:
the solvent is selected from the group consisting of water, molten salts, organic solvents, and ionic liquids;
the acid is selected from the group consisting of sulfuric acid, acetic acid, hydrochloric acid, nitric acid, hydrofluoric acid, boric acid, citric acid, and phosphoric acid;
the feedstock ion source is selected from the group consisting of copper sulfate, copper chloride, copper fluoroborate, copper pyrophosphate, copper cyanide, nickel sulfate, nickel ammonium sulfate, nickel chloride, nickel fluoroborate, zinc sulfate, sodium thiocyanate, zinc chloride, and ammonium chloride; and
the plating additive is selected from the group consisting of an accelerator, a suppressor, a brightener, a grain refiner, a leveler, and co-deposition particulates.
13. The method of claim 11 , wherein:
the electrolyte-altering device is the filter; and
the filter changes the one or more characteristics of the electrolyte solution by removing at least a part of the plating additive from the electrolyte solution.
14. The method of claim 13 , wherein flowing the electrolyte solution through the filter is selectively controlled using a valve.
15. The method of claim 1 , wherein the one or more characteristics of the electrolyte solution are measured using one or more of a thermocouple, a pH meter, an ultraviolet and visible light range (UV-Vis) spectrometer, an inline process mass spectrometer, a high-performance liquid chromatography (HPLC) device, a cyclic voltammetric stripping (CVS) device, or a potentiostat.
16. The method of claim 1 , wherein the one or more characteristics are measured before the electrolyte solution enters the gap.
17. The method of claim 1 , wherein the one or more characteristics are measured after the electrolyte solution has exited the gap.
18. The method of claim 1 , wherein:
the gap has a first height value when flowing an electrolyte solution into the gap;
the gap has a second height value during depositing the target material; and
the first height value is greater than the second height value.
19. The method of claim 1 , wherein the one or more characteristics of the electrolyte solution, which are changed, comprise the acid concentration.
20. The method of claim 1 , wherein the one or more characteristics of the electrolyte solution, which are changed, comprise the feedstock ion concentration.