# US 11,306,407 B2 · Methods for electrodeposition

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- Number: US 11,306,407 B2
- Document ID: US11306407B2
- Status: Granted
- Kind: B2
- Application number: 16/722,237
- Filed: 2019-12-20
- Published: 2020-06-25
- Granted: 2022-04-19
- Earliest claimed: 2018-12-21
- Assignees: The Board of Trustees of The University of Alabama
- Applicants: The Board of Trustees of the University of Alabama
- Inventors: Qiang Huang
- Web page: https://patentgrep.com/patent/US11306407B2

## CPC

- C25D 3/12: of nickel or cobalt
- C25D 3/20: of iron
- C25D 3/22: of zinc
- C25D 3/54: of metals not provided for in groups C25D3/04 - C25D3/50
- C25D 3/56: of alloys
- C25D 3/562: {containing more than 50% by weight of iron or nickel or cobalt}
- C25D 5/10: Electroplating with more than one layer of the same or of different metals (for bearings C25D7/10)
- C25D 5/50: by heat-treatment
- C25D 5/605: {Surface topography of the layers, e.g. rough, dendritic or nodular layers}
- C25D 5/611: {Smooth layers}
- C25D 5/617: {Crystalline layers}
- C25D 5/619: {Amorphous layers}
- C25D 5/625: {Discontinuous layers, e.g. microcracked layers}
- C25D 5/627: {Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance}
- C25D 9/02: with organic materials
- H10N 60/01: Manufacture or treatment
- H10N 60/0128: {of composite superconductor filaments (comprising copper oxide H10N60/0268)}
- C25D: PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- H10N: ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR

## Abstract

Methods for electrodeposition using aqueous electrolytes where water molecules are depleted are described herein. Methods of electrodepositing superconducting thin films from aqueous electrolytes where water molecules are depleted are also described herein.

## Claims

### Claim 1

A method of electrodeposition, the method comprising:
applying an electric potential to a working electrode,
wherein the working electrode is in electrochemical contact with an aqueous electrolyte and the aqueous electrolyte is further in electrochemical contact with a counter electrode;
wherein the aqueous electrolyte comprises a solvate, a salt, and water;
wherein the solvate comprises an alkali metal salt, an alkaline earth metal salt, an organic compound, or a combination thereof;
wherein a fully hydrated solution of the solvate in water has a first molar ratio of water to solvate;
wherein the aqueous electrolyte has a second molar ratio of water to solvate, and the second molar ratio is less than the first molar ratio, such that the aqueous electrolyte has a decreased number of free water molecules than the corresponding fully hydrated solution of the solvate in water;
wherein the salt comprises a metal, a metalloid, a nonmetal, or a combination thereof;
wherein the solvate and the salt are different; and
wherein the solvate has a lower reduction potential than the salt;
thereby reducing at least a portion of the salt in the aqueous electrolyte and electrodepositing a layer comprising the metal, the metalloid, the nonmetal, or combination thereof; and
wherein the method has a suppressed H+ reduction compared to the corresponding method performed using the fully hydrated solution of the solvate in water due to the decreased number of free water molecules in the aqueous electrolyte compared to the corresponding fully hydrated solution of the solvate in water.

### Claim 2 (depends on 1)

The method of claim 1, wherein the solvate comprises an alkali metal salt comprising an alkali metal selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, and combinations thereof.

### Claim 3 (depends on 1)

The method of claim 1, wherein the solvate comprises an alkaline earth metal salt comprising an alkaline earth metal selected from the group consisting of magnesium, calcium, strontium, barium, and combinations thereof.

### Claim 4 (depends on 1)

The method of claim 1, wherein the solvate comprises an organic compound comprising an element selected from the group consisting of sulfur, oxygen, nitrogen, phosphorous, other non-metallic elements, and combinations thereof.

### Claim 5 (depends on 1)

The method of claim 1, wherein the solvate comprises an organic compound selected from the group consisting of choline, ammonia, an ammonium salt, imine, imide, fructose, glucose, sucrose, and combinations thereof.

### Claim 6 (depends on 1)

The method of claim 1, wherein the solvate comprises ammonium acetate, ammonium chloride, ammonium formate, ammonium nitrate, ammonium thiocyanate, tetrabutylammonium chloride, tetrabutylammonium sulfate, cesium acetate, cesium chloride, cesium formate, calcium chloride, indium chloride, lithium acetate, lithium chloride (LiCl), lithium formate, lithium thiocyanate, lithium bis(trifluoromethane sulfonyl) imide (LiTFSI), potassium acetate, potassium chloride, potassium thiocyanate, sodium chloride, sodium formate, zinc chloride, choline chloride, fructose, glucose, mannose, sucrose, xylose, urea, thiourea, polyethyleneimine, polyethylene glycol, dioxime, dimethyl glyoxime, mercapto-propylsulfonate, saccharin, or a combination thereof.

### Claim 7 (depends on 1)

The method of claim 1, wherein the concentration of the solvate is 5 moles per liter (M) or more.

### Claim 8 (depends on 1)

The method of claim 1, wherein the metal, the metalloid, the nonmetal, or combination thereof comprising the salt is/are selected from the group consisting of Al, Si, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, and combinations thereof.

### Claim 9 (depends on 1)

The method of claim 1, wherein the metal, the metalloid, the nonmetal, or combination thereof comprising the salt is/are selected from the group consisting Re, W, Ru, Pd, Zn, Fe, Co, Mn, Se, Ni, Ga, As, Cu, In, Sn, Si, Ge, and combinations thereof.

### Claim 10 (depends on 1)

The method of claim 1, wherein the salt has a concentration in the aqueous electrolyte of from 0.001 M to 1 M.

### Claim 11 (depends on 1)

The method of claim 1, wherein the electrodeposited layer comprises Re, Mn, Nb, Si, Ge, Ga, Mo, Ru, ReW, ReRu, ReMn, ReFe, ReCo, ReNi, ReMo, PdZn, RuFe, RuCo, RuNi, RuMo, FeMn, CoMn, NiFeMo, FeCoMn, FeCoSe, NiFeSe, GaAs, CulnGa, CuInGaSe, or combinations thereof.

### Claim 12 (depends on 1)

The method of claim 1, wherein the electrodeposited layer has a lower amount of hydrogen incorporated therein, an improved morphology, an improved property, or a combination thereof compared to the corresponding electrodeposited layer resulting from the corresponding method performed using the fully hydrated solution of the solvate in water.

### Claim 13 (depends on 12)

A sample comprising the electrodeposited layer made using the method of claim 12.

### Claim 14 (depends on 13)

The sample of claim 13, wherein the electrodeposited layer exhibits superconductivity.

### Claim 15 (depends on 13)

A method of use of the sample of claim 13, the method of use comprising using the sample as a coating, in an electronic device, in a microdevice, in an aerospace device, or a combination thereof.

### Claim 16 (depends on 1)

The method of claim 1, wherein the aqueous electrolyte further comprises an additional solvent, wherein the additional solvent comprises ethanol, isopropanol, ethylene glycol, polyethylene glycol, glycerol, alkane diol, or combinations thereof.

### Claim 17 (depends on 1)

The method of claim 1, wherein the applied electric potential is from −3 volts (V) to −0.2 V.

### Claim 18 (depends on 1)

The method of claim 1, further comprising annealing the electrodeposited layer at a temperature of from 100° C. to 2000° C.