IP Library Granted Patent US 11,105,013
Granted Patent B2
US 11,105,013 · App. 14/686,184 · Granted Aug 31, 2021

Ionic liquid electrolyte and method to electrodeposit metals

Inventors: Patrick Benaben (Saint-Maximin, FR); Joan Brennecke (Notre Dame, IN); Edward Maginn (Notre Dame, IN); Mauricio Quiroz-Guzman (South Bend, IN)
Assignees: Neo Industries LLC; University of Notre Dame Du Lac; Ionic Research Technologies LLC
C25D3/10C25D3/06C25D3/665C25D3/08
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Quick Facts
Patent No.
US 11,105,013
App. No.
14/686,184
Granted
Aug 31, 2021
Kind
B2
Abstract

An electrolyte and a method to electroplate a metal on a substrate using the electrolyte are described. The electrolyte includes an imidazolium compound, a metal salt, and water. The imidazolium compound has formula (I) wherein R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from an H atom and an organic radical. L − is a compatible anion. The metal salt can include but is not limited to salts of the metals Li, Mg, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb, Bi, La, Ce, Al, Ag, Au, Ga, V, In, Nb, Mo, and W.

Claims (14)

1. An electrolyte for electrodepositing metals on a substrate comprising an imidazolium compound, a metal salt, and water, wherein the imidazolium compound has formula (1):

wherein R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from the group consisting of an H atom and an organic radical, and L − is a compatible anion, wherein the ratio of imidazolium compound to metal salt is from 0.1:4 to 200:1, and wherein the water is present in the electrolyte in an amount from 6 M to 50 M.

2. The electrolyte of claim 1 , wherein R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from the group consisting of an H atom and an organic radical of from 1 to 20 carbon atoms.

3. The electrolyte of claim 1 , wherein L − is selected from the group consisting of chloride, carboxylate anions, oxides, organic sulfite or sulfate, inorganic sulfite or sulfate, sulfonate, sulfamate, carbonate, nitrate, nitrite, thiocyanate, hydroxide, sulfonylimide, phosphates, phosphonates, phosphinates, phosphites, phosphonites and phosphinites, borates, carboxylates, and acetates.

4. The electrolyte of claim 1 , wherein L − is nitrate, chloride, sulfonate, or sulfamate.

5. The electrolyte of claim 1 , wherein the metal salt is a hydrated metal salt.

6. The electrolyte of claim 1 , wherein the metal salt is selected from the group consisting of Li, Mg, Ca, Cr, Mn, Fe, Co Ni, Cu, Zn, Cd, Pb, Bi, La, Ce, Al, Ag, Au, Ga, V, In, Nb, Mo, and W.

7. The electrolyte of claim 1 , wherein the imidazolium compound is selected from the group consisting of 1-Methyl-3-Methylimidazolium (MMIM) chloride, nitrate, alkyl sulfonate, and alkyl sulfamate; 1-Ethyl-3-Methylimidazolium (EMIM) chloride, nitrate, alkyl sulfonate, and alkyl sulfamate; 1-Butyl-3-Methylimidazolium (BMIM) chloride, nitrate, alkyl sulfonate, and alkyl sulfamate; 1-Hexyl-3-Methylimidazolium (HMIM) chloride, nitrate, alkyl sulfonate, and alkyl sulfamate, and wherein the metal salt is selected from the group consisting of ZnCl 2 .2H 2 O, CaCl 2 .6H 2 O, MgCl 2 .6H 2 O, CrCl 3 .6H 2 O, CoCl 2 .6H 2 O, LaCl 3 .6H 2 O, CuCl 2 .2H 2 O, LiCl.5H 2 O, MoCl 5 , WCl 6 , Ca(NO 3 ) 2 .4H 2 O, Cr(NO 3 ) 3 .9H 2 O, Mn(NO 3 ) 2 .4H 2 O, Fe(NO 3 ) 3 .9H 2 O, Co(NO 3 ) 2 .6H 2 O, Ni(NO 3 ) 2 .6H 2 O, Cu(NO 3 ) 2 .3H 2 O, Li(NO 3 ).H 2 O, Mg(NO 3 ) 2 .6H 2 O, La(NO 3 ) 3 .6H 2 O, Cd(NO 3 ) 2 .4H 2 O, Ce(NO 3 ) 3 .6H 2 O, Bi(NO 3 ) 3 .5H 2 O, Zn(NO 3 ) 2 .4H 2 O, Cd(OAc) 2 .2H 2 O, Pb(OAc) 2 .3H 2 O, and Cr 2 (SO 4 ) 3 .15H 2 O.

8. The electrolyte of claim 7 , wherein the imidazolium compound is selected from the group consisting of 1-Methyl-3-Methylimidazolium (MMIM) chloride, 1-Ethyl-3-Methylimidazolium (EMIM) chloride, 1-Butyl-3-Methylimidazolium (BMIM) chloride, and 1-Hexyl-3-Methylimidazolium (HMIM) chloride, and the metal salt is CrCl 3 .6H 2 O.

9. The electrolyte of claim 1 , wherein the water is present at a concentration of 6 M to 40 M.

10. The electrolyte of claim 1 , wherein the water is present at a concentration of 6 M to 30 M.

11. The electrolyte of claim 1 , wherein the molar ratio of imidazolium compound to metal salt is between 0.5:1 and 100:1.

12. The electrolyte of claim 1 , wherein the metal of the metal salt is Cr.

13. The electrolyte of claim 1 , wherein the imidazolium compound, the metal salt, and water are present in sufficient quantities to electrodeposit a thickness of a metal on the substrate from 1 μm to 500 μm.

Assignments (6)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 12, 2021
From: IONIC RESEARCH TECHNOLOGIES, LLC
To: ILS-TRION, LLC
Reel/Frame 057164/0128 →
CORRECTIVE ASSIGNMENT TO CORRECT THE ASSIGNEE'S NAME FROM "NEO INDUSTRIES" TO NEO INDUSTRIES, LLC PREVIOUSLY RECORDED ON REEL 040004 FRAME 0661. ASSIGNOR(S) HEREBY CONFIRMS THE PATRICK BENABEN TO NEO INDUSTRIES - DOCUMENT ID 504048591. Recorded Oct 19, 2016
From: BENABEN, PATRICK
To: NEO INDUSTRIES, LLC
Reel/Frame 040420/0098 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 13, 2016
From: BENABEN, PATRICK
To: NEO INDUSTRIES
Reel/Frame 040004/0661 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 13, 2016
From: BRENNECKE, JOAN; MAGINN, EDWARD
To: UNIVERSITY OF NOTRE DAME DU LAC
Reel/Frame 040004/0715 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 13, 2016
From: QUIROZ-GUZMAN, MAURICIO
To: IONIC RESEARCH TECHNOLOGIES LLC
Reel/Frame 040004/0774 →
CONFIRMATORY LICENSE Recorded Sep 8, 2016
From: UNIVERSITY OF NOTRE DAME
To: NATIONAL SCIENCE FOUNDATION
Reel/Frame 039675/0764 →
Continuity (2)
Provisional Application 61979705 · Apr 15, 2014
Related Publication 20150292098A1 · Oct 15, 2015
Cited By (1)
US 12,573,664