Electrochemical Deposition of Elements in Aqueous Media

Abstract

The disclosure relates to a method for the electrodeposition of at least one metal onto a surface of a conductive substrate. In some embodiments, the electrodeposition is conducted at a temperature from about 10° C. to about 70° C., about 0.5 atm to about 5 atm, in an atmosphere comprising oxygen. In some embodiments, the method comprises electrodepositing the at least one metal via electrochemical reduction of a metal complex dissolved in a substantially aqueous medium.

1 .- 23 . (canceled) 
     
     
         24 . A method for electrodeposition of at least one reactive metal onto a surface of a conductive substrate at a temperature from about 10° C. to about 70° C., about 0.5 atm (50.66 kPa) to about 5 atm (506.62 kPa), in an atmosphere comprising oxygen, the method comprising electrodepositing the at least one reactive metal via electrochemical reduction of a metal complex dissolved in a substantially aqueous medium the metal complex comprising a metal center and ligands;
 wherein: 
 the reactive metal comprises at least one of aluminum, titanium, manganese, gallium, vanadium, zirconium, and niobium; and the ligands are at least one of sulfonate ligands and sulfonimide ligands. 
 
     
     
         25 . The method of  claim 24 , wherein the at least one sulfonate ligand is a ligand of a formula SO 3 R 1 , wherein R 1  is halo; substituted or unsubstituted C 6 -C 18 -aryl; substituted or unsubstituted C 1 -C 6 -alkyl; and substituted or unsubstituted C 6 -C 18 -aryl-C 1 -C 6 -alkyl. 
     
     
         26 . The method of  claim 24 , wherein the at least one sulfonimide ligand is a ligand of a formula N(SO 2 R 1 ), wherein R 1  is halo; substituted or unsubstituted C 6 -C 18 -aryl; substituted or unsubstituted C 1 -C 6 -alkyl; and substituted or unsubstituted C 6 -C 18 -aryl-C 1 -C 6 -alkyl. 
     
     
         27 . The method of  claim 24 , wherein the at least one sulfonate ligand comprises a sulfonate ligand of a formulae: 
       
         
           
           
               
               
           
         
       
     
     
         28 . The method of  claim 24 , wherein the at least one sulfonimide ligand comprises a sulfonimide ligand of a formula: 
       
         
           
           
               
               
           
         
       
     
     
         29 . The method of  claim 24 , wherein the metal complex is at least one metal complex of a formula Al(SO 3 R 1 ) n , wherein R 1  is halo; substituted or unsubstituted C 6 -C 18 -aryl; substituted or unsubstituted C 1 -C 6 -alkyl; n is an integer from 2 to 8; and Al[N(SO 3 R 1 ) 2 ] n , wherein R 1  is halo; substituted or unsubstituted C 6 -C 18 -aryl; substituted or unsubstituted C 1 -C 6 -alkyl; substituted or unsubstituted C 6 -C 18 -aryl-C 1 -C 6 -alkyl; and n is an integer from 1 to 4. 
     
     
         30 . The method of  claim 24 , wherein the substantially aqueous medium comprises an electrolyte. 
     
     
         31 . The method of  claim 30 , wherein the electrolyte comprises at least one of a halide electrolyte; a perchlorate electrolyte; an amidosulfonate electrolyte; hexafluorosilicate electrolyte; a tetrafluoroborate electrolyte; methanesulfonate electrolyte; and a carboxylate electrolyte. 
     
     
         32 . The method of  claim 31 , wherein the electrolyte comprises at least one of compounds of a formula R 3 CO 2 —, wherein R 3  is substituted or unsubstituted C 6 -C 18 -aryl; or substituted or unsubstituted C 1 -C 6 -alkyl. 
     
     
         33 . The method of  claim 31 , wherein the electrolyte comprises at least one of polycarboxylates; and lactones. 
     
     
         34 . The method of  claim 24 , wherein the pH of the substantially aqueous medium is buffered at a pH from about 1 to about 7. 
     
     
         35 . The method of  claim 24 , wherein the substantially aqueous medium comprises a water-miscible organic solvent. 
     
     
         36 . The method of  claim 35 , wherein the water-miscible organic solvent comprises at least one of an C 1 -C 6 -alkanol, a C 2 -C 10 -polyol, a (poly)alkylene glycol ether, a C 2 -C 10 -carboxylic acid; a C 2 -C 10 -ketone; a C 2 -C 10 -aldehyde; a pyrrolidone; a C 2 -C 10 -nitrile; a phthalate; a C 2 -C 10 -dialkylamine; a C 2 -C 10 -dialkylformamide; a C 2 -C 10 -dialkyl sulfoxide; a C 4 -C 10 -heterocycloalkane; an aminoalcohol; and a C4-C10-heteroarylene. 
     
     
         37 . The method of  claim 36 , wherein the C 1 -C 6 -alkanol comprises ethanol. 
     
     
         38 . The method of  claim 24 , wherein the electrodepositing comprises electrodepositing at least one layer of the at least one metal onto the surface of the substrate. 
     
     
         39 . The method of  claim 24 , wherein the electrodepositing comprises electrodepositing at least a first layer and a second layer of the at least one metal onto the surface of the substrate. 
     
     
         40 . The method of  claim 39 , wherein the first layer comprises a different at least one metal relative to the second layer. 
     
     
         41 . A method for electrodeposition of at least one metal onto a surface of a conductive substrate at a temperature from about 10° C. to about 70° C., about 0.5 atm (50.66 kPa) to about 5 atm (506.62 kPa), in an atmosphere comprising oxygen, the method comprising electrodepositing the at least one metal via electrochemical reduction of a metal complex dissolved in a substantially aqueous medium;
 wherein: 
 the metal complex comprises a metal center and ligands, wherein at least one of the ligands is an electron withdrawing ligand and the ligands are sufficiently electron withdrawing such that the reduction potential of the metal in the metal complex is decreased below the over-potential for the evolution of hydrogen gas due to water splitting; and the at least one metal is at least one of reactive and non-reactive metals; or 
 the ligands are at least one of sulfonate ligands and sulfonimide ligands. 
 
     
     
         42 . A method for electrodeposition of at least one reactive metal onto a surface of a conductive substrate at a temperature from about 10° C. to about 70° C., about 0.5 atm (50.66 kPa) to about 5 atm (506.62 kPa), in an atmosphere comprising oxygen, the method comprising electrodepositing the at least one reactive metal via electrochemical reduction of a metal complex dissolved in a substantially aqueous medium;
 wherein: 
 the reactive metal comprises at least one of aluminum, titanium, manganese, gallium, vanadium, zirconium, and niobium; and the metal complex comprises a metal center and ligands, wherein at least one of the ligands is an electron withdrawing ligand, and are sufficiently electron withdrawing such that the reduction potential of the metal in the metal complex is decreased below the over-potential for the evolution of hydrogen gas due to water splitting. 
 
     
     
         43 . A method for electrodeposition of at least one reactive metal onto a surface of a conductive substrate at a temperature from about 10° C. to about 70° C., about 0.5 atm (50.66 kPa) to about 5 atm (506.62 kPa), in an atmosphere comprising oxygen, the method comprising electrodepositing the at least one reactive metal via electrochemical reduction of a metal complex dissolved in a medium that is at least about 50% aqueous, the metal complex comprising a metal center and ligands;
 wherein: 
 the reactive metal comprises at least one of aluminum, titanium, manganese, gallium, vanadium, zirconium, and niobium; and 
 the ligands are at least one of sulfonate ligands and sulfonimide ligands. 
 
     
     
         44 . The method of  claim 43 , wherein the medium is at least about 60% aqueous. 
     
     
         45 . The method of  claim 44 , wherein the medium is at least about 70% aqueous. 
     
     
         46 . The method of  claim 45 , wherein the medium is at least about 80% aqueous. 
     
     
         47 . The method of  claim 46 , wherein the medium is at least about 90% aqueous. 
     
     
         48 . The method of  claim 47 , wherein the medium is at least about 99% aqueous. 
     
     
         49 . The method of  claim 24 , wherein the reactive metal is aluminum, and the medium consists essentially of water.