Methods and electrolytes for electrodeposition of smooth films

Abstract

Electrodeposition involving an electrolyte having a surface-smoothing additive can result in self-healing, instead of self-amplification, of initial protuberant tips that give rise to roughness and/or dendrite formation on the substrate and/or film surface. For electrodeposition of a first conductive material (C1) on a substrate from one or more reactants in an electrolyte solution, the electrolyte solution is characterized by a surface-smoothing additive containing cations of a second conductive material (C2), wherein cations of C2 have an effective electrochemical reduction potential in the solution lower than that of the reactants.

1 . An electrolyte solution for electrodeposition of a first conductive material (C1) on a substrate from one or more reactants in the electrolyte solution, the electrolyte solution characterized by a soluble, surface-smoothing additive comprising cations of a second conductive material (C2), wherein cations of C2 have an effective electrochemical reduction potential in the solution lower than that of the reactants. 
     
     
         2 . The electrolyte solution of  claim 1 , wherein C1 is a metallic material and the reactants comprise cations of C1. 
     
     
         3 . The electrolyte solution of  claim 2 , wherein C1 comprises a metal selected from the group consisting of Li, Na, Mg, Al, Sn, Ti, Fe, Ni, Cu, Zn, Ag, Pt, Au, and combinations thereof. 
     
     
         4 . The electrolyte solution of  claim 1 , wherein C1 comprises an electronic conductive polymer and the reactants comprise monomers of the polymer. 
     
     
         5 . The electrolyte solution of  claim 1 , wherein the cations of C2 are metal cations. 
     
     
         6 . The electrolyte solution of  claim 5 , wherein the cations of C2 comprise a metal selected from the group consisting of Cs, Rb, K, Ba, Sr, Ca, Li, and combinations thereof. 
     
     
         7 . The electrolyte solution of  claim 1 , wherein the cations of C2 have an activity in solution such that the effective electrochemical reduction potential of cations of C2 is lower than that of the reactants. 
     
     
         8 . The electrolyte solution of  claim 1 , wherein the cations of C2 have a concentration in solution such that the effective electrochemical reduction potential of cations of C2 is lower than that of the reactants. 
     
     
         9 . The electrolyte solution of  claim 1 , wherein the concentration of C2 cations is less than, or equal to, 30% of that of the reactants. 
     
     
         10 . The electrolyte solution of  claim 1 , wherein the concentration of C2 cations is less than, or equal to, 5% of that of the reactants. 
     
     
         11 . The electrolyte solution of  claim 1 , wherein the surface-smoothing additive comprises an anion selected from the group consisting of PF 6   − , AsF 6   − , BF 4   − , N(SO 2 CF 3 ) 2   − , N(SO 2 F) 2   − , CF 3 SO 3   − , ClO 4   − , I − , Cl − , OH − , NO 3   − , SO 4   2−  and combinations thereof. 
     
     
         12 . The electrolyte solution of  claim 1 , wherein the substrate is an electrode. 
     
     
         13 . The electrolyte solution of  claim 12 , wherein the electrode comprises lithium. 
     
     
         14 . The electrolyte solution of  claim 12 , wherein the electrode comprises carbon. 
     
     
         15 . The electrolyte solution of  claim 12 , wherein the electrode is an electrode in an energy storage device. 
     
     
         16 . The electrolyte solution of  claim 1 , wherein the cations of C2 are not chemically or electrochemically reactive with respect to C1 or the reactants. 
     
     
         17 . The electrolyte solution of  claim 1 , wherein the cations of C2 have a standard electrical reduction potential that is greater than the effective electrochemical reduction potential of the reactants. 
     
     
         18 . The electrolyte solution of  claim 2 , wherein C1 comprises lithium.