Prevention of dendritic plating of lithium

• US 3,953,302 A
• Filed: 08/16/1973
• Issued: 04/27/1976
• Est. Priority Date: 08/16/1973
• Status: Expired due to Term

• Current Assignee: Duracell Incorporated (Berkshire Hathaway Incorporated)
• Original Assignee: P R Mallory & Company Incorporated (Tupperware Brands Corporation)
• Inventors: Schlaikjer, Carl R., Rao, Bhaskara M. L.
• Primary Examiner(s): Edmundson, F. C.
• Application Number:
  US05/388,870
• Time in Patent Office: 985 Days
• Field of Search: 204/59 AM, 204/59 M, 204/60, 204/43 R, 204/44, 204/14 N, 136/6 LN
• US Class Current: 205/234
• CPC Class Codes: C25D 3/42 of light metals
• CPC Class Codes: C25D 3/56 of alloys

Abstract

A method, a cell, an electrolyte and an additive for the non-dendritic deposition of lithium is described.

The additive which causes the non-dendritic deposition of lithium from non-aqueous electrolytes and particularly organic electrolytes is a metal, reducible by lithium and capable of forming lithium-rich metallics or alloys.

Claims

1. A method for non-dendritic plating of lithium at lithium deposition voltages by utilizing non-aqueous electrolytes containing lithium salts aprotic organic solvents and addition agents having metallic elements capable of coplating with lithium to form lithium rich intermetallics or alloys wherein the concentration of said additive agents does not exceed the amount which will render the lithium more noble by one and a half volts from the normal lithium EMF activity.

2. The method according to claim 1 wherein the addition agent is a compound containing metal ions of a metal which is reducible by lithium.

3. The method according to claim 1 wherein the addition agent is a metallic ion or a metal-included complex ion having an electromotive force (EMF) in the electromotive series with respect to lithium to exchange with and coplate with said lithium at lithium deposition voltages in said electrolyte.

4. The method according to claim 1 wherein said additive is a metal or metal ion more noble than lithium whereby it will exchange and coplate an alloy with lithium during the electrochemical deposition of lithium from an aprotic medium as the electrolyte.

5. A non-aqueous electrolyte for non-dendritic lithium plating comprising a non-aqueous aprotic solvent selected from the following:

Propylene carbonate, alkyl formates, alkyl acetates, butyrates, methyl orthoacetate, ethyl orthoacetate, ethyl orthoformate, tetrahydrofuran, methoxymethane, methyoxyethane, esters derived from ethylene glycol and polyethylene glycol, dioxane, dioxolane, acetaldehyde, acetone, acetonitrile, propionitrile, benzonitrile, formamide, N, N dimethylacetamide, N, N dimethyl methyl carbamate, and tetramethylurea,

having dissolved therein a conductive salt of lithium and an additive agent having a metal component reducible by lithium and capable of coplating with lithium at lithium deposition voltages in the form of lithium rich intermetallics or alloys.

6. The electrolyte according to claim 5 wherein said additive is selected from the group consisting of metals and salts soluble in said electrolyte selected from the group consisting of alkaline earth salts, transition metal salts, of transition metal elements more noble than lithium in said solvent and selected from the group consisting of Sc, Ti, Hg, Zn, Cd, Cr, Mn, Fe, Co, Ni, Cu, Y, Ag, La, Ga, In, Tl, Sn, Pb, Bi, and rare earths and complex salts of said metals more noble than lithium in which said metal is present as an anionic or cationic complex which in solution in said electrolyte dissociates into charged complex ions.

7. The electrolyte according to claim 6 wherein the concentration of said additive agent does not exceed the amount which will render the lithium more noble by one and a half volts from the normal lithium EMF activity.

8. The non-aqueous electrolyte as in claim 5 wherein said non-aqueous aprotic solvent contains sulfur dioxide.