Surface protection of lithium metal anode

Abstract

A method and apparatus for forming metal electrode structures, more specifically lithium-containing anodes, high performance electrochemical devices, such as primary and secondary electrochemical devices, including the aforementioned lithium-containing electrodes. In one implementation, the method comprises forming a lithium metal film on a current collector. The current collector comprises copper and/or stainless steel. The method further comprises forming a protective film stack on the lithium metal film, comprising forming a first protective film on the lithium metal film. The first protective film is selected from a bismuth chalcogenide film, a copper chalcogenide film, a tin chalcogenide film, a gallium chalcogenide film, a germanium chalcogenide film, an indium chalcogenide film, a silver chalcogenide film, a dielectric film, a lithium fluoride film, or a combination thereof.

1 . A method of fabricating a lithium-containing electrode, the method comprising:
 forming a lithium metal film on a current collector, the current collector comprising copper, stainless steel, or combinations thereof; and   forming a protective film stack on the lithium metal film, the protective film stack comprising:
 forming a first protective film on the lithium metal film, the first protective film comprising bismuth, silver, tin, a bismuth chalcogenide, a tin chalcogenide, a silver chalcogenide, or combinations thereof; and 
 forming a second protective film on the first protective film, the second protective film comprising LiF, an aluminum oxide, an aluminum oxyhydroxide (AlO(OH)), or combinations thereof. 
   
     
     
         2 . The method of  claim 1 , wherein the second protective film comprises the LiF. 
     
     
         3 . The method of  claim 2 , wherein the first protective film is selected from the group consisting of bismuth, silver, tin, and combinations thereof. 
     
     
         4 . The method of  claim 1 , wherein the second protective film is selected from the group consisting of aluminum oxide, aluminum oxyhydroxide, and combinations thereof. 
     
     
         5 . The method of  claim 1 , wherein the first protective film has a thickness of 100 nanometers or less. 
     
     
         6 . The method of  claim 1 , further comprising exposing the current collector to a plasma treatment or corona discharge process to remove organic materials from exposed surfaces of the current collector prior to forming the lithium metal film on the current collector. 
     
     
         7 . The method of  claim 1 , wherein forming the first protective film comprises performing at least one of a sputtering process, a thermal evaporation process, an e-beam evaporation process, and a chemical vapor deposition (CVD) process. 
     
     
         8 . The method of  claim 1 , wherein forming the second protective film comprises performing at least one of a sputtering process, a thermal evaporation process, an e-beam evaporation process, and a chemical vapor deposition (CVD) process. 
     
     
         9 . An anode electrode structure, comprising:
 a current collector comprising copper, stainless steel, or combinations thereof;   a lithium metal film formed on the current collector; and   a protective film stack formed on the lithium metal film, the protective film stack comprising:
 a first protective film on the lithium metal film, the first protective film comprising bismuth, silver, tin, a bismuth chalcogenide, a tin chalcogenide, a silver chalcogenide, or combinations thereof; and 
 a second protective film on the first protective film, the second protective film comprising LiF, an aluminum oxide, an aluminum oxyhydroxide (AlO(OH)), or combinations thereof. 
   
     
     
         10 . The anode electrode structure of  claim 9 , wherein the second protective film comprises the LiF. 
     
     
         11 . The anode electrode structure of  claim 10 , wherein the first protective film is selected from the group consisting of bismuth, silver, tin, and combinations thereof. 
     
     
         12 . The anode electrode structure of  claim 9 , wherein the second protective film is selected from the group consisting of aluminum oxide, aluminum oxyhydroxide, and combinations thereof. 
     
     
         13 . The anode electrode structure of  claim 12 , wherein, when the second protective film is selected from the group consisting of aluminum oxide, aluminum oxyhydroxide, and combinations thereof, the first protective film is selected from the group consisting of bismuth, silver, tin, and combinations thereof. 
     
     
         14 . The anode electrode structure of  claim 9 , wherein the first protective film has a thickness of 100 nanometers or less. 
     
     
         15 . An energy storage device, comprising:
 the anode electrode structure of  claim 9 ;   a cathode electrode structure; and   a solid electrolyte film formed between the anode electrode structure and the cathode electrode structure.   
     
     
         16 . The energy storage device of  claim 15 , wherein the solid electrolyte film is comprised of LiPON, doped variants of either crystalline or amorphous phases of Li 7 La 3 Zr 2 O 12 , doped anti-perovskite compositions, argyrodite compositions, lithium-sulfur-phosphorous materials, Li 2 S—P 2 S 5 , Li 10 GeP 2 S 12 , and Li 3 PS 4 , lithium phosphate glasses, (1-x)LiI-(x)Li 4 SnS 4 , xLiI-(1-x)Li 4 SnS 4 , mixed sulfide and oxide electrolytes (crystalline LLZO, amorphous (1-x)LiI-(x)Li 4 SnS 4  mixture, amorphous xLiI-(1-x)Li 4 SnS 4 ), Li 3 S(BF 4 ) 0.5 Cl 0.5 , Li 4 Ti 5 O 12 , lithium doped lanthanum titanate (LATP), Li 2+2x Zn 1-x GeO 4 , LiTi 2 (PO 4 ) 3 , LiHf 2 (PO 4 ) 3 , LiGe 2 (PO 4 ) 3 , or combinations thereof. 
     
     
         17 . An anode electrode structure, comprising:
 a current collector comprising copper, stainless steel, or combinations thereof;   a lithium metal film formed on the current collector; and   a protective film stack formed on the lithium metal film, the protective film stack comprising:
 a first protective film on the lithium metal film, the first protective film comprising bismuth, silver, tin, a bismuth chalcogenide, a tin chalcogenide, a silver chalcogenide, or combinations thereof, the first protective film having a thickness of 100 nanometers or less; and 
 a second protective film on the first protective film, the second protective film comprising LiF, an aluminum oxide, an aluminum oxyhydroxide (AlO(OH)), or combinations thereof. 
   
     
     
         18 . The anode electrode structure of  claim 17 , wherein the second protective film comprises the LiF. 
     
     
         19 . The anode electrode structure of  claim 18 , wherein the first protective film comprises the bismuth, silver, tin, or combinations thereof. 
     
     
         20 . The anode electrode structure of  claim 17 , wherein the second protective film comprises the aluminum oxide, aluminum oxyhydroxide, or combinations thereof.