Annealed garnet electrolyte separators
Set forth herein are pellets, thin films, and monoliths of lithium-stuffed garnet electrolytes having engineered surfaces. These engineered surfaces have a list of advantageous properties including, but not limited to, low surface area resistance, high Li + ion conductivity, low tendency for lithium dendrites to form within or thereupon when the electrolytes are used in an electrochemical cell. Other advantages include voltage stability and long cycle life when used in electrochemical cells as a separator or a membrane between the positive and negative electrodes. Also set forth herein are methods of making these electrolytes including, but not limited to, methods of annealing these electrolytes under controlled atmosphere conditions. Set forth herein, additionally, are methods of using these electrolytes in electrochemical cells and devices. The instant disclosure further includes electrochemical cells which incorporate the lithium-stuffed garnet electrolytes set forth herein.
1. An electrolyte separator,
wherein the electrolyte separator is bound to a substrate selected from a polymer, a glass, or a metal;
wherein the electrolyte separator comprises a bulk, wherein the bulk has a thickness from about 10 nm to about 100 μm;
wherein the bulk is characterized by the chemical formula Li A La B M′ c M″ D Zr E O F ,
wherein 4<A<8.5, 1.5<B<4, 0≤C≤2, 0≤D≤2; 0≤E<2, 10<F<13, M′ is Al, and M″ is selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, and Ta; and
wherein either a top or bottom surface of the electrolyte separator is characterized as having a less than 1 μm layer thereupon comprising lithium carbonate, lithium hydroxide, lithium oxide, a hydrate thereof, an oxide thereof, or a combination thereof.
2. The electrolyte separator of claim 1 , wherein the substrate is a metal.
3. The electrolyte separator of claim 2 , wherein the metal comprises nickel (Ni), copper (Cu), steel, stainless steel, combinations thereof, or alloys thereof.
4. The electrolyte separator of claim 3 , wherein the metal comprises nickel (Ni).
5. The electrolyte separator of claim 3 , wherein the metal comprises copper (Cu).
6. The electrolyte separator of claim 3 , wherein the metal comprises steel or stainless steel.
7. The electrolyte separator of claim 1 , wherein either the top or bottom surface of the electrolyte separator is characterized as having substantially no layer thereupon comprising lithium carbonate, lithium hydroxide, lithium oxide, lithium peroxide, a hydrate thereof, an oxide thereof, or a combination thereof, as characterized by Raman spectroscopy.
8. The electrolyte separator of claim 1 , wherein either the top or bottom surface of the electrolyte separator is characterized as having substantially no layer thereupon comprising lithium carbonate, lithium hydroxide, lithium oxide, lithium peroxide, a hydrate thereof, an oxide thereof, or a combination thereof, as characterized by FT-IR.
9. The electrolyte separator of claim 1 , wherein either the top or bottom surface of the electrolyte separator is characterized as having substantially no layer thereupon comprising lithium carbonate, lithium hydroxide, lithium oxide, lithium peroxide, a hydrate thereof, an oxide thereof, or a combination thereof, as characterized by XPS.
10. The electrolyte separator of claim 1 , having a Li-metal interface area specific resistance between 0 and 15 Ωcm 2 at 60° C.
11. The electrolyte separator of claim 10 , having a Li-metal interface area specific resistance less than 2 Ωcm 2 at 60° C.
12. The electrolyte separator of claim 1 , having a Li-metal interface area specific resistance less than 2 Ωcm 2 at 25° C.
13. The electrolyte separator of claim 1 , having a Li-metal interface area specific resistance less than 20 Ωcm 2 at −25° C.
14. The electrolyte separator of claim 1 , having a top or bottom surface that has a carbon concentration at the surface of less than 5 atomic %.
15. The electrolyte separator of claim 1 , having a top or bottom surface that has a hydrogen concentration at the surface of less than 5 atomic %.
16. An electrochemical cell comprising the electrolyte separator of claim 1 .
17. The electrochemical cell of claim 16 further comprising a lithium metal anode.
18. The electrochemical cell of claim 16 , further comprising an electrolyte wherein the electrolyte comprises a lithium salt.
19. The electrochemical cell of claim 18 , wherein the lithium salt is LiFTSi or LiPF 6 .
20. The electrochemical cell of claim 19 , wherein the electrolyte further comprises a solvent selected from ethylene carbonate, dimethyl carbonate, and a combination thereof.
21. A method of cycling lithium through an electrolyte separator, comprising
providing an electrolyte separator according to claim 1 ;
and cycling at least 10 μm of lithium metal at a current of at least 1 mA/cm 2 or greater.
22. The method of claim 21 , comprising cycling at least 20 μm of lithium metal at a current of at least 2 mA/cm 2 or greater.