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. A method of cycling lithium through a solid-state lithium ion conducting ceramic, comprising:
providing an electrolyte separator in contact with a lithium metal anode;
wherein the electrolyte separator comprises top and bottom surfaces and a bulk therebetween, wherein the bulk has a thickness;
wherein the top surface or bottom surface length or width is greater than the thickness of the bulk by a factor of ten or more, and the thickness of the bulk is 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;
wherein either the top surface 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; and
cycling at least 10 μm of lithium metal at a current of at least 1 mA/cm 2 or greater.
2. The method of claim 1 , wherein a total pressure applied to the electrolyte separator is 1 atmosphere.
3. The method of claim 1 , comprising applying pressure of at least 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240, 245, 250, 255, 260, 265, 270, 275, 280, 285, 290, 295, 300, 305, 310, 315, or 320 PSI to the electrolyte separator and anode.
4. The method of claim 1 , wherein the electrolyte separator is a pellet, a film, free-standing film, or a monolith.
5. The method of claim 4 , wherein the electrolyte separator is a film with a thickness is from 10 nm to about 100 μm.
6. The method of claim 1 , wherein either the top surface or bottom surface of the electrolyte separator is characterized by XPS or FT-IR.
7. The method of claim 1 , wherein the top and bottom surfaces of the electrolyte separator are 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.
8. The method of claim 7 , wherein the top and bottom surfaces of the electrolyte separator are characterized by XPS or FT-IR.
9. The method of claim 1 , wherein the electrolyte separator has a Li-metal interface area specific resistance is less than 2 Ωcm 2 at 60° C.
10. The method of claim 1 , wherein the electrolyte separator has a Li-metal interface area specific resistance less than 2 Ωcm 2 at 25° C.
11. The method of claim 1 , wherein the electrolyte separator has a Li-metal interface area specific resistance less than 20 Ωcm 2 at −25° C.
12. The method of claim 1 , wherein the top or bottom surface of the electrolyte separator is in direct contact with lithium metal.
13. An electrochemical cell comprising:
an electrolyte separator in contact with a lithium metal anode;
wherein the electrolyte separator comprises top and bottom surfaces and a bulk therebetween, wherein the bulk has a thickness;
wherein the top surface or bottom surface length or width is greater than the thickness of the bulk by a factor of ten or more, and the thickness of the bulk is 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;
wherein either the top surface 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; and
a gel electrolyte.
14. The electrochemical cell of claim 13 , further comprising a negative electrode.
15. The electrochemical cell of claim 13 , wherein the gel comprises a solvent, a lithium salt, and a polymer.
16. The electrochemical cell of claim 15 , wherein the solvent is ethylene carbonate, propylene carbonate, diethylene carbonate, methylene carbonate, or a combination thereof.
17. The electrochemical cell of claim 16 , wherein the lithium salt is LiPF 6 , LiBOB, or LFTSi.
18. The electrochemical cell of claim 15 , wherein the polymer is PVDF-HFP.
19. The electrochemical cell of claim 13 , wherein the electrolyte separator is a pellet, a film, free-standing film, or a monolith.
20. The electrochemical cell of claim 19 , wherein the electrolyte separator is a film with a thickness is from 10 nm to about 100 μm.
21. The electrochemical cell of claim 13 , wherein either the top surface or bottom surface of the electrolyte separator is characterized by XPS or FT-IR.
22. The electrochemical cell of claim 13 , wherein the top and bottom surfaces of the electrolyte separator are 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.
23. The electrochemical cell of claim 22 , wherein the top and bottom surfaces of the electrolyte separator are characterized by XPS or FT-IR.