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,
having 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 comprises lithium carbonate, lithium hydroxide, lithium oxide, lithium peroxide, a hydrate thereof, an oxide thereof, or a combination thereof.
2. The electrolyte separator of claim 1 , wherein 6≤A≤8.
3. The electrolyte separator of claim 1 , wherein A is 6, 6.5, 7.0, 7.5, or 8.0.
4. The electrolyte separator of claim 1 , wherein 2≤B≤4.
5. The electrolyte separator of claim 1 , wherein B is 2, 2.5, 3.0, 3.5, or 4.0.
6. The electrolyte separator of claim 1 , wherein 0.5≤C≤2.
7. The electrolyte separator of claim 1 , wherein C is 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0.
8. The electrolyte separator of claim 1 , wherein either the top surface or bottom surface is characterized as having a layer of varying thickness between 0 and 0.5 μm thick thereupon comprising a lithium carbonate, lithium hydroxide, lithium oxide, lithium peroxide, a hydrate thereof, an oxide thereof, or a combination thereof.
9. The electrolyte separator of claim 8 , wherein either the top surface or bottom surface is characterized as having a layer of varying thickness between 0 and 0.1 μm thick thereupon comprising a lithium carbonate, lithium hydroxide, lithium oxide, lithium peroxide, a hydrate thereof, an oxide thereof, or a combination thereof.
10. The electrolyte separator of claim 9 , wherein either the top surface or bottom surface is characterized as having a layer of varying thickness between 0 and 0.05 μm thick thereupon comprising a lithium carbonate, lithium hydroxide, lithium oxide, lithium peroxide, a hydrate thereof, an oxide thereof, or a combination thereof.
11. The electrolyte separator of claim 1 , wherein both the top surface and bottom surfaces are characterized as having no secondary phases present on the top surface or bottom surface, wherein secondary phases are selected from LiAlO 2 , Li 2 ZrO 3 , LaAlO 3 , Li 5 AlO 4 , Li 6 Zr 2 O 7 , La 2 (Li x Al 1-x )O 4 , wherein x is from 0 to 1, or combinations thereof.
12. The electrolyte separator of claim 1 , having a Li-metal interface area specific resistance between 0 and 15 Ω cm 2 at 60° C.
13. The electrolyte separator of claim 1 , having a Li-metal interface area specific resistance of less than 2 Ω cm 2 at 25° C.
14. The electrolyte separator of claim 1 , wherein the separator is a pellet, a film, free-standing film, or a monolith.
15. An electrochemical cell comprising the electrolyte separator of claim 1 , wherein the electrochemical cell further includes a gel electrolyte.
16. The electrochemical cell of claim 15 , wherein the gel comprises a solvent, a lithium salt, and a polymer.
17. The electrochemical cell of claim 16 , wherein the solvent is ethylene carbonate, propylene carbonate, diethylene carbonate, methylene carbonate, or a combination thereof.
18. The electrochemical cell of claim 16 , wherein the lithium salt is LiPF 6 , LiBOB, or LFTSi.
19. The electrochemical cell of claim 16 , wherein the polymer is PVDF-HFP.
20. A method of cycling lithium through a solid-state lithium ion conducting ceramic, comprising:
providing an electrolyte separator according claim 1 , in contact with a lithium metal anode;
applying a pressure of at least 300 pounds per square inch (PSI) to the electrolyte separator and anode; and
cycling at least 10 μm of lithium metal at a current of at least 1 mA/cm 2 or greater.
21. A method of cycling lithium through a solid-state lithium ion conducting ceramic, comprising:
providing an electrolyte separator according to claim 1 , in contact with a lithium metal anode;
applying a pressure of at least 20 PSI to the electrolyte separator and anode; and
cycling at least 20 μm of lithium metal at a current of at least 2 mA/cm 2 or greater.