Catholytes for solid state rechargeable batteries, battery architectures suitable for use with these catholytes, and methods of making and using the same
Provided herein are electrochemical cells having a solid separator, a lithium metal anode, and a positive electrode catholyte wherein the electrochemical cell includes a nitrile, dinitrile, or organic sulfur-including solvent and a lithium salt dissolved therein. Also set forth are methods of making and using these electrochemical cells.
1. A catholyte comprising,
an organic sulfur-including solvent;
a carbonate solvent comprising ethylene carbonate; and
a lithium salt;
wherein the organic sulfur-including solvent is sulfolane;
wherein the ratio of ethylene carbonate to sulfolane is 1:9 to 9:1;
wherein the lithium salt is selected from LiPF 6 , LiBOB, LiTFSI, LiBF 4 , LiClO 4 , LiFSI, LiAsF 6 , LiI, and a combination thereof;
and wherein the catholyte is chemically stable when in contact with a solid separator.
2. The catholyte of claim 1 , further comprising a solvent selected from diethylene carbonate, diethyl carbonate, dimethyl carbonate (DMC), ethyl-methyl carbonate (EMC), tetrahydrofuran (THF), γ-Butyrolactone (GBL), fluoroethylene carbonate (FEC), fluoromethyl ethylene carbonate (FMEC), trifluoroethyl methyl carbonate (F-EMC), 1,1,2,2-tetrafluoro-3-(1,1,2,2-tetrafluoroethoxy)propane (F-EPE), fluorinated cyclic carbonate (F-AEC), propylene carbonate (PC), dioxolane, acetonitrile (ACN), succinonitrile, adiponitrile, hexanedinitrile, pentanedinitrile, acetophenone, isophorone, benzonitrile, dimethyl sulfate, dimethyl sulfoxide (DMSO), ethyl acetate, methyl butyrate, dimethyl ether (DME), diethyl ether, propylene carbonate, dioxolane, glutaronitrile, and combinations thereof.
3. The catholyte of claim 1 , wherein the ethylene carbonate to sulfolane ratio is 3:7 by volume.
4. The catholyte of claim 1 , wherein the lithium salt is selected from LiPF 6 , LiBOB, LiTFSI, and combinations thereof.
5. The catholyte of claim 1 , wherein the lithium salt is LiPF 6 and is present at a concentration of 0.5 M to 2 M.
6. The catholyte of claim 1 , wherein the lithium salt is LiTFSI and is present at a concentration of 0.5 M to 2 M.
7. The catholyte of claim 1 , wherein the catholyte has a lithium transference number of greater than 0.2.
8. The catholyte of claim 1 , wherein the catholyte has a total ionic conductivity of greater than 1e-4 S/cm at 25° C.
9. The catholyte of claim 1 , wherein the organic sulfur-including solvent is stable up to 4.7 V v. Lithium.
10. The catholyte of claim 1 , wherein the organic sulfur-including solvent is stable down to 1.5 V v. Lithium.
11. The catholyte of claim 1 , wherein the organic sulfur-including solvent has a total ionic conductivity of greater than 1e-4 S/cm at room temperature.
12. The catholyte of claim 1 , the lithium salt is selected from LiPF 6 , LiBOB, LiTFSI, LiFSI, LiAsF 6 , LiI, LiBF 4 , and combination thereof.
13. The catholyte of claim 1 , wherein the lithium salt is LiBF 4 .
14. The catholyte of claim 1 , wherein the lithium salt is present in the organic sulfur-including solvent at a concentration of about 5-20 mol %.
15. The catholyte of claim 1 , wherein the lithium salt is present in the organic sulfur-including solvent at a concentration of about 12 mol %.
16. The catholyte of claim 1 , wherein the lithium salt is present in the organic sulfur-including solvent at a concentration of about 4-25 mol %.
17. The catholyte of claim 1 , wherein a lithium salt is present in the organic sulfur-including solvent at a concentration of about 0.5-3.5 M.
18. The catholyte of claim 1 , wherein the catholyte comprises LiBF 4 , LiCF 3 SO 3 , LIN(CF 3 SO 2 ) 2 , or a combination thereof.
19. The catholyte of claim 1 , further comprising LiBF 4 or LiN(CF 3 SO 2 ) 2 .
20. The catholyte of claim 1 , further comprising an additives selected from VC (vinylene carbonate), VEC (vinyl ethylene carbonate), succinic anhydride, PES (prop-1-ene, 1-3 sultone), tris(trimethylsilyl) phosphite, ethylene sulfate, PBF, TMS (1,3-propylene sulfate), propylene sulfate, trimethoxyboroxine, FEC, and combinations thereof.
21. The catholyte of claim 1 , wherein the ratio of ethylene carbonate to sulfolane is 1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2, or 9:1.