Solid electrolyte for a negative electrode of a secondary battery including first and second solid electrolytes with different affinities for metal deposition electronchemical cell and method of manufacturing

1. A solid electrolyte for a negative electrode of a secondary battery, the solid electrolyte comprising:

a first solid electrolyte having a first surface; and

a second solid electrolyte on the first solid electrolyte, the second solid electrolyte having a second surface,

wherein the first solid electrolyte and the second solid electrolyte each have an ionic conductivity effective for a deposition metal,

wherein the first surface and the second surface are different in composition or composition and structure,

wherein a ratio of a length L 1 of the first solid electrolyte to a length L 2 of the second solid electrolyte is 0.1 to 1, and

wherein the solid electrolyte has a total length (L 1 +L 2 ) if 10 to 1,000 micrometers.

2. The solid electrolyte of claim 1 , further comprising an insulating frame surrounding one or both of the first and second solid electrolyte, wherein the insulating frame is non-porous.

3. The solid electrolyte of claim 1 , wherein the deposition metal comprises Li, Na, K, Mg, Zn, Ag, Al, or a combination thereof.

4. The solid electrolyte of claim 1 , wherein the deposition metal comprises Li, Na, Mg, or combination thereof.

5. The solid electrolyte of claim 1 , wherein the deposition metal is Li.

6. The solid electrolyte of claim 1 , wherein the first solid electrolyte and the second solid electrolyte are different in bulk composition, morphology, or both.

7. The solid electrolyte of claim 1 , wherein the first solid electrolyte and the second solid electrolyte each independently have an ionic conductivity for Li, Na, K, Mg, Zn, Ag, Al, or a combination thereof of at least 10 −3 S/m.

8. The solid electrolyte of claim 1 , wherein at least one of the first solid electrolyte or the second solid electrolyte is porous.

9. The solid electrolyte of claim 8 , wherein the first solid electrolyte and the second solid electrolyte comprise a void, wherein the void extends through the first solid electrolyte and the second solid electrolyte, and wherein the void is defined by the first surface of the first solid electrolyte and the second surface of the second solid electrolyte.

10. The solid electrolyte of claim 1 , wherein the first solid electrolyte and the second solid electrolyte each independently comprise a glass, a ceramic, a polymer, or a combination thereof.

11. The solid electrolyte of claim 10 , wherein the first solid electrolyte and the second solid electrolyte each independently comprise a ceramic comprising a lithium ceramic or a glass ceramic.

12. The solid electrolyte of claim 11 , wherein the lithium ceramic or glass ceramic comprises Li 7 La 3 Zr 2 O 12 ; Li 3 OX wherein X is Cl, Br, or I; Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , Li 6 PS 5 Cl; Li 10 MP2S 12 wherein M is Ge, Si, or Sn; Li 3 PS 4 ; Li 7 P 3 S 11 ; Li 3 N; Li 2 S; LiBH 4 ; Li 3 BO 3 ; Li 2 S—P 2 S 5 ; Li 2 S—P 2 S 5 -L 4 SiO 4 ; Li 2 S—Ga 2 S 3 —GeS 2 ; Li 2 S—Sb 2 S 3 —GeS 2 ; Li 3.25 —Ge 0.25 —P 0.75 S 4 ; (La 1-x Li x )TiO 3 wherein 0<x<1; Li 6 La 2 CaTa 2 O 12 ; Li 6 La 2 ANb 2 O 12 wherein A comprises Ca, Sr, Ba; Li 6 La 3 Zr 1.5 WO 12 ; Li 6.5 La 3 Zr 1.5 TaO 12 ; Li 6.625 Al 0.25 La 3 Zr 2 O 12 ; Li 3 BO 2.5 N 0.5 ; Li 9 SiAlO 8 ; Li 1+x Al x Ge 2-x (PO 4 ) 3 ; Li 1+x Al x Ti 2-x (PO 4 ) 3 ; Li 1+x Ti 2-x Al x Si y (PO 4 ) 3-y wherein 0<x<1 and 0≤y<1; LiAl x Zr 2-x (PO 4 ) 3 ; LiTi x Zr 2-x (PO 4 ) 3 wherein 0<x<2, or a combination thereof.

13. The solid electrolyte of claim 11 , wherein the lithium ceramic or glass ceramic comprises

a garnet oxide of the formula L 5+x+2 y(D y La 3-y )(Me z Zr 2-z )O d , wherein L is a monovalent cation or a divalent cation, and provided that at least a part of or all of L is Li, wherein D is a monovalent or divalent cation, Me is one of a trivalent, tetravalent, pentavalent, and a hexavalent cation, 0<x+2y≤3, 0<y≤0.5, 0≤z<2, and 0<d≤12, optionally wherein O is partially or totally substituted with a pentavalent anion, a hexavalent anion, a heptavalent anion, or combination thereof;

an antiperovskite of the formula A 3 RX wherein A is Li or Na; X is Cl, Br, I, or a super halide, or a combination thereof; and R is O or S;

an oxide solid electrolyte of the formula Li 1+/−x M1 x M2 2-x (PO 4 ) 3 , wherein M1 is Al, Ga, In, Sc, Cr, Fe, Ta, or Nb; M2 is Ti, Zr, Hf, or Ge, and 0<x<1; or (La 1-x Li x )TiO 3 wherein 0<x<1;

a sulfide ceramic or glass electrolyte comprising Li 6 PS 5 X wherein X is Cl, Br, or I; Li 10 MP 2 S 12 wherein M is Ge, Si, or Sn; Li 2 S—P 2 S 5 ; Li 2 S—P 2 S 5 -L 4 SiO 4 ; Li 2 S—Ga 2 S 3 —GeS 2 ; Li 2 S—Sb 2 S 3 —GeS 2 ; Li 3.25 —Ge 0.25 —P 0.75 S 4 ; Li 3 PS 4 ; Li 7 P 3 S 11 ; Li 3 N; Li 2 S; LiBH 4 ; or Li 3 BO 3 ;

or a combination thereof.

14. The solid electrolyte of claim 1 , wherein the first surface has a first surface energy towards the deposition metal and the second surface has a second surface energy towards the deposition metal, and wherein the first surface energy is greater than the second surface energy.

15. The solid electrolyte of claim 1 , wherein the first surface has a composition that is different from a bulk composition of the first solid electrolyte, the second surface has a composition that is different from a bulk composition of the second solid electrolyte, or the first surface has a composition that is different from a bulk composition of the first solid electrolyte and the second surface has a composition that is different from a bulk composition of the second solid electrolyte.

16. The solid electrolyte of claim 1 ,

wherein the first surface has a first surface energy towards the deposition metal and the second surface has a second surface energy towards the deposition metal, and wherein the first surface energy is greater than the second surface energy, and

wherein the first surface has a first charge transfer resistance for deposition of the deposition metal and the second surface has a second charge transfer resistance for deposition of the deposition metal, and wherein the first charge transfer resistance is greater than the second charge transfer resistance.

17. The solid electrolyte of claim 1 , wherein an area of the first surface is less than or equal to an area of the second surface.

18. The solid electrolyte of claim 17 , wherein a ratio of the area of the first surface to the area of the second surface is 0.1 to 1.

19. The solid electrolyte of claim 1 , wherein the first surface has a first charge transfer resistance for deposition of the deposition metal and the second surface has a second charge transfer resistance for deposition of the deposition metal, and wherein the first charge transfer resistance is greater than the second charge transfer resistance.

20. The solid electrolyte of claim 19 , wherein a ratio of the first charge transfer resistance to the second charge transfer resistance is greater than 30.

21. The solid electrolyte of claim 1 , wherein the first surface and the second surface each independently further comprise a carbonate, a halogen, an oxide, a polymer, a silicide, a phosphide, a sulfide, a metal of Groups 2 to 16, or a combination thereof.

22. The solid electrolyte of claim 21 , wherein the first surface comprises the carbonate, the halogen, the oxide, the polymer, or combination thereof in a first amount, the second surface comprises the oxide, the carbonate, the silicide, the phosphide, the sulfide, the aluminum oxide, the magnesium, the niobium, the gold, the silver, the calcium, the indium, the tin, the antimony, the zinc, the polymer, or a combination thereof in a second amount, and the first amount and the second amount are different.

23. The solid electrolyte of claim 21 ,

wherein the polymer comprises a polyacetal, a polyolefin, a poly(alkylene oxide), a poly(meth)acrylate, a polycarbonate, a polystyrene, a polyester, a polyamide, a polyamideimide, a polyarylate, a polyarylsulfone, a polyethersulfone, a polyphenylene sulfide, a polyvinyl chloride, a polysulfone, a polyimide, a polyetherimide, a polytetrafluoroethylene, a polyetherketone, a polyether etherketone, a polyether ketone ketone, a polybenzoxazole, a polyphthalide, a polyanhydride, a polyvinyl ether, a polyvinyl thioether, a polyvinyl alcohol, a polyvinyl ketone, a polyvinyl halide, a polyvinyl nitrile, a polyvinyl ester, a polysulfonate, a polysulfide, a polythioester, a polysulfone, a polysulfonamide, a polyurea, a polyphosphazene, a polysilazane, a polyethylene terephthalate, a polybutylene terephthalate, a polyurethane, an ethylene propylene diene rubber, a polytetrafluoroethylene, a fluorinated ethylene propylene, a perfluoroalkoxyethylene, a polychlorotrifluoroethylene, a polyvinylidene fluoride, or a combination thereof.

24. The solid electrolyte of claim 21 , wherein the first surface further comprises a carbonate, a halogen, an oxide, a polymer, or combination thereof.

25. The solid electrolyte of claim 24 , wherein the carbonate comprises lithium carbonate, the halogen comprises lithium fluoride, and the oxide comprises lithium oxide, lanthanum oxide, zirconium oxide, lanthanum zirconium oxide, hafnium oxide, calcium oxide, gadolinium oxide, samarium oxide, yttrium oxide, or combination thereof.

26. The solid electrolyte of claim 24 , wherein the polymer comprises polyethylene, polypropylene, polystyrene, poly(ethylene oxide), poly(methacrylate), poly(imide), or a combination thereof.

27. The solid electrolyte of claim 21 , wherein the second surface further comprises an oxide, a silicide, a phosphide, a sulfide, a carbonate, an aluminum oxide, magnesium, niobium, gold, silver, calcium, indium, tin, antimony, zinc, a polymer, or a combination thereof.

28. The solid electrolyte of claim 27 , wherein the second surface further comprises lithium oxide, lithium carbonate, lithium silicide, lithium phosphide, lithium sulfide, lithium aluminum oxide, a lithium-magnesium alloy, lithium nitride, a lithium-niobium alloy, a lithium-gold alloy, a lithium-silver alloy, a lithium-aluminum alloy, a lithium-calcium alloy, a lithium-indium alloy, a lithium-tin alloy, a lithium-antimony alloy, a lithium-zinc alloy, or a combination thereof.

29. The solid electrolyte of claim 27 , wherein the polymer comprises polyethylene, polypropylene, polystyrene, poly(ethylene oxide), poly(methacrylate), poly(imide), polypropylene oxide, polyvinylidene fluoride, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyacrylonitrile, polyester sulfide, poly(ethylene oxide) doped with a sodium salt, poly(ethylene oxide) doped with a lithium salt, or a combination thereof.

30. An electrode assembly for an electrochemical cell, the electrode assembly comprising:

at least one of a current collector and a separator; and

the solid electrolyte of claim 1 ;

wherein the solid electrolyte is disposed on the current collector if present, on the separator if present, or between the current collector and the separator if both are present,

wherein the first surface of the first solid electrolyte and the second surface of the second solid electrolyte define a void, which extends through the solid electrolyte.

31. The electrode assembly of claim 30 , wherein the separator has a composition that is the same as a bulk composition of the first solid electrolyte.

32. The electrode assembly of claim 31 , wherein the composition of the separator and the bulk composition of the first solid electrolyte are the same as a bulk composition of the second solid electrolyte.

33. An electrochemical cell comprising:

a positive electrode; and

the electrode assembly of claim 30 disposed on the positive electrode.

34. The electrochemical cell of claim 33 , further comprising the deposition metal disposed on the current collector, the first surface of the first solid electrolyte, the second surface of the second solid electrolyte, or a combination thereof.

35. The electrochemical cell of claim 34 , wherein an amount of the deposition metal disposed on the first surface is less than an amount of the deposition metal disposed on the second surface.

36. The electrochemical cell of claim 34 , wherein at least a portion of the void adjacent to the separator and defined by the first surface of the first solid electrolyte is substantially free of the deposition metal at all states of charge of the electrochemical cell.

37. A solid electrolyte for a negative electrode for a secondary battery, the solid electrolyte comprising:

a first solid electrolyte having a first surface; and

a second solid electrolyte on the first solid electrolyte, the second solid electrolyte having a second surface;

wherein the first solid electrolyte and the second solid electrolyte each have an ionic conductivity effective for a deposition metal,

wherein the first surface and the second surface each independently further comprise a carbonate, a halogen, an oxide, a polymer, an oxide, a silicide, a phosphide, a sulfide, an oxide, a metal of Groups 2 to 16, or a combination thereof,

wherein the first surface and the second surface are different in composition or composition and structure,

wherein a ratio of a length L 1 of the first solid electrolyte to a length L 2 of the second solid electrolyte is 0.1 to 1; and

wherein the solid electrolyte has a total length (L 1 +L 2 ) of 10 to 1,000 micrometers.

38. The solid electrolyte of claim 37 , wherein the first surface and the second surface each comprise the carbonate, wherein the carbonate is present on the first surface in a first amount and the carbonate is present on the second surface in a second amount, wherein the first amount is greater than the second amount.

39. An electrochemical cell comprising:

a positive electrode;

a separator disposed adjacent to the positive electrode;

negative electrode comprising

a first porous solid electrolyte adjacent to the separator and opposite the positive electrode,

a second porous solid electrolyte adjacent to the first porous solid electrolyte and opposite the separator,

wherein the first porous solid electrolyte and the second porous solid electrolyte define a void which is adjacent the separator; and

a current collector disposed on the second porous solid electrolyte and opposite the first porous solid electrolyte,

wherein a first surface of the first porous solid electrolyte and a second surface of the second solid electrolyte are different in composition or composition and structure,

wherein a ratio of a length L 1 of the first solid electrolyte to a length L 2 of the second solid electrolyte is 0.1 to 1, and

wherein the solid electrolyte has a total length (L 1 +L 2 ) of 10 to 1,000 micrometers.

40. The electrochemical cell of claim 39 ,

wherein the first surface has as first surface energy towards a deposition metal and the second surface has a second surface energy towards the deposition metal, and wherein the first surface energy is greater than the second surface energy; or

wherein the first surface has as first charge transfer resistance for deposition of the deposition metal and the second surface has a second charge transfer resistance for deposition of the deposition metal, and wherein the first charge transfer resistance is greater than the second charge transfer resistance.

41. The electrochemical cell of claim 40 ,

wherein the deposition metal comprises Li, Na, K, Mg, Zn, Ag, Al, or a combination thereof, and

wherein the deposition metal is disposed on the surface of the second porous solid electrolyte.