BOROHYDRIDE-SULFIDE INTERFACIAL LAYER IN ALL SOLID-STATE BATTERY

1 . A composition comprising A(LiBH 4 )(1−A)(P 2 S 5 ), wherein 0.05≤A≤0.95.

2 . The composition of claim 1 , wherein 0.5<A<0.95.

3 . The composition of claim 1 or 2 , wherein A is 0.85, 0.9, or 9.95.

4 . The composition of claim 1 , 2 , or 3 , wherein the composition comprises 0.9(LiBH 4 )0.1(P 2 S 5 ).

5 . The composition of any one of claims 1 - 4 , wherein the composition is amorphous.

6 . The composition of any one of claims 1 - 4 , wherein the composition is semi-crystalline.

7 . The composition of any one of claims 1 - 4 , wherein the composition is polycrystalline.

8 . The composition of any one of claims 1 - 7 , wherein the composition is a thin film.

9 . The composition of claim 8 , wherein the thin film has a thickness of about 1 μm-200 μm.

10 . The composition of claim 9 , wherein the thickness is about 10 μm-100 μm.

11 . The composition of any one of claims 1 - 7 , wherein the composition is a monolith.

12 . The composition of any one of claims 1 - 7 , wherein the composition is a pressed pellet.

13 . The composition of claim 12 , wherein the pellet has a thickness of about 1 mm-100 mm.

14 . The composition of any one of claims 5 - 13 , wherein the composition has porosity of <5% by volume.

15 . The composition of claim 14 , wherein the porosity is less than 0.5% volume.

16 . The composition of any one of claims 1 - 15 , further comprising an oxide, a sulfide, a sulfide-halide, or a combination thereof.

17 . The composition of any one of claims 1 - 15 , further comprising an electrolyte.

18 . The composition of claim 16 , wherein the oxide is a lithium-stuffed garnet characterized by the formula Li x La y Zr z O t .qAl 2 O 3 , wherein 4<x<10, 1<y<4, 1<z<3, 6<t<14, 0≤q≤1.

19 . The composition of claim 16 , wherein the oxide is a lithium-stuffed garnet doped with Nb, Ga, and/or Ta.

20 . The composition of claim 16 , wherein the oxide is a lithium-stuffed garnet characterized by the formula Li a La b Zr c Al d Me″ e O f , wherein 5<a<8.5; 2<b<4; 0≤c≤2.5; 0≤d<2; 0≤e<2, and 10<f<13 and Me″ is a metal selected from the group consisting of Nb, Ga, Ta, and combinations thereof.

21 . The composition of claim 16 , wherein the sulfide or sulfide-halide is selected from LSS, SLOPS, LSTPS, LSTPSCl, SLOBS, LATS, or LPS+X, wherein X is selected from the group consisting of Cl, I, and Br.

22 . The composition of claim 16 , wherein the sulfide or sulfide-halide is selected from LSS, SLOPS, LSTPS, SLOBS, LATS, or LPS+X, wherein X is selected from the group consisting of Cl, I, and Br.

23 . The composition of claim 22 , wherein the LPS+X is LPSI.

24 . The composition of claim 16 , wherein the oxide is a lithium-stuffed garnet oxide characterized by the formula Li u La v Zr x O y .zAl 2 O 3 , wherein

u is a rational number from 4 to 8;

v is a rational number from 2 to 4;

x is a rational number from 1 to 3;

y is a rational number from 10 to 14; and

z is a rational number from 0.05 to 1;

wherein u, v, x, y, and z are selected so that the lithium-stuffed garnet oxide is charge neutral.

25 . The composition of claim 16 , wherein the sulfide is a lithium sulfide characterized by one of the following formula:

Li a Si b Sn c P d S e O f , wherein 2≤a≤8, 0≤b≤1, 0≤c≤1, b+c=1, 0.5≤d≤2.5, 4≤e≤12, and 0<f≤10;

Li a Si b P c S d X e , wherein 8<a<12, 1<b<3, 1<c<3, 8<d<14, and 0<e<1, wherein X is F, Cl, Br, or I;

Li g As h Sn j S k O l , wherein 2≤g≤6, 0≤h≤1, 0≤j≤1, 2≤k≤6, and 0≤1≤10;

Li m P n S p I q , wherein 2≤m≤6, 0≤n≤1, 0≤p≤1, 2≤q≤6;

a mixture of (Li 2 S):(P 2 S 5 ) having a molar ratio of Li 2 S:P 2 S 5 from about 10:1 to about 6:4 and LiI, wherein the ratio of [(Li 2 S):(P 2 S 5 )]:LiI is from 95:5 to 50:50;

LPS+X, wherein X is selected from Cl, I, or Br;

vLi 2 S+wP 2 S 5 +yLiX;

vLi 2 S+wSiS 2 +yLiX; or

vLi 2 S+wB 2 S 3 +yLiX.

26 . The composition of claim 16 or 25 , wherein the composition comprises:

a mixture of LiI and Al 2 O 3 ;

Li 3 N;

a mixture of LiBH 4 and LiX wherein X is selected from Cl, I, or Br; or

vLiBH 4 +wLiX+yLiNH 2 , wherein X is selected from Cl, I, or Br; and

wherein coefficients v, w, and y are rational numbers from 0 to 1.

27 . The composition of claim 17 , wherein the electrolyte is selected from the group consisting of:

LIRAP;

LATP;

LAGP;

a mixture of LiI and Al 2 O 3 ;

Li 3 N;

a mixture of LiBH 4 and LiX wherein X is selected from Cl, I, or Br; and

vLiBH 4 +wLiX+yLiNH 2 , wherein X is selected from Cl, I, or Br;

wherein coefficients v, w, and y are rational numbers from 0 to 1.

28 . The composition of claim 16 , wherein the oxide is a lithium-stuffed garnet oxide characterized by the formula Li u La v Zr x O y .zTa 2 O 5 , wherein

u is a rational number from 4 to 10;

v is a rational number from 2 to 4;

x is a rational number from 1 to 3;

y is a rational number from 10 to 14; and

z is a rational number from 0 to 1;

wherein u, v, x, y, and z are selected so that the lithium-stuffed garnet oxide is charge neutral.

29 . The composition of claim 16 , wherein the oxide is a lithium-stuffed garnet oxide characterized by the formula Li u La v Zr x O y .zNb 2 O 5 , wherein

u is a rational number from 4 to 10;

v is a rational number from 2 to 4;

x is a rational number from 1 to 3;

y is a rational number from 10 to 14; and

z is a rational number from 0 to 1;

wherein u, v, x, y, and z are selected so that the lithium-stuffed garnet oxide is charge neutral.

30 . The composition of claim 16 , wherein the oxide is a lithium-stuffed garnet oxide characterized by the formula Li u La v Zr x O y .zGa 2 O 3 , wherein

u is a rational number from 4 to 10;

v is a rational number from 2 to 4;

x is a rational number from 1 to 3;

y is a rational number from 10 to 14; and

z is a rational number from 0 to 1;

wherein u, v, x, y, and z are selected so that the lithium-stuffed garnet oxide is charge neutral.

31 . The composition of claim 16 , wherein the oxide is a lithium-stuffed garnet oxide characterized by the formula Li u La v Zr x O y .zTa 2 O 5 .bAl 2 O 3 , wherein

u is a rational number from 4 to 10;

v is a rational number from 2 to 4;

x is a rational number from 1 to 3;

y is a rational number from 10 to 14;

z is a rational number from 0 to 1;

b is a rational number from 0 to 1;

wherein z+b≤1; and

u, v, x, y, and z are selected so that the lithium-stuffed garnet oxide is charge neutral.

32 . The composition of claim 16 , wherein the oxide is a lithium-stuffed garnet oxide characterized by the formula Li u La v Zr x O y .zNb 2 O 5 .bAl 2 O 3 , wherein

u is a rational number from 4 to 10;

v is a rational number from 2 to 4;

x is a rational number from 1 to 3;

y is a rational number from 10 to 14;

z is a rational number from 0 to 1;

b is a rational number from 0 to 1;

wherein z+b≤1; and

u, v, x, y, and z are selected so that the lithium-stuffed garnet oxide is charge neutral.

33 . The composition of claim 16 , wherein the oxide is:

a lithium-stuffed garnet oxide characterized by the formula Li u La v Zr x O y .zGa 2 O 3 .bAl 2 O 3 , wherein

u is a rational number from 4 to 10;

v is a rational number from 2 to 4;

x is a rational number from 1 to 3;

y is a rational number from 10 to 14; and

z is a rational number from 0 to 1;

b is a rational number from 0 to 1;

wherein z+b≤1; and

u, v, x, y, and z are selected so that the lithium-stuffed garnet oxide is charge neutral.

34 . The composition of claim 16 , wherein the oxide is Li 6.4 Ga 0.2 La 3 Zr 2 O 12 .

35 . The composition of any one of claims 1 - 34 , wherein the total effective lithium ion conductivity is greater than 10 −3 S/cm at 45° C.

36 . The composition of any one of claims 1 - 34 , wherein the lithium interfacial area-specific resistance is less than 20 Ωcm 2 at 45° C.

37 . A composition comprising a lithium-stuffed garnet and a composition of any one of claims 1 - 36 , wherein the composition of any one of claims 1 - 36 coats the surface of the lithium-stuffed garnet.

38 . A composition comprising a lithium-stuffed garnet and a composition of any one of claims 1 - 36 , wherein the composition of any one of claims 1 - 36 is conformally bonded to the surface of the lithium-stuffed garnet.

39 . A composition comprising a lithium-stuffed garnet and a composition of any one of claims 1 - 36 , wherein the composition of any one of claims 1 - 36 is bonded to defects in the lithium-stuffed garnet.

40 . The composition of any one of claims 1 - 10 and 14 - 39 , wherein the composition is a thin film and wherein the thin film has a thickness greater than 10 nm and less than 30 μm.

41 . The composition of claim 40 , wherein the thickness is less than 20 μm.

42 . The composition of claim 40 , wherein the thickness is less than 10 μm.

43 . The composition of claim 40 , wherein the thickness is less than 5 μm.

44 . The composition of claim 40 , wherein the thickness is less than 1 μm.

45 . The composition of any one of claims 1 - 10 and 14 - 39 , wherein the composition is a thin film and wherein the thin film has a porosity less than 5 percent.

46 . The composition of claim 45 , wherein the porosity is less than 4 percent.

47 . The composition of claim 45 , wherein the porosity is less than 3 percent.

48 . The composition of claim 45 , wherein the porosity is less than 2 percent.

49 . The composition of claim 45 , wherein the porosity is less than 1 percent.

50 . The composition of claim 45 , wherein the porosity is less than 0.5 percent.

51 . An electrochemical cell comprising a composition of any one of claims 1 - 50 .

52 . The electrochemical cell of claim 51 , wherein the electrochemical cell is a rechargeable battery.

53 . An electrochemical cell comprising:

a lithium metal negative electrode;

a solid separator; and

a positive electrode,

wherein the solid separator is between and in direct contact with the lithium metal negative electrode and the positive electrode; and

wherein the solid separator is a composition of any one of claims 1 - 50 .

54 . The electrochemical cell of claim 53 , wherein the solid separator is less than 20 μm thick.

55 . A method for making a thin film comprising A.(LiBH 4 )1−A.(P 2 S 5 ), wherein 0.05≤A≤0.95, comprising:

(a) providing a powder mixture, wherein the powder mixture comprises: A(LiBH 4 )(1−A)(P 2 S 5 ), wherein 0.05≤A≤0.95;

(b) Milling the powder mixture;

(c) mixing the powder mixture with a solvent or a binder or both a solvent and a binder;

(d) casting or coating the powder mixture on a substrate;

(e) spinning the substrate at 3000 rpm to form a thin film;

( 0 evaporating the solvent, if present;

(g) placing the film and the substrate under pressure.

56 . The method of claim 55 , further comprising heating the film and the substrate.

57 . The method of claim 56 , wherein the heating is to at least 300° C.

58 . The method of claim 56 , wherein the heating is to at least 500° C.

59 . The method of claim 56 , wherein the heating is to at least 7300° C.

60 . The method of claim 56 , wherein the heating is to at least 1000° C.

61 . The method of claim 56 , wherein the heating is to at maximum of 1500° C.

62 . The method of any one of claims 54 - 61 , wherein the solvent is selected from the group consisting of toluene, hexane, and tert-butyl amine.

63 . The method of claim 54 , wherein the binder is an ethylene alpha-olefin copolymer.

64 . An electrochemical device comprising of:

a lithium metal negative electrode;

a solid-state electrolyte;

a solid-state positive electrode; and

a composition of claim 1 - 50 or a thin film made by the method of claims 54 - 63 ;

wherein:

the solid-state electrolyte is between and in contact with the lithium metal negative electrode and the solid-state positive electrode; and

the composition of claim 1 - 50 or the thin film made by the method of claims 54 - 63 is between and in contact with the solid-state electrolyte and the solid-state positive electrode.

65 . The electrochemical device of claim 64 , where the solid-state positive electrode comprises active material selected from the group consisting of NCA, LNMO, and NMC.

66 . The electrochemical device of claim 64 or 65 , where the solid-state positive electrode comprises a sulfide catholyte.

67 . The electrochemical device of claim 66 , where the sulfide catholyte is LSTPS LSPSCl.

68 . The electrochemical device of any one of claims 64 - 67 , wherein the solid-state positive electrode further comprises a binder.

69 . The electrochemical device of any one of claims 64 - 68 , wherein the solid-state positive electrode further comprises a conductive additive.

70 . The electrochemical device of any one of claims 64 - 69 , wherein the solid-state electrolyte is a thin film.

71 . The electrochemical device of claim 70 , wherein the thin film has a thickness of about 1-200 μm.

72 . The electrochemical device of any one of claims 64 - 69 , wherein the solid-state electrolyte is a monolith.

73 . The electrochemical device of any one of claims 64 - 69 , wherein the solid-state electrolyte is a pressed pellet.

74 . The electrochemical device of claim 73 , wherein the solid-state electrolyte is 1 mm-100 mm in length.

75 . The electrochemical device of any one of claims 64 - 74 , wherein the solid-state electrolyte has porosity of <5%.

76 . The electrochemical device of claim 75 , wherein the porosity is less than 0.5%.

77 . The electrochemical device of any one of claims 64 - 74 , wherein the solid-state electrolyte is a lithium-stuffed garnet oxide characterized by the formula Li u La v Zr x O y .zAl 2 O 3 , wherein

u is a rational number from 4 to 8;

v is a rational number from 2 to 4;

x is a rational number from 1 to 3;

y is a rational number from 10 to 14; and

z is a rational number from 0.05 to 1;

wherein u, v, x, y, and z are selected so that the lithium-stuffed garnet oxide is charge neutral.

78 . A method for making a multilayer component comprising the composition of claim 1 , comprising:

(a) providing a first composition, wherein the composition comprises: A(LiBH 4 )(1−A)(P 2 S 5 ), wherein 0.05≤A≤0.95;

(b) dropping or spraying a powder of the first composition on a substrate;

(c) heating the powder on the substrate to above the powder melting point but below than the powder mixture decomposition temperature;

(e) providing a layer of a second composition on top of the powder on a substrate to form a multilayer;

(f) applying 1 pounds-per-square inch (PSI) to 1000 PSI pressure to the multilayer; and

(f) cooling the powder on a substrate to room temperature.

79 . The method of claim 78 , further comprising spinning the substrate at high speed, for example 100 to 5000 rpm.

80 . The method of claim 79 , further comprising spinning the substrate at high speed, for example 100 to 5000 rpm before cooling the powder mixture on a substrate to room temperature.

81 . The method of any one of claims 78 - 80 , wherein the second composition is an electrolyte.

82 . The method of any one of claims 78 - 80 , wherein the second composition is a lithium-stuffed garnet.

83 . The method of any one of claim 55 - 63 or 78 - 82 , wherein the substrate is a metal selected from the group consisting of copper and nickel.

84 . The method of any one of claim 55 - 63 or 78 - 82 , wherein the substrate is a foil.

85 . The method of any one of claim 55 - 63 or 78 - 82 , wherein the substrate is LPSI.

86 . The method of any one of claim 55 - 63 or 78 - 82 , wherein the substrate is LPSI composite.

87 . The method of any one of claim 55 - 63 or 78 - 82 , wherein the substrate is LSTPS.

88 . The method of any one of claim 55 - 63 or 78 - 82 , wherein the substrate is LSTPS composite.

89 . The method of any one of claim 55 - 63 or 78 - 82 , wherein the substrate is solid state positive electrode comprising:

an active material selected from NCA or NMC;

a sulfide catholyte;

carbon; and

binder.

90 . A composite comprising a lithium-stuffed garnet and a composition of any one of claims 1 - 50 ,

wherein the composition of any one of claims 1 - 59 infiltrates at least 90% of the through-pores or surface pores of the lithium-stuffed garnet.

91 . A composite comprising a lithium-stuffed garnet and composition of any one of claims 1 - 50 ,

wherein the composition of any one of claims 1 - 50 fills at least 90% of the through-pores or surface pores of the lithium-stuffed garnet.

92 . A composition comprising a roughened lithium-stuffed garnet having a coating of a composition of any one of claims 1 - 50 on the lithium-stuffed garnet.

93 . A composition comprising a curved lithium-stuffed garnet having a coating of a composition of any one of claims 1 - 50 on the lithium-stuffed garnet.

94 . A composition comprising a corrugated lithium-stuffed garnet having a coating of a composition of any one of claims 1 - 50 on the lithium-stuffed garnet.

95 . A composition comprising a lithium-stuffed garnet and a composition of any one of claims 1 - 50 interdigitated within the lithium-stuffed garnet.

96 . A method for coating a lithium-ion conducting separator electrolyte, the method comprising:

a) providing the lithium-ion conducting separator electrolyte; and

b) pressing a composition of A(LiBH 4 )(1−A)(P 2 S 5 ) on to at least one surface of the lithium-ion conducting separator electrolyte;

wherein the pressing is at a temperature between 100-280° C. and at a pressure of 10-2000 PSI.

97 . The method of claim 96 , wherein the temperature is below the melting point (T m ) of the separator.

98 . The method of claim 96 , wherein the temperature is about 0.8T m Kelvin (K).

99 . The method of any one of claims 96 - 98 , further comprising c) pressing for 1-300 minutes (min).

100 . The method of any one of claims 96 - 98 , further comprising d) cooling while pressing for 10-1000 min.

101 . The method of claim 100 , wherein the cooling is to room temperature.

102 . A method for coating a lithium-ion conducting electrolyte separator, the method comprising:

a) providing a lithium-ion conducting electrolyte separator;

b) providing a mixture of a solvent and a composition of any one of claims 1 - 50 ; and

c) depositing the mixture on the separator by spray coating, melt spin coating, spin coating, dip coating, slot die coating, gravure coating, or microgravure coating.

103 . The method of claim 102 , wherein the solvent is selected from the group consisting of tetrahydrofuran, diethyl ether, pyridine, methanol, and ethanol.

104 . The method of claim 103 , wherein the solvent is selected from the group consisting of tetrahydrofuran, diethyl ether, methanol and ethanol.

105 . The method of any one of claims 102 - 104 , wherein the lithium-ion conducting electrolyte separator has defects on the surface.

106 . The method of claim 102 , wherein prior to step (a) the method comprises preparing a composition of any one of claims 1 - 50 .

107 . The composition of claim 1 , wherein A>0.5

108 . The composition of claim 1 , wherein A>0.75