ELECTROLYTE SEPARATORS INCLUDING LITHIUM BOROHYDRIDE AND COMPOSITE ELECTROLYTE SEPARATORS OF LITHIUM-STUFFED GARNET AND LITHIUM BOROHYDRIDE

1 . A composition, comprising:

A·(LiBH 4 )·B·(LiX)·C·(LiNH 2 ),

wherein X is fluorine, bromine, chlorine, iodine, or a combination thereof, and

wherein 0.1≤A≤4, 0.1≤B≤5, and 0<C≤9.5.

2 . A composition, comprising:

A·(LiBH 4 )·B·(LiX)·C·(LiNH 2 ),

wherein X is fluorine, bromine, chlorine, iodine, or a combination thereof, and

wherein 0.1≤A≤3, 0.1≤B≤4, and 0<C≤9.

3 . The composition of claim 1 or 2 , wherein X is bromine, chlorine, iodine, or a combination thereof.

4 . The composition of any one of claims 1-3 , wherein X is chlorine.

5 . The composition of any one of claims 1-3 , wherein X is bromine.

6 . The composition of any one of claims 1-3 , wherein X is iodine.

7 . The composition of any one of claims 1-5 , wherein 2.5<A<3.5, 1.5<B<2.5, and 2.5<C<3.5.

8 . The composition of any one of claims 1-5 , wherein 2.5<A<3.5, 3.5<B<4.5, and 8.5<C<9.5.

9 . The composition of any one of claims 1-3 wherein the composition is 3LiBH 4 ·2LiCl·3LiNH 2 or 3LiBH 4 ·4LiCl·9LiNH 2 .

10 . The composition of any one of claims 1-3 and 5 , wherein the composition is 3LiBH 4 ·2LiBr·3LiNH 2 or 3LiBH 4 ·4LiBr·9LiNH 2 .

11 . The composition of any one of claims 1-3 and 6 , wherein the composition is 3LiBH 4 ·2LiI·3LiNH 2 or 3LiBH 4 ·4LiI·9LiNH 2 .

12 . The composition of any one of claims 1-11 , wherein the composition is amorphous.

13 . The composition of any one of claims 1-11 , wherein the composition is semi-crystalline.

14 . The composition of any one of claims 1-13 , wherein the composition has a lithium ion conductivity greater than 1×10 −4 S/cm at 60° C.

15 . The composition of any one of claims 1-14 , wherein the composition has grains with a d 90 grain size of less than 20 μm.

16 . The composition of any one of claims 1-15 , wherein the composition has grains with a d 90 grain size of less than 10 μm.

17 . The composition of any one of claims 1-16 , wherein the composition has grains with a d 90 grain size of less than 5 μm.

18 . The composition of any one of claims 1-17 , wherein the composition has grains with a d 90 grain size of less than 2 μm.

19 . The composition of any one of claims 1-18 , wherein the composition has grains with a d 90 grain size of less than 1 μm.

20 . The composition of any one of claims 1-19 , wherein the composition is a thin film.

21 . The composition of any one of claims 1-19 , wherein the composition is a monolith.

22 . The composition of any one of claims 1-19 , wherein the composition is a pressed pellet.

23 . The composition of any one of claims 1-22 , further comprising an oxide, a sulfide, a sulfide-halide, or a combination thereof.

24 . The composition of any one of claims 1-23 , further comprising an electrolyte.

25 . The composition of claim 20 , 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, and 0≤q≤1.

26 . The composition of claim 25 , wherein the lithium-stuffed garnet is doped with Nb, Ga, and/or Ta.

27 . The composition of claim 23 , wherein the oxide is a lithium-stuffed garnet characterized by the formula Li a La b Zr e 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.

28 . The composition of claim 23 , wherein the sulfide or sulfide-halide is selected from LSS, SLOPS, LSTPS, LSTPSCI, SLOBS, LATS, or LPS+X, wherein X is selected from the group consisting of Cl, I, and Br.

29 . The composition of claim 23 , 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.

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

31 . The composition of claim 23 , 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;

z is a rational number from 0.05 to 1; and

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

32 . The composition of claim 23 , 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≤l≤10;

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

33 . The composition of claim 23 or 32 , 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.

34 . The composition of claim 24 , 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;

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.

35 . The composition of claim 23 , 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.

36 . The composition of claim 23 , 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.

37 . The composition of claim 23 , 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.

38 . The composition of claim 23 , 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.

39 . The composition of claim 23 , 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.

40 . The composition of claim 23 , 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.

41 . The composition of claim 23 , wherein the oxide is Li 6.4 Ga 0.2 La 3 Zr 2 O 12 .

42 . The composition of any one of claims 1-41 , wherein the total effective lithium ion conductivity is greater than 10 −4 S/cm at 25° C.

43 . The composition of any one of claims 1-41 , wherein the lithium interfacial area-specific resistance is less than 20 Ωcm 2 at 25° C.

44 . The composition of any one of claims 1-43 , wherein the composition has a transmission coefficient of greater than 0.05 at 500 nm incident wavelength and the transmission properties of the composition vary by less than 50% over a surface area of at least 100 μm 2 .

45 . The composition of any one of claims 1-43 , wherein the composition has a transmission coefficient of greater than 0.05 at 500 nm incident wavelength and is less than 1 mm thick.

46 . A composition comprising a lithium-stuffed garnet and a composition of any one of claims 1-45 , wherein the composition of any one of claims 1-45 coats the surface of the lithium-stuffed garnet.

47 . A composition comprising a lithium-stuffed garnet and a composition of any one of claims 1-45 , wherein the composition of any one of claims 1-45 is conformally bonded to the surface of the lithium-stuffed garnet.

48 . A composition comprising a lithium-stuffed garnet and a composition of any one of claims 1-45 , wherein the composition of any one of claims 1-45 is bonded to defects in the lithium-stuffed garnet.

49 . The composition of any one of claims 1-20 and 23-47 , wherein the composition is a thin film and wherein the thin film has a thickness greater than 10 nm and less than 30 μm.

50 . The composition of claim 49 , wherein the thickness is less than 20 μm.

51 . The composition of claim 49 , wherein the thickness is less than 10 μm.

52 . The composition of claim 49 , wherein the thickness is less than 5 μm.

53 . The composition of claim 49 , wherein the thickness is less than 1 μm.

54 . The composition of any one of claims 1-20 and 23-53 , wherein the composition is a thin film and wherein the thin film has a porosity less than 5 percent.

55 . The composition of claim 54 , wherein the porosity is less than 4 percent.

56 . The composition of claim 54 , wherein the porosity is less than 3 percent.

57 . The composition of claim 54 , wherein the porosity is less than 2 percent.

58 . The composition of claim 54 , wherein the porosity is less than 1 percent.

59 . The composition of claim 54 , wherein the porosity is less than 0.5 percent.

60 . An electrochemical cell comprising a composition of any one of claims 1-59 .

61 . The electrochemical cell of claim 60 , wherein the electrochemical cell is a rechargeable battery.

62 . 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 1-59 .

63 . The electrochemical cell of claim 62 , wherein the solid separator is less than 20 μm thick.

64 . A method for making a thin film comprising the composition of claim 1 , comprising:

(a) providing a powder mixture, wherein the mixture comprises:

A·(LiBH 4 )·B·(LiX)·C·(LiNH 2 );

wherein X is F, Br, Cl, I or a combination thereof, and

wherein 0.1≤A≤3, 0.1≤B≤4, and 0≤C≤9;

(b) dropping, casting, or spraying the powder mixture on a substrate;

(c) heating the powder mixture with substrate to the mixture melting point but lower than the powder mixture decomposition temperature; and

(d) cooling the substrate to room temperature.

65 . A method for making a thin film comprising the composition of claim 1 , comprising:

(a) providing a powder mixture, wherein the mixture comprises:

A·(LiBH 4 )·B·(LiX)·C·(LiNH 2 );

wherein X is F, Br, Cl, I or a combination thereof, and

wherein 0.1≤A≤4, 0.1≤B≤4, and 0≤C≤9;

(b) dropping, casting, or spraying the powder mixture onto a substrate;

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

(c) spinning the substrate; and

(d) cooling the substrate to room temperature.

66 . The method of claim 65 , wherein the spinning the substrate is at 100 to 5000 revolutions per minute (rpm).

67 . A method for making a thin film comprising the composition of claim 1 , comprising:

(a) providing a powder mixture, wherein the mixture comprises:

A·(LiBH 4 )·B·(LiX)·C·(LiNH 2 );

wherein X is F, Br, Cl, I or a combination thereof; and

wherein 0.1≤A≤4, 0.1≤B≤4, and 0≤C≤9;

(b) mixing the powder mixture with a solvent to form a suspension;

(c) dropping, casting, or spraying the suspension on a substrate; and

(c) evaporating the solvent.

68 . A method for making a thin film comprising the composition of claim 1 , comprising:

(a) providing a molten mixture, wherein the mixture comprises:

A·(LiBH 4 )·B·(LiX)·C·(LiNH 2 );

wherein X is F, Br, Cl, I or a combination thereof; and

wherein 0.1≤A≤4, 0.1≤B≤4, and 0≤C≤9;

(b) dip-coating a substrate in the molten mixture,

(c) withdrawing the substrate; and

(d) cooling the substrate to room temperature.

69 . A method for making a thin film comprising the composition of claim 1 , comprising:

(a) providing a molten mixture, wherein the mixture comprises:

A·(LiBH 4 )·B·(LiX)·C·(LiNH 2 );

wherein X is F, Br, Cl, I or a combination thereof; and

wherein 0.1≤A≤3, 0.1≤B≤4, and 0≤C≤9;

(b) dip-coating a substrate in the molten mixture,

(c) withdrawing the substrate; and

(d) cooling the substrate.

70 . The method of any one of claims 64-69 , wherein the thin film has a thickness greater than 10 nm and less than 30 μm.

71 . The method of any one of claim 70 , wherein the thickness is less than 20 μm.

72 . The method of any one of claim 70 , wherein the thickness is less than 10 μm.

73 . The method of any one of claim 70 , wherein the thickness is less than 5 μm.

74 . The method of any one of claim 70 , wherein the thickness is less than 1 μm

75 . The method of any one of claims of any one of claims 64-69 , wherein the thin film has an Li + ion conductivity greater than 1×10 −4 S/cm at 60° C.

76 . The method of any one of claims of any one of claims 64-69 , wherein the substrate is a solid separator-electrolyte for a lithium battery.

77 . The method of any one of claims 64-69 , wherein the substrate is a lithium-stuffed garnet.

78 . The method of any one of claims 64-69 , wherein the substrate is a metal selected from the group consisting of copper and nickel.

79 . The method of any one of claims 64-69 , wherein the substrate is a foil.

80 . The method of any one of claims 64-69 , wherein the substrate is LPSI.

81 . The method of any one of claims 64-69 , wherein the substrate is LPSI composite.

82 . The method of any one of claims 64-69 , wherein the substrate is solid-state positive electrode comprising:

an active material selected from NCA or NMC;

a sulfide catholyte;

carbon; and

binder.

83 . 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 )·B·(LiX)·C·(LiNH 2 );

wherein X is F, Br, Cl, I or a combination thereof, and

wherein 0.1≤A≤4, 0.1≤B≤4, and 0≤C≤9;

(b) dropping or spraying the powder mixture on a substrate;

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

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

(f) applying 1 PSI to 1000 PSI pressure to the multilayer; and

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

84 . The method of claim 83 , further comprising spinning the substrate at high speed, for example 100 to 5000 rpm.

85 . The method of claim 83 , 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.

86 . The method of any one of claims 83-85 , wherein the second composition is an electrolyte.

87 . The method of any one of claims 83-85 , wherein the second composition is a lithium-stuffed garnet.

88 . The method of any one of claims 64-69 or 83-85 , wherein the substrate is a metal selected from the group consisting of copper and nickel.

89 . The method of any one of claims 64-69 or 83-85 , wherein the substrate is a foil.

90 . The method of any one of claims 64-69 or 83-85 , wherein the substrate is LPSI.

91 . The method of any one of claims 64-69 or 83-85 , wherein the substrate is LPSI composite.

92 . The method of any one of claims 64-69 or 83-85 , wherein the substrate is LSTPS.

93 . The method of any one of claims 64-69 or 83-85 , wherein the substrate is LSTPS composite.

94 . The method of any one of claims 64-69 or 83-85 , wherein the substrate is solid-state positive electrode comprising:

an active material selected from NCA or NMC;

a sulfide catholyte;

carbon; and

binder.

95 . A composite comprising a lithium-stuffed garnet and a composition of any one of claims 1-59 ,

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.

96 . A composite comprising a lithium-stuffed garnet and composition of any one of claims 1-59 ,

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

97 . A composition comprising a roughened lithium-stuffed garnet having a coating of a composition of any one of claims 1-59 on the lithium-stuffed garnet.

98 . A composition comprising a curved lithium-stuffed garnet having a coating of a composition of any one of claims 1-59 on the lithium-stuffed garnet.

99 . A composition comprising a corrugated lithium-stuffed garnet having a coating of a composition of any one of claims 1-59 on the lithium-stuffed garnet.

100 . A composition comprising a lithium-stuffed garnet and a composition of any one of claims 1-59 interdigitated within the lithium-stuffed garnet.

101 . 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 )·B·(LiX)·C·(LiNH 2 ),

wherein X is fluorine, bromine, chloride, iodine, or a combination thereof, and

wherein 0.1≤A≤3, 0.1≤B≤4, and 0≤C≤9 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.

102 . The method of claim 101 , wherein the temperature is below the melting point (T m ) of the separator.

103 . The method of claim 101 , wherein the temperature is about 0.8 T m Kelvin (K).

104 . The method of any one of claims 101-103 , further comprising c) pressing for 1-300 minutes (min).

105 . The method of any one of claims 101-104 , further comprising d) cooling while pressing for 10-1000 min.

106 . The method of claim 105 , wherein the cooling is to room temperature.

107 . 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 1-59 ; 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.

108 . The method of claim 107 , wherein the solvent is selected from the group consisting of tetrahydrofuran, diethyl ether, pyridine, methanol, and ethanol.

109 . The method of claim 108 , wherein the solvent is selected from the group consisting of tetrahydrofuran, diethyl ether, methanol and ethanol.

110 . The method of any one of claims 107-109 , wherein the lithium-ion conducting electrolyte separator has defects on the surface.

111 . The method of claim 107 , wherein prior to step (a) the method comprises preparing a composition of any one of claims 1-59 .