Lithium metal sulfides as lithium super ionic conductors, solid electrolyte and coating layer for lithium metal battery and lithium-ion battery
Solid-state lithium ion electrolytes of lithium metal sulfide based composites are provided which contain an anionic framework capable of conducting lithium ions. Composites of specific formulae are provided and methods to alter the composite materials with inclusion of aliovalent ions shown. Lithium batteries containing the composite lithium ion electrolytes are also provided. Electrodes containing the lithium metal sulfide based materials and batteries with such electrodes are also provided.
1. A solid-state lithium ion electrolyte, comprising:
at least one material selected from the group of materials consisting of compounds of formulae (I), (II), (III), (IV) and (V):
Li y (M1) x1 InSiS 6 (I)
wherein x1 is a number from greater than 0 to less than 2, y is a value such that charge neutrality of the formula is obtained, and M1 is at least one element different from Li selected from elements of groups 1, 2, 13 and a transition metal;
Li y In 2-x2 (M2) x2 SiS 6 (II)
wherein
x2 is a number from greater than 0 to less than 2; y is a value such that the formula (II) is charge neutral; and M2 is at least one element different from In selected from elements of groups 3, 4, 5, 6, 8, 9, 11, 13, 14, 16 and 17;
Li y In 2 Si 1-x3 (M3) x3 S 6 (III)
wherein x3 is from greater than 0 to less than 1; y is a value such that the formula (III) is charge neutral, and M3 is at least one element different from Si selected from elements of groups 2, 3, 5, 6, 7, 8, 9, 10, 12, 14, 15 and 16;
Li y In 2 SiS 6-x4 (X) x4 (IV)
wherein x4 is from greater than 0 to less than 6, y is a value such that the formula (IV) is charge neutral and X is an element different from S selected from elements of groups 16 and 17;
and
Li 2 In 2 SiS 6 (V)
wherein the at least one material selected from the group of materials consisting of compounds of formulae (I), (II), (III), (IV) and (V) comprises a monoclinic structure.
2. The solid state lithium ion electrolyte according to claim 1 , wherein
a lithium ion (Li + ) conductivity of the solid state lithium ion electrolyte is from 0.01 to 10 mS/cm at 300K.
3. The solid state lithium ion electrolyte according to claim 1 , wherein an activation energy of the material is from 0.27 to 0.37 eV.
4. The solid state lithium ion electrolyte according to claim 1 wherein an X-ray Diffraction Analysis obtained based on Cu-Kα radiation with wavelength of 1.54184 Å of the material comprises the following major peaks:
Peak Position
Relative Intensity
14.838
100.0
15.619
10.75
17.926
15.359
17.994
35.928
23.5
24.121
25.741
16.463
26.575
26.533
26.643
37.352
30.013
28.165
31.236
21.595
31.537
25.513
32.359
13.816
32.403
24.448
34.76
15.66
35.136
17.504
39.48
10.189
40.69
12.65
41.851
10.322
44.786
11.36
47.637
12.686.
5. A solid state lithium battery, comprising:
an anode;
a cathode; and
a solid state lithium ion electrolyte located between the anode and the cathode;
wherein
the solid state lithium ion electrolyte comprises at least one material selected from the group of materials consisting compounds of formulae (I), (II), (III), (IV) and (V):
Li y (M1) x1 InSiS 6 (I)
wherein x1 is a number from greater than 0 to less than 2, y is a value such that charge neutrality of the formula is obtained, and M1 is at least one element different from Li selected from elements of groups 1, 2, 13 and a transition metal;
Li y In 2-x2 (M2) x2 SiS 6 (II)
wherein
x2 is a number from greater than 0 to less than 2; y is a value such that the formula (II) is charge neutral, and M2 is at least one element different from In selected from elements of groups 3, 4, 5, 6, 8, 9, 11, 13, 14, 16 and 17;
Li y In 2 Si 1-x3 (M3) x3 S 6 (III)
wherein x3 is from greater than 0 to less than 1, y is a value such that the formula (III) is charge neutral, and M3 is at least one element different from Si selected from elements of groups 2, 3, 5, 6, 7, 8, 9, 10, 12, 14, 15 and 16;
Li y In 2 SiS 6-x4 (X) x4 (IV)
wherein x4 is from greater than 0 to less than 6, y is a value such that the formula (IV) is charge neutral and X is an element different from S selected from elements of groups 16 and 17;
and
Li 2 In 2 SiS 6 (V)
wherein the at least one material selected from the group of materials consisting of compounds of formulae (I), (II), (III), (IV) and (V) comprises a monoclinic structure.
6. The solid state lithium ion battery according to claim 5 , wherein the battery is a lithium metal battery or a lithium ion battery.
7. An electrode for a solid state lithium battery, comprising:
a current collector; and
an electrode active layer on the current collector;
wherein the electrode active layer comprises at least one compound selected from the group consisting of compounds of formulae (I), (II), (III), (IV) and (V):
Li y (M1) x1 InSiS 6 (I)
wherein x1 is a number from greater than 0 to less than 2, y is a value such that charge neutrality of the formula is obtained, and M1 is at least one element different from Li selected from elements of groups 1, 2, 13 and a transition metal;
Li y In 2-x2 (M2) x2 SiS 6 (II)
wherein
x2 is a number from greater than 0 to less than 2; y is a value such that the formula (II) is charge neutral, and M2 is at least one element different from In selected from elements of groups 3, 4, 5, 6, 8, 9, 11, 13, 14, 16 and 17;
Li y In 2 Si 1-x3 (M3) x3 S 6 (III)
wherein x3 is from greater than 0 to less than 1, y is a value such that the formula (III) is charge neutral, and M3 is at least one element different from Si selected from elements of groups 2, 3, 5, 6, 7, 8, 9, 10, 12, 14, 15 and 16;
Li y In 2 SiS 6-x4 (X) x4 (IV)
wherein x4 is from greater than 0 to less than 6, y is a value such that the formula (IV) is charge neutral and X is an element different from S selected from elements of groups 16 and 17;
and
Li 2 In 2 SiS 6 (V)
wherein the at least one material selected from the group of materials consisting of compounds of formulae (I), (II), (III), (IV) and (V) comprises a monoclinic structure.
8. An electrode for a solid state lithium battery, comprising:
a current collector;
an electrode active layer on the current collector; and a coating layer on the electrode active layer;
wherein the coating layer on the electrode active layer comprises at least one compound selected from the group consisting of compounds of formulae (I), (II), (III), (IV) and (V):
Li y (M1) x1 InSiS 6 (I)
wherein x1 is a number from greater than 0 to less than 2, y is a value such that charge neutrality of the formula is obtained, and M1 is at least one element different from Li selected from elements of groups 1, 2, 13 and a transition metal;
Li x In 2-x2 (M2) x2 SiS 6 (II)
wherein
x2 is a number from greater than 0 to less than 2, y is a value such that the formula is charge neutral, and M2 is at least one element different from In selected from elements of groups 3, 4, 5, 6, 8, 9, 11, 13, 14, 16 and 17;
Li y In 2 Si 1-x3 (M3) x3 S 6 (III)
wherein x3 is from greater than 0 to less than 1, y is a value such that the formula (III) is charge neutral, and M3 is at least one element different from Si selected from elements of groups 2, 3, 5, 6, 7, 8, 9, 10, 12, 14, 15 and 16;
Li y In 2 SiS 6-x4 (X) x4 (IV)
wherein x4 is from greater than 0 to less than 6, y is a value such that the formula (IV) is charge neutral and X is an element different from S selected from elements of groups 16 and 17; and
Li 2 In 2 SiS 6 (V)
wherein the at least one material selected from the group of materials consisting of compounds of formulae (I), (II), (III), (IV) and (V) comprises a monoclinic structure.
9. A solid state lithium battery comprising the electrode of claim 7 , wherein the solid state lithium battery is a lithium ion battery or a lithium metal battery.
10. A solid state lithium battery comprising the electrode of claim 8 , wherein the solid state lithium battery is a lithium ion battery or a lithium metal battery.
11. A solid-state lithium ion electrolyte, comprising:
at least one material selected from the group of materials consisting of compounds of formulae (VI), (VII), (VIII), (IX) and (X):
Li y (M4) z1 MnGe 2 S 7 (VI)
wherein z1 is a number from greater than 0 to less than 4, y is a value such that charge neutrality of the formula is obtained, and M4 is at least one element different from Li selected from elements of groups 1, 2, 13 and a transition metal;
Li y Mn 1-z2 (M5) z2 Ge 2 S 7 (VII)
wherein z2 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the formula is obtained, and M5 is at least one element different from Mn selected from elements of groups 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15 and 16;
Li y MnGe 2-z3 (M6) z3 S 7 (VIII)
wherein z3 is a number from greater than 0 to less than 2, y is a value such that charge neutrality of the formula is obtained, and M6 is at least one element different from Ge selected from elements of groups 2, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16 and 17;
Li y MnGe 2 S 7-z4 (X) z4 (IX)
wherein z4 is from greater than 0 to less than 7, y is a value such that the formula (IX) is charge neutral and X is an element different from S selected from elements of groups 16 and 17; and
Li 4 MnGe 2 S 7 (X)
wherein the at least one material selected from the group of materials consisting of compounds of formulae (VI), (VII), (VIII), (IX) and (X) comprises a monoclinic structure.
12. The solid state lithium ion electrolyte according to claim 11 , wherein
a lithium ion (Li + ) conductivity of the solid state lithium ion electrolyte is from 0.01 to 10 mS/cm at 300K.
13. The solid state lithium ion electrolyte according to claim 11 , wherein an activation energy of the material is from 0.24 to 0.38 eV.
14. The solid state lithium ion electrolyte according to claim 11 wherein an X-ray Diffraction Analysis obtained based on Cu-Kα radiation with wavelength of 1.54184 Å of the material comprises the following major peaks:
Peak Position
Relative Intensity
16.494
100.0
16.958
11.807
17.586
56.016
20.678
17.405
21.185
34.809
23.03
13.109
26.384
78.009
26.572
42.309
28.795
72.26
29.758
10.389
29.807
16.133
30.292
19.414
30.442
26.573
31.736
12.026
38.944
15.716
39.581
14.339
39.949
12.201
46.451
29.165
46.797
55.974
51.246
23.982
51.963
22.761
52.463
24.483
54.798
11.51
55.493
19.897
56.264
15.766.
15. A solid state lithium battery, comprising:
an anode;
a cathode; and
a solid state lithium ion electrolyte located between the anode and the cathode;
wherein
the solid state lithium ion electrolyte comprises at least one material selected from the group of materials consisting compounds of formulae (VI), (VII), (VIII), (IX) and (X):
Li y (M4) z1 MnGe 2 S 7 (VI)
wherein z1 is a number from greater than 0 to less than 4, y is a value such that charge neutrality of the formula is obtained, and M4 is at least one element different from Li selected from elements of groups 1, 2, 13 and a transition metal;
Li y Mn 1-z2 (M5) z2 Ge 2 S 7 (VII)
wherein z2 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the formula is obtained, and M5 is at least one element different from Mn selected from elements of groups 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15 and 16;
Li y MnGe 2-z3 (M6) z3 S 7 (VIII)
wherein z3 is a number from greater than 0 to less than 2, y is a value such that charge neutrality of the formula is obtained, and M6 is at least one element different from Ge selected from elements of groups 2, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16 and 17;
Li y MnGe 2 S 7-z4 (X) z4 (IX)
wherein z4 is from greater than 0 to less than 7, y is a value such that the formula (IX) is charge neutral and X is an element different from S selected from elements of groups 16 and 17; and
Li 4 MnGe 2 S 7 (X)
wherein the at least one material selected from the group of materials consisting of compounds of formulae (VI), (VII), (VIII), (IX) and (X) comprises a monoclinic structure.
16. The solid state lithium ion battery according to claim 15 , wherein the battery is a lithium metal battery or a lithium ion battery.
17. An electrode for a solid state lithium battery, comprising:
a current collector; and
an electrode active layer on the current collector;
wherein the electrode active layer comprises at least one compound selected from the group consisting of compounds of formulae (VI), (VII), (VIII), (IX) and (X):
Li y (M4) z1 MnGe 2 S 7 (VI)
wherein z1 is a number from greater than 0 to less than 4, y is a value such that charge neutrality of the formula is obtained, and M4 is at least one element different from Li selected from elements of groups 1, 2, 13 and a transition metal;
Li y Mn 1-x2 (M5) z2 Ge 2 S 7 (VII)
wherein z2 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the formula is obtained, and M5 is at least one element different from Mn selected from elements of groups 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15 and 16;
Li y MnGe 2-z3 (M6) z3 S 7 (VIII)
wherein z3 is a number from greater than 0 to less than 2, y is a value such that charge neutrality of the formula is obtained, and M6 is at least one element different from Ge selected from elements of groups 2, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16 and 17;
Li y MnGe 2 S 7-z4 (X) z4 (IX)
wherein z4 is from greater than 0 to less than 7, y is a value such that the formula (IX) is charge neutral and X is an element different from S selected from elements of groups 16 and 17; and
Li 4 MnGe 2 S 7 (X)
wherein the at least one material selected from the group of materials consisting of compounds of formulae (VI), (VII), (VIII), (IX) and (X) comprises a monoclinic structure.
18. An electrode for a solid state lithium battery, comprising:
a current collector;
an electrode active layer on the current collector; and a coating layer on the electrode active layer;
wherein the coating layer on the electrode active layer comprises at least one compound selected from the group consisting of compounds of formulae (VI), (VII), (IX) and (X):
Li y (M4) z1 MnGe 2 S 7 (VI)
wherein z1 is a number from greater than 0 to less than 4, y is a value such that charge neutrality of the formula is obtained, and M4 is at least one element different from Li selected from elements of groups 1, 2, 13 and a transition metal;
Li y Mn 1-z2 (M5) z2 Ge 2 S 7 (VII)
wherein z2 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the formula is obtained, and M5 is at least one element different from Mn selected from elements of groups 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15 and 16;
Li y MnGe 2-z3 (M6) z3 S 7 (VIII)
wherein z3 is a number from greater than 0 to less than 2, y is a value such that charge neutrality of the formula is obtained, and M6 is at least one element different from Ge selected from elements of groups 2, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16 and 17;
Li y MnGe 2 S 7-z4 (X) z4 (IX)
wherein z4 is from greater than 0 to less than 7, y is a value such that the formula (IX) is charge neutral and X is an element different from S selected from elements of groups 16 and 17; and
Li 4 MnGe 2 S 7 (X)
wherein the at least one material selected from the group of materials consisting of compounds of formulae (VI), (VII), (VIII), (IX) and (X) comprises a monoclinic structure.
19. A solid state lithium battery comprising the electrode of claim 17 , wherein the solid state lithium battery is a lithium ion battery or a lithium metal battery.
20. A solid state lithium battery comprising the electrode of claim 18 , wherein the solid state lithium battery is a lithium ion battery or a lithium metal battery.