Lithium potassium element oxide compounds as Li super-ionic conductor, solid electrolyte and coating layer for lithium metal battery and lithium-ion battery
Solid-state lithium ion electrolytes of lithium potassium element oxide based compounds are provided which contain an anionic framework capable of conducting lithium ions. The element atoms are Ir, Sb, I Nb and W. An activation energy of the lithium potassium element oxide compounds is from 0.15 to 0.50 eV and conductivities are from 10 −3 to 22 mS/cm at 300K. Compounds of specific formulae are provided and methods to alter the materials with inclusion of aliovalent ions shown. Lithium batteries containing the composite lithium ion electrolytes are also provided. Electrodes containing the lithium potassium element oxide 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) and (IV):
Li y (M1) x1 KMO 6 (I)
wherein M is selected from the group consisting of Ir, Sb, I, Nb and W, x1 is a number from greater than 0 to less than 6, y is a value such that charge neutrality of the formula is obtained, and M1 is an aliovalent substitute for Li and is at least one element different from Li selected from elements of groups 1, 2, 13 and transition metals;
Li y K 1-x2 (M2) x2 MO 6 (II)
wherein x2 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the composite formula is obtained, and M2 is an aliovalent substitute for K and is at least one element different from K selected from elements of groups 1, 2, 3, 4, 5, 6, 7,8, 9, 10, 11, 12 and 13;
Li y KM 1-x3 (M3) x3 O 6 (III)
wherein x3 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 M3 is an aliovalent substitute for M and is at least one element different from M selected from elements of groups 1-13; and
Li 6 KMO 6 (IV).
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 10 −3 to 22 mS/cm at 300K.
3. The solid state lithium ion electrolyte according to claim 1 , wherein an activation energy of the material is from 0.15 to 0.50 eV.
4. The solid state lithium ion electrolyte according to claim 1 , wherein the material comprises a trigonal structure.
5. The solid state lithium ion electrolyte according to claim 1 wherein the compound is of formula (IVa):
Li 6 KIrO 6 (Iva)
wherein an X-ray Diffraction Analysis obtained based on Cu-Kα radiation with wavelength of 1.54184 Å, of the material comprises the following peaks having an intensity of 10 or more relative to the peak of highest intensity being 100:
Peak Position
Relative Intensity
17.669
100.00
21.686
97.25
28.106
57.45
28.110
40.92
35.777
21.83
35.780
10.33
38.032
23.92
42.224
63.66
44.194
14.00
44.202
17.90
47.955
17.72
53.204
15.27
54.870
18.76
58.117
10.18
58.119
10.57
59.698
13.15
62.771
18.41
62.780
11.22
68.715
10.15
6. The solid state lithium ion electrolyte according to claim 1 wherein the compound is of formula (IVb):
Li 6 KNbO 6 (IVb)
wherein an X-ray Diffraction Analysis obtained based on Cu-Kα radiation with wavelength of 1.54184 Å, of the material comprises the following peaks having an intensity of 10 or more relative to the peak of highest intensity being 100:
Peak Position
Relative Intensity
17.255
98.935
21.364
69.654
27.292
100.0
27.591
49.651
34.918
24.734
37.452
17.457
41.301
67.781
43.519
15.403
47.145
12.810
51.432
10.900
52.133
13.685
53.492
20.157
60.921
28.242
67.568
11.551
7. The solid state lithium ion electrolyte according to claim 1 wherein the compound is of formula (IVc):
Li 6 KSbO 6 (IVc)
wherein an X-ray Diffraction Analysis obtained based on Cu-Kα radiation with wavelength of 1.54184 Å, of the material comprises the following peaks having an intensity of 10 or more relative to the peak of highest intensity being 100:
Peak Position
Relative Intensity
17.279
82.727
21.291
100.0
27.410
66.749
27.549
38.662
34.967
13.175
37.322
16.748
41.303
42.265
43.366
14.012
61.139
11.808
8. The solid state lithium ion electrolyte according to claim 1 wherein the compound is of formula (IVd):
Li 6 KIO 6 (IVd)
wherein an X-ray Diffraction Analysis obtained based on Cu-Kα radiation with wavelength of 1.54184 Å, of the material comprises the following peaks having an intensity of 10 or more relative to the peak of highest intensity being 100:
Peak Position
Relative Intensity
16.968
100.0
20.834
79.733
26.967
56.304
26.990
33.974
34.322
16.507
36.501
21.599
40.492
70.471
42.399
19.989
50.970
12.874
52.538
13.645
60.022
14.777
9. The solid state lithium ion electrolyte according to claim 1 wherein the compound is of formula (IVe):
Li 6 KWO 6 (IVe)
wherein an X-ray Diffraction Analysis obtained based on Cu-Kα radiation with wavelength of 1.54184 Å, of the material comprises the following peaks having an intensity of 10 or more relative to the peak of highest intensity being 100:
Peak Position
Relative Intensity
17.152
100.0
17.368
97.436
17.369
97.455
21.215
94.95
21.287
97.823
21.288
97.834
27.365
60.072
27.408
42.143
27.700
57.895
27.798
39.479
34.704
22.886
35.152
21.284
35.153
21.283
37.228
24.666
37.229
24.67
37.358
23.317
41.033
34.473
41.189
33.605
41.734
31.553
41.735
31.559
43.205
19.707
43.357
18.248
43.358
18.241
53.324
11.123
54.235
10.91
56.563
10.221
57.425
10.257
67.043
10.577
67.297
10.609
67.299
10.61
10. 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) and (IV):
Li y (M1) x1 KMO 6 (I)
wherein M is selected from the group consisting of Ir, Sb, I, Nb and W, x1 is a number from greater than 0 to less than 6, y is a value such that charge neutrality of the formula is obtained, and M1 is an aliovalent substitute for Li and is at least one element different from Li selected from elements of groups 1, 2, 13 and transition metals;
Li y K 1-x2 (M2) x2 MO 6 (II)
wherein x2 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the composite formula is obtained, and M2 is an aliovalent substitute for K and is at least one element different from K selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 13;
Li y KM 1-x3 (M3) x3 O 6 (III)
wherein x3 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 M3 is an aliovalent substitute for M and is at least one element different from M selected from elements of groups 1-13; and
Li 6 KMO 6 (IV).
11. The solid state lithium ion battery according to claim 6 , wherein the battery is a lithium metal battery or a lithium ion battery.
12. 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) and (IV):
Li y (M1) x1 KMO 6 (I)
wherein M is selected from the group consisting of Ir, Sb, I, Nb and W, x1 is a number from greater than 0 to less than 6, y is a value such that charge neutrality of the formula is obtained, and M1 is an aliovalent substitute for Li and is at least one element different from Li selected from elements of groups 1, 2, 13 and transition metals;
Li y K 1-x2 (M2) x2 MO 6 (II)
wherein x2 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the composite formula is obtained, and M2 is an aliovalent substitute for K and is at least one element different from K selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 13;
Li y KM 1-x3 (M3) x3 O 6 (III)
wherein x3 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 M3 is an aliovalent substitute for M and is at least one element different from M selected from elements of groups 1-13; and
Li 6 KMO 6 (V).
13. 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), (I) and (IV):
Li y (M1) x1 KMO 6 (I)
wherein M is selected from the group consisting of r, Sb, I, Nb and W, x1 is a number from greater than 0 to less than 6, y is a value such that charge neutrality of the formula is obtained, and M1 is an aliovalent substitute for Li and is at least one element different from Li selected from elements of groups 1, 2, 13 and transition metals;
Li y K 1-x2 (M2) x2 MO 6 (II)
wherein x2 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the composite formula is obtained, and M2 is an aliovalent substitute for K and is at least one element different from K selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 13;
Li y KM 1-x3 (M3) x3 O 6 (III)
wherein x3 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 M3 is an aliovalent substitute for M and is at least one element different from M selected from elements of groups 1-13; and
Li 6 KMO 6 (IV).
14. A solid state lithium battery comprising the electrode of claim 12 , wherein the solid state lithium battery is a lithium ion battery or a lithium metal battery.
15. A solid state lithium battery comprising the electrode of claim 13 , wherein the solid state lithium battery is a lithium ion battery or a lithium metal battery.