Lithium potassium element oxide compounds as Li super-ionic conductor, solid electrolyte and coating layer for lithium metal battery and lithium-ion battery

Patent metadata

Field	Value
Publication number	US-11018375-B2
Application number	US-201916570888-A
Country	US
Kind code	B2
Filing date	Sep 13, 2019
Priority date	Sep 13, 2019
Publication date	May 25, 2021
Grant date	May 25, 2021

Abstract

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.

First claim

The invention claimed is:

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 intensit

Assignees

• Univ Maryland
• Toyota Eng & Mfg North America

Inventors

• Mo Yifei
• Bai Qiang
• He Xingfeng
• Ling Chen

Classifications

• H01M2300/0071

  Oxides · CPC title

• H01M10/0562 Primary

  Solid materials · CPC title

• H01M4/0404

  by coating on electrode collectors · CPC title

• H01M4/366

  as layered products · CPC title

• H01M10/052

  Li-accumulators · CPC title