Lithium metal sulfides as lithium super-ionic conductors

Patent metadata

Field	Value
Publication number	US-10854916-B2
Application number	US-201816142217-A
Country	US
Kind code	B2
Filing date	Sep 26, 2018
Priority date	Sep 26, 2018
Publication date	Dec 1, 2020
Grant date	Dec 1, 2020

Abstract

Solid-state lithium ion electrolytes of lithium metal sulfide based composites are provided which contain an anionic framework capable of conducting lithium ions. An activation energy of the lithium metal sulfide composites is from 0.2 to 0.45 eV and conductivities are from 10−4 to 3.0 mS/cm at 300K. 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 composites 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) and (III)
Li y (M1) x1 AlS 2   (I)

wherein x1 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 M1 is at least one element different from Li selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12
Li y Al 1-x2 (M2) x2 S 2   (II)

wherein
x2 is a number from greater than 0 to less than 1, y is a value such that the formula (II) is charge neutral, and M2 is at least one element different from Al selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 16 and 17
Li y AlS 2-x3 (X) x3   (III)

wherein
x3 is from greater than 0 to less than 2, y is a value such that the formula (III) is charge neutral, and X is at least one element different from S selected from elements of groups 15, 16 and 17.

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 −4 to 3.0 mS/cm at 300K.

3. The solid state lithium ion electrolyte according to claim 1 , wherein
an activation energy of the material is from 0.2 to 0.45 eV.

4. The solid state lithium ion electrolyte according to claim 1 , wherein the material comprises a crystal lattice structure having an orthorhombic phase of the Space group Pna21.

5. 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:

degree
intensity

17.71895
34.42914

18.23311
47.59152

26.48376
100

27.51246
49.68874

28.85635
98.53228

30.22914
91.76909

31.14418
50.35734

39.56583
37.876

40.29339
17.22383

46.1055
37.3375

48.01919
65.74971

51.99837
60.87182

52.58863
28.1332

54.53236
11.56327

55.30797
24.52453

56.68777
12.70951

56.99487
44.79432

72.49036
19.48009

74.43896
10.14738

83.16481
16.05707

86.81575
10.24815

89.8654
11.25153

6. 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) and (III):
Li y (M1) x1 AlS 2   (I)

wherein x1 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 M1 is at least one element different from Li selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12
Li y Al 1-x2 (M2) x2 S 2   (II)

wherein
x2 is a number from greater than 0 to less than 1, y is a value such that the formula (II) is charge neutral, and M2 is at least one element different from Al selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 16 and 17
Li y Al S 2-x3 (X) x3   (III)

wherein
x3 is from greater than 0 to less than 2, y is a value such that the formula (III) is charge neutral, and X is at least one element different from S selected from elements of groups 15, 16 and 17.

7. The solid state lithium ion battery according to claim 6 , wherein the battery is a lithium metal battery or a lithium ion battery.

8. 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)-(IV):
Li y (M1) x AlS 2   (I)

wherein x1 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 M1 is at least one element different from Li selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12
Li y Al 1-x2 (M2) x2 S 2   (II)

wherein
x2 is a number from greater than 0 to less than 1, y is a value such that the formula (II) is charge neutral, and M2 is at least one element different from Al selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 16 and 17
Li y AlS 2-x3 (X) x3   (III)

wherein
x3 is from greater than 0 to less than 2, y is a value such that the formula (III) is charge neutral, and X is at least one element different from S selected from elements of groups 15, 16 and 17.

9. 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)-(III):
Li y (M1) x1 AlS 2   (I)

wherein x1 is a number

Assignees

• Univ Maryland
• Toyota Eng & Mfg North America

Inventors

• Mo Yifei
• He Xingfeng
• Ling Chen
• Zhang Ying

Classifications

• H01M10/0562 Primary

  Solid materials · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title

• C01B17/22

  Alkali metal sulfides or polysulfides · CPC title

• H01M10/0525 Primary

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M4/62

  Selection of inactive substances as ingredients for active masses, e.g. binders, fillers · CPC title