Lithium silicate 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-10938063-B2
Application number	US-201916264294-A
Country	US
Kind code	B2
Filing date	Jan 31, 2019
Priority date	Jan 31, 2019
Publication date	Mar 2, 2021
Grant date	Mar 2, 2021

Abstract

Solid-state lithium ion electrolytes of lithium silicate 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.

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), (IV) and (V):
Li y (M1) 2,x1 ZnSiO 4   (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 Zn 1-x2 (M2) x2 SiO 4   (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 Zn selected from elements of groups 2, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16 and 17;
Li y ZnSi 1-x3 (M3) x3 O 4   (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 ZnSiO 4-x4 (X) x4   (IV)

wherein x4 is from greater than 0 to less than 4, y is a value such that the formula (IV) is charge neutral and X is an element different from O selected from elements of groups 16 and 17;

and
Li 2 AnSiO 4   (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 10 −2 to 40 mS/cm at 300K.

3. The solid state lithium ion electrolyte according to claim 1 , wherein
an activation energy of the material is from 0.12 to 0.28 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

16.441
65.092

21.969
35.241

22.601
48.121

24.128
38.027

24.316
100.0  

24.419
16.218

28.411
10.022

28.509
11.565

29.013
66.026

30.944
12.949

33.234
74.638

33.819
40.416

35.768
67.218

37.755
13.032

38.006
13.876

42.487
13.67 

47.82
17.465

48.789
15.738

49.419
10.95 

49.824
11.192

50.044
11.255

50.803
13.267

59.005
22.039

60.129
41.178

61.285
10.379

68.701
10.046

71.812
11.138

72.137
 11.516.

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) 2-x1 ZnSiO 4   (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 Zn 1-x2 (M2) x2 SiO 4   (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 Zn selected from elements of groups 2, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16 and 17;
Li y ZnSi 1-x3 (M3) x3 O 4   (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 ZnSiO 4-x4 (X) x4   (IV)

wherein x4 is from greater than 0 to less than 4, y is a value such that the formula (IV) is charge neutral and X is an element different from O selected from elements of groups 16 and 17; and
Li 2 ZnSiO 4   (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 a

Assignees

• Univ Maryland
• Toyota Eng & Mfg North America

Inventors

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

Classifications

• H01M2300/0068

  inorganic · CPC title

• H01M4/13

  Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof · CPC title

• H01M4/62

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

• Y02E60/10

  Energy storage using batteries · CPC title

• H01M10/0525

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