Lithium phosphate derivative 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-11056717-B2
Application number	US-201916264445-A
Country	US
Kind code	B2
Filing date	Jan 31, 2019
Priority date	Jan 31, 2019
Publication date	Jul 6, 2021
Grant date	Jul 6, 2021

Abstract

Solid-state lithium ion electrolytes of lithium phosphate derivative compounds are provided which contain an anionic framework capable of conducting lithium ions. The activation energy of the lithium phosphate derivative compounds is from 0.2 to 0.45 eV and conductivities are from 0.01 to 10 mS/cm at 300K. Materials 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 phosphate derivative 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) 3-x1 In 2 (PO 4 ) 3   (I)

wherein x1 is a number from greater than 0 to less than 3, 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 (PO 4 ) 3   (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 P 3-x3 (M3) x3 O 12   (III)

wherein x3 is from greater than 0 to less than 3, y is a value such that the formula (III) is charge neutral, and M3 is at least one element different from P selected from elements of groups 2, 3, 4, 5, 9, 10, 14, 15 and 16;
Li y In 2 P 3 O 12-x4 (X) x4   (IV)

wherein x4 is from greater than 0 to less than 12, 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.

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 0.21 to 0.31 eV.

4. The solid state lithium ion electrolyte according to claim 1 , wherein the material comprises a monoclinic structure.

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:

Peak Position
Relative Intensity

16.044
12.365

19.934
30.619

20.374
100.0

20.676
23.232

22.984
11.738

24.066
13.492

28.875
35.491

29.063
13.313

32.541
18.188

32.731
20.858

35.154
17.828

35.494
11.833

35.935
11.846

36.038
29.528

41.43
10.52

46.465
10.319

56.564
10.449.

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), (III) and (IV):
Li y (M1) 3-x1 In 2 (PO 4 ) 3   (I)

wherein x1 is a number from greater than 0 to less than 3, 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 (PO 4 ) 3   (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 P 3-x3 (M3) x3 O 12   (III)

wherein x3 is from greater than 0 to less than 3, y is a value such that the formula (III) is charge neutral, and M3 is at least one element different from P selected from elements of groups 2, 3, 4, 5, 6, 7, 9, 10, 14, 15 and 16;
Li y In 2 P 3 O 12-x4 (X) x4   (IV)

wherein x4 is from greater than 0 to less than 12, y is a value such that the formula (IV) is charge neutral and X is an element different from 0 selected from elements of groups 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.

Assignees

• Univ Maryland
• Toyota Eng & Mfg North America

Inventors

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

Classifications

• H01M4/13

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

• H01M2300/0068

  inorganic · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title

• H01M10/052

  Li-accumulators · CPC title

• H01M10/0562 Primary

  Solid materials · CPC title