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-11784346-B2
Application number	US-202117342590-A
Country	US
Kind code	B2
Filing date	Jun 9, 2021
Priority date	Jan 31, 2019
Publication date	Oct 10, 2023
Grant date	Oct 10, 2023

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 0.18 to 0.34 eV and conductivities are from 10−3 to 12 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 (VI), (VII), (VIII), and (IX):
Li y (M4) z1 B(PO 4 ) 2   (VI)

wherein z1 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 M4 is at least one element different from Li selected from elements of groups 1, 2, 13 and a transition metal;
Li y B 1-z2 (M5) z2 (PO 4 ) 2   (VII)

wherein z2 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 M5 is at least one element different from B selected from elements of groups 3, 6, 7, 12, 13, 14, 15, 16 and 17;
Li y BP 2-z3 (M6) z3 O 8   (VIII)

wherein z3 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 M6 is at least one element different from P selected from elements of groups 2, 3, 4, 5, 6, 7, 8, 9, 10, 14, 15 and 16; and
Li y BP 2 O 8-z4 (X) z4   (IX)

wherein z4 is from greater than 0 to less than 8, y is a value such that the formula (IX) 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 10 −3 to 12 mS/cm at 300K.

3. The solid state lithium ion electrolyte according to claim 1 , wherein
an activation energy of the at least one material is from 0.18 to 0.34 eV.

4. The solid state lithium ion electrolyte according to claim 1 , wherein the at least one material comprises a triclinic 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 at least one material comprises the following major peaks:

Peak Position
Relative Intensity

12.329
78.97

17.545
100.0

20.191
32.618

20.959
34.486

21.626
60.485

24.222
31.293

24.252
14.806

24.762
10.164

24.803
41.864

25.397
39.684

28.659
16.257

28.772
10.356

29.749
68.838

29.931
63.267

30.631
74.733

31.511
39.743

32.33
30.266

32.39
50.054

34.411
25.572

34.458
26.732

35.065
12.112

35.951
13.113

37.345
22.712

38.824
11.685

40.679
39.383

42.75
23.22

48.326
11.759

51.341
10.562

54.362
14.883

54.455
11.93

58.753
11.16

59.696
11.989

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 (VI), (VII), (VIII), and (IX):
Li y (M4) z1 B(PO 4 ) 2   (VI)

wherein z1 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 M4 is at least one element different from Li selected from elements of groups 1, 2, 13 and a transition metal;
Li y B 1-z2 (M5) z2 (PO 4 ) 2   (VII)

wherein z2 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 M5 is at least one element different from B selected from elements of groups 3, 6, 7, 12, 13, 14, 15, 16 and 17;
Li y BP 2-z3 (M6) z3 O 8   (VIII)

wherein z3 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 M6 is at least one element different from P selected from elements of groups 2, 3, 4, 5, 6, 7, 8, 9, 10, 14, 15 and 16; and
Li y BP 2 O 8-z4 (X) z4   (IX)

wherein z4 is from greater than 0 to less than 8, y is a value such that the formula (IX) is charge neutral and X is an element different from O 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

Assignees

• Univ Maryland
• Toyota Eng & Mfg North America

Inventors

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

Classifications

• H01M10/0562 Primary

  Solid materials · CPC title

• H01M10/0525

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

• H01M2300/0068

  inorganic · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title

• H01M10/052

  Li-accumulators · CPC title