Borate compounds as Li super-ionic conductor, solid electrolyte, and coating layer for Li metal battery and Li-ion battery

Patent metadata

Field	Value
Publication number	US-10818969-B2
Application number	US-201816144757-A
Country	US
Kind code	B2
Filing date	Sep 27, 2018
Priority date	Sep 27, 2018
Publication date	Oct 27, 2020
Grant date	Oct 27, 2020

Abstract

Solid-state lithium ion electrolytes of lithium borate based composites are provided which contain an anionic framework capable of conducting lithium ions. Materials 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 provided. Electrodes containing the lithium borate based materials and batteries containing the 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 compounds of formulae (I), (II), (III) and (IV):
Li y (M1) x1 Al(BO 3 ) 2   (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, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 13;
Li y Al(M2) x2 (BO 3 ) 2   (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 at least one element different from Al selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16 and 17;
Li y AlB(M3) x3 O 6   (III)

wherein x3 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 M3 is at least one element different from B selected from elements of groups 13, 14 and 15;
Li y AlB 2 O 6 (X) x4   (IV)

wherein x4 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 X is at least one element different from O selected from elements of groups 15, 16 and 17; and
Li 3 Al(BO 3 ) 2   (V).

2. The solid state lithium ion electrolyte according to claim 1 , wherein
the material is of a P-1 triclinic crystal structure,
an activation energy of the composite is from 0.2 to 0.5 eV, and
a lithium ion conductivity is from 10 −4 to 2.0 mS/cm at 300K.

3. The solid state lithium ion electrolyte according to claim 1 , wherein an X-ray Diffraction (XRD) analysis of the material obtained based on Cu—Kα radiation with wavelength of 1.54184 Å comprises the following major peaks:

Peak

Position

Degree
Relative

2θ
intensity

14.85249
25.19684

16.23356
10.66437

18.19505
11.4209

21.23348
16.71158

21.5603
15.33622

23.49761
10.43319

24.11379
23.81099

24.33971
22.23227

30.20583
29.13861

30.54321
18.30925

32.80487
100

36.1757
21.52103

36.27486
28.08666

36.87026
28.53754.

4. 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 compounds of formulae (I), (II), (III), (IV) and (V):
Li y (M1) x1 Al(BO 3 ) 2   (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, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 13;
Li y Al 1-x2 (M2) x2 (BO 3 ) 2   (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 at least one element different from Al selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16 and 17;
Li y AlB 2-x3 (M3) x3 O 6   (III)

wherein x3 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 M3 is at least one element different from B selected from elements of groups 13, 14 and 15;
Li y AlB 2 O 6-x4 (X) x4   (IV)

wherein x4 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 X is at least one element different from O selected from elements of groups 15, 16 and 17; and
Li 3 Al(BO 3 ) 2   (V)

5. The solid state lithium battery of claim 4 , wherein
the material is of a P-1 triclinic crystal structure,
an activation energy of the material is from 0.2 to 0.5 eV, and
a lithium ion conductivity is from 10 −4 to 2.0 mS/cm at 300K.

6. The solid state lithium battery of claim 5 , wherein an XRD analysis of the material obtained based on Cu—Kα radiation with wavelength of 1.54184 Å comprises the following major peaks:

Peak

Position

Degree
Relative

2θ
intensity

14.85249
25.19684

16.23356
10.66437

18.19505
11.4209

21.23348
16.71158

21.5603
15.33622

23.49761
10.43319

24.11379
23.81099

24.33971
22.23227

30.20583
29.13

Assignees

• Univ Maryland
• Toyota Eng & Mfg North America

Inventors

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

Classifications

• H01M10/0525

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

• Y02E60/10

  Energy storage using batteries · CPC title

• H01M10/0562 Primary

  Solid materials · CPC title

• H01M2300/0068

  inorganic · CPC title

• H01M4/62

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