Solid-state lithium-ion conductor and methods of manufacture thereof

Patent metadata

Field	Value
Publication number	US-11769878-B2
Application number	US-202117484444-A
Country	US
Kind code	B2
Filing date	Sep 24, 2021
Priority date	Feb 18, 2021
Publication date	Sep 26, 2023
Grant date	Sep 26, 2023

Abstract

A solid-state ion conductor includes a compound of Formula (I):Li4+xB7O12+0.5xX1aX21−a   Formula (I)wherein, in Formula (I), 0≤x≤1; X1 is a pseudohalogen; X2 is a halogen; and 0<a≤1.

First claim

What is claimed is:

1. A solid-state ion conductor comprising a compound of Formula (I):
Li 4+x B 7 O 12+0.5x X 1 a X 2 1−a   Formula (I)

wherein, in Formula (I),
0≤x≤1;
X 1 is BH 4 − , BF 4 − , AlH 4 − , NH 2 − , OH − , SH − , or a combination thereof;
X 2 is a halogen; and
0<a≤1.

2. The solid-state ion conductor of claim 1 , wherein X 2 is F − , Cl − , Br − , I − , or a combination thereof.

3. The solid-state ion conductor of claim 1 having an ionic conductivity of greater than 10 −4 mS/cm at 300 K.

4. The solid-state ion conductor of claim 1 , wherein x=0.

5. The solid-state ion conductor of claim 1 , wherein 0<x≤1.

6. The solid-state ion conductor of claim 1 , wherein a=1.

7. The solid-state ion conductor of claim 1 , wherein X 1 is NH 2 − , OH − , SH − , or a combination thereof.

8. The solid-state ion conductor of claim 1 , wherein X 1 is OH − , SH − , or a combination thereof.

9. The solid-state ion conductor of claim 1 , wherein X 1 is OH − .

10. The solid-state ion conductor of claim 9 having an ionic conductivity of greater than 1 mS/cm at 300 K.

11. The solid-state ion conductor of claim 1 , wherein X 1 is SH − .

12. The solid-state ion conductor of claim 11 , having an ionic conductivity of greater than 1 mS/cm at 300 K.

13. A method of preparing a solid-state ion conductor, the method comprising:
contacting
a lithium compound;
a boron oxide;
an X 1 precursor; and
optionally, an X 2 precursor;

to provide a mixture; and
treating the mixture to provide the compound of Formula (I)
Li 4+x B 7 O 12+0.5x X 1 a X 2 1−a   Formula (I),

wherein, in Formula (I),
0≤x≤1;
X 1 is BH 4 − , BF 4 − , AlH 4 − , NH 2 − , OH − , SH − , or a combination thereof;
X 2 is a halogen; and
0<a≤1.

14. A positive electrode comprising:
a positive active material layer comprising a lithium transition metal oxide, a lithium transition metal phosphate, or a combination thereof; and
the solid-state ion conductor of claim 1 on the positive active material layer.

15. A negative electrode comprising:
a negative active material layer comprising lithium metal, a lithium metal alloy, or a combination thereof; and
the solid-state ion conductor of claim 1 on the negative active material layer.

16. A negative electrode for a lithium secondary battery, the electrode comprising:
a current collector; and
the solid-state ion conductor of claim 1 on the current collector.

17. An electrochemical cell comprising:
a positive electrode;
a negative electrode; and
an electrolyte layer between the positive electrode and the negative electrode;
wherein at least one of the positive electrode, the negative electrode, or the electrolyte layer comprises the solid-state ion conductor of claim 1 .

18. The solid-state ion conductor of claim 1 , comprising Li 4 B 7 O 12 (OH), Li 4 B 7 O 12 SH, Li 4 B 7 O 12 NH 2 , Li 4 B 7 O 12 BH 4 , Li 4 B 7 O 12 BF 4 , Li 4 B 7 O 12 AlH 4 , Li 10 B 14 O 25 (OH) 2 , Li 10 B 14 O 25 (SH) 2 , Li 10 B 14 O 25 (NH 2 ) 2 , Li 10 B 14 O 25 (BH 4 ) 2 , Li 10 B 14 O 25 (BF 4 ) 2 , Li 10 B 14 O 25 (AlH 4 ) 2 , Li 10 B 14 O 25 (OH)Cl, Li 10 B 14 O 25 (SH)Br, Li 10 B 14 O 25 (NH 2 )Cl, Li 10 B 14 O 25 (BH 4 )Br, Li 10 B 14 O 25 (BF 4 )I, Li 10 B 14 O 25 (AlH 4 )Br, Li 4 B 7 O 12 (OH) 0.5 Cl 0.5 , Li 4 B 7 O 12 (OH) 0.5 Br 0.5 , or Li 4 B 7 O 12 (OH) 0.5 I 0.5 .

19. The solid-state ion conductor of claim 1 , comprising Li 4 B 7 O 12 (OH), Li 4 B 7 O 12 SH, Li 4 B 7 O 12 NH 2 , Li 4 B 7 O 12 BH 4 , Li 4 B 7 O 12 BF 4 , Li 4 B 7 O 12 AlH 4 , Li 10 B 14 O 25 (OH) 2 , Li 4 B 7 O 12 (OH) 0.5 Cl 0.5 , Li 4 B 7 O 12 (OH) 0.5 Br 0.5 , or Li 4 B 7 O 12 (OH) 0.5 I 0.5 .

Assignees

• Samsung Electronics Co Ltd
• Univ California

Inventors

• Ceder Gerbrand
• Ouyang Bin
• Sun Yingzhi
• Wang Yan
• Miara Lincoln James

Classifications

• H01M4/582 Primary

  Halogenides · CPC title

• H01M4/134

  Electrodes based on metals, Si or alloys · CPC title

• H01M10/0525

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

• H01M2004/027

  Negative electrodes · CPC title

• H01M2004/028

  Positive electrodes · CPC title