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

Patent metadata

Field	Value
Publication number	US-11843106-B2
Application number	US-202117494391-A
Country	US
Kind code	B2
Filing date	Oct 5, 2021
Priority date	Feb 18, 2021
Publication date	Dec 12, 2023
Grant date	Dec 12, 2023

Abstract

A solid-state ion conductor includes a compound of Formula (I):

Li 4+(b−a)y+cδ+(a−γ)x M 1 3+x+y M 2 3−y M″ x O 12 X 1 c X 2 1−c   Formula (I)

wherein, M 1 is a cationic element having an oxidation state of +2 or +3; M 2 is a cationic element having an oxidation state of +4 or +5; M″ is a cationic element having an oxidation state of γ, wherein γ is less than b; X 1 is a cluster anion having an oxidation state of (−1-δ), wherein δ is 0 or 1; X 2 is a halogen; 0<c≤1; 0≤x≤1; and 0≤y≤2.

First claim

What is claimed is:

1. A solid-state ion conductor comprising a compound of Formula (I):
Li 4+(b−a)y+cδ+(a−γ)x M 1 3+x+y M 2 3−y M″ x O 12 X 1 c X 2 1−c   Formula (I)

wherein, in Formula (I),
M 1 is a cationic element having an oxidation state of a, wherein a is +3;
M 2 is a cationic element having an oxidation state of b, wherein b is +4;
M″ is a cationic element having an oxidation state of γ, wherein γ is less
X 1 is a cluster anion having an oxidation state of (−1−δ), wherein δ is 0 or
X 2 is a halogen;
0<c≤1;
0≤x≤1; and
0≤y≤2.

2. The solid-state ion conductor of claim 1 , wherein M 1 is Al, B, Ga, In, Sc, Y, Fe, Mn, Co, Ni, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Lu, or a combination thereof.

3. The solid-state ion conductor of claim 2 , wherein M 1 is Al.

4. The solid-state ion conductor of claim 1 , wherein M 2 is Si, Ti, Zr, Hf, Ge, Sn, or a combination thereof.

5. The solid-state ion conductor of claim 4 , wherein M 2 is Si.

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

7. The solid-state ion conductor of claim 1 , wherein 0<x≤1 and M″ is Al, B, Ga, In, Sc, Y, Fe, Mn, Co, Ni, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Lu, Be, or a combination thereof.

8. The solid-state ion conductor of claim 1 , wherein δ is 0 and the cluster anion X 1 has an oxidation state of −1.

9. The solid-state ion conductor of claim 8 , wherein X 1 is BH 4 − , BF 4 − , AlH 4 − , OH − , SH − , NH 2 − or a combination thereof.

10. The solid-state ion conductor of claim 1 , wherein δ is 1 and the cluster anion X 1 has an oxidation state of −2 and X 1 comprises S 2− , SO 4 2− , or a combination thereof.

11. The solid-state ion conductor of claim 1 , wherein c=1.

12. The solid-state ion conductor of claim 1 , wherein 0<c<1 and X 2 is F, Cl, Br, I, or a combination thereof.

13. The solid-state ion conductor of claim 1 , wherein M 2 is a cationic element having an oxidation state b of +4, and the solid-state ion conductor is of Formula (IA)
Li 4+y+cδ+(3−γ)x M +3 3+x+y M +4 3−y M″ x O 12 X 1 c X 2 1−c   Formula (IA).

14. The solid-state ion conductor of claim 1 , wherein
M 1 is Al;
M 2 is Si;
x is 0;
y is 1;
X 1 is BH 4 − , BF 4 − , AlH 4 − , OH − , SH − , NH 2 − , S 2− , SO 4 2− , or a combination thereof; and
c is 1.

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

to provide a mixture; and
treating the mixture to provide the compound of Formula (I)
Li 4+(b−a)y+cδ+(a−γ)x M 1 3+x+y M 2 3−y M″ x O 12 X 1 c X 2 1−c   Formula (I)

wherein, in Formula (I),
M 1 is a cationic element having an oxidation state of a, wherein a is +3; than b;
M 2 is a cationic element having an oxidation state of b, wherein b is +4;
M″ is a cationic element having an oxidation state of γ, wherein γ is less than b;
X 1 is a cluster anion having an oxidation state of (−1−δ), wherein δ is 0 or 1;
X 2 is a halogen;
0<c≤1;
0≤x≤1; and
0≤y≤2.

16. 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.

17. 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.

18. 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.

19. 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 .

Assignees

• Samsung Electronics Co Ltd
• Univ California

Inventors

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

Classifications

• H01M4/131 Primary

  Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx · CPC title

• H01M4/0442

  Anodisation, Oxidation (electrolytic coating by anodisation C25D9/00) · CPC title

• H01M4/1391

  of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx · 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