Lithium ion-conducting garnet-like compounds

Patent metadata

Field	Value
Publication number	US-9761905-B2
Application number	US-201214233940-A
Country	US
Kind code	B2
Filing date	May 21, 2012
Priority date	Jul 19, 2011
Publication date	Sep 12, 2017
Grant date	Sep 12, 2017

Abstract

A lithium ion-conducting compound, having a garnet-like crystal structure, and having the general formula: Li n [A (3-a′-a″) A′ (a′) A″ (a″) ][B (2-b′-b″) B′ (b′) B″ (b″) ][C′ (c′) C″ (c″) ]O 12 , where A, A′, A″ stand for a dodecahedral position of the crystal structure, where A stands for La, Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and/or Yb, A′ stands for Ca, Sr and/or Ba, A″ stands for Na and/or K, 0<a′<2 and 0<a″<1, where B, B′, B″ stand for an octahedral position of the crystal structure, where B stands for Zr, Hf and/or Sn, B′ stands for Ta, Nb, Sb and/or Bi, B″ stands for at least one element selected from the group including Te, W and Mo, 0<b′<2 and 0<b″<2, where C and C″ stand for a tetrahedral position of the crystal structure, where C stands for Al and Ga, C″ stands for Si and/or Ge, 0<c′<0.5 and 0<c″<0.4, and where n=7+a′+2·a″−b′−2·b″−3·c′−4·c″ and 5.5<n<6.875.

First claim

What is claimed is:

1. A lithium ion conductor, comprising:
a compound that includes a garnet-like crystal structure of the general chemical formula Li n [A (3-a′-a″) A′ (a′) A″ (a″) ][B (2-b′-b″) B′ (b′) B″ (b″) ][C′ (c′) C″ (c″) ]O 12 , wherein:
A stands for a dodecahedral position of the garnet-like crystal structure and stands for at least one element selected from the group consisting of La, Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb;
A′ stands for a dodecahedral position of the garnet-like crystal structure and stands for at least one element selected from the group consisting of Ca, Sr and Ba;
A″ stands for a dodecahedral position of the garnet-like crystal structure and stands for at least one element selected from the group consisting of Na and K;
0≦ a′< 2;

0≦ a″< 1;

B stands for an octahedral position of the garnet-like crystal structure and stands for at least one element selected from the group consisting of Zr, Hf and Sn;
B′ stands for an octahedral position of the garnet-like crystal structure and stands for at least one element selected from the group consisting of Ta, Nb, Sb and Bi;
B″ stands for an octahedral position of the garnet-like crystal structure and stands for at least one element selected from the group consisting of Te, W and Mo;
0≦ b′≦ 2;

0≦ b″≦ 2;

C′ stands for a tetrahedral position of the garnet-like crystal structure and stands for at least one element selected from the group consisting of Al and Ga;
C″ stands for a tetrahedral position of the garnet-like crystal structure and stands for at least one element selected from the group consisting of Si and Ge;
0≦ c′≦ 0.5;

0≦ c″≦ 0.4;

n= 7+ a′+ 2· a″−b′− 2· b″− 3· c′− 4· c″;

5.5≦ n≦ 6.875;

when b′=2, 6.0<n<6.875 or 5.5≦n≦6.875, and c′+c″>0; and
when B′ is Nb, 6.0<n<6.4 or 5.5≦n≦6.875 and at least one of c′+c″>0 and a′+a″>0.

2. The lithium ion conductor of claim 1 , wherein 5.9≦n≦6.6.

3. The lithium ion conductor of claim 1 , wherein 6.0<n<6.5.

4. The lithium ion conductor of claim 1 , wherein B′ stands for Ta.

5. The lithium ion conductor of claim 1 , wherein:
0< b′≦ 2, and
B′ stands for Ta and at least one element selected from the group consisting of Nb, Sb and Bi.

6. The lithium ion conductor of claim 1 , wherein b′+b″>0.

7. The lithium ion conductor of claim 1 , wherein at least one of C′ stands for Al, C″ stands for Si, and c′+c″>0.

8. The lithium ion conductor of claim 1 , wherein a′+a″>0.

9. The lithium ion conductor of claim 1 , wherein:
the garnet-like crystal structure is of the general chemical formula Li n [La (3-a′) A′ (a′) ][Zr (2-b′) B′ (b′) ][Al (c′) Si (c″) ]O 12 ;
La and A′ stand for a dodecahedral position of the garnet-like crystal structure;
A′ stands for at least one element selected from the group including Ca, Sr and Ba;
0< a′< 2;

Zr stands for an octahedral position of the garnet-like crystal structure;
B′ stands for an octahedral position of the garnet-like crystal structure and stands for at least one element selected from the group including Ta, Nb, Sb and Bi;
0< b′≦ 2;

Al and Si stand for a tetrahedral position of the garnet-like crystal structure;
0≦ c′≦ 0.5;

0< c″≦ 0.4;
c′+c″> 0;
n= 7+ a′+ 2· a″−b′− 2· b″− 3· c′− 4· c ″; and

5.5≦ n≦ 6.875.

10. The lithium ion conductor of claim 9 , wherein 5.9≦n≦6.6.

11. The lithium ion conductor of claim 9 , wherein 6.0≦n≦6.5.

12. The lithium ion conductor of claim 9 , wherein 0<c′≦0.5.

13. The lithium ion conductor of claim 1 , wherein C′ and C″ stand for tetrahedral position 24d of the garnet-like crystal structure.

14. The lithium ion conductor of claim 13 , wherein C′ stands for Al.

15. The lithium ion conductor of claim 13 , wherein C″ stands for Si.

16. The lithium ion conductor of claim 1 , wherein B, B′ and B″ stand for octahedral position 16a of the garnet-like crystal structure.

17. The lithium ion conductor of claim 16 , wherein B stands for Zr.

18. The lithium ion conductor of claim 1 , wherein A, A′ and A″ stand for the dodecahedral position 24c of the garnet-like crystal structure.

19. The lithium ion conductor of claim 1 , wherein A′ stands for the dodecahedral position 24c of the garnet-like crystal structure.

20. The lithium ion conductor of claim 1 , wherein the lithium ion conductor is part of a galvanic cell.

21. The lithium ion conductor of claim 20 , wherein the galvanic cell is a lithium-sulfur cell, a lithium-oxygen cell, a lithium-ion cell, or a battery thereof.

22. The lithium ion conductor of claim 20 , wherein the lithium ion conductor separates a cathode and an anode of the cell.

23. The lithium ion conductor of claim 1 , wherein:
the lithium ion conductor is synthesized by:
(a) providing a powder mixture that includes:
at least one lithium compound;
at least one compound of an element selected from the group consisting of La, Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb; and
at least one compound of an element selected from the group consisting of Zr, Hf, Sn, Ta, Nb, Sb, Bi, Te, W and Mo;

(b) calcining the powder mixture at a temperature t1 in a temperature range of from 600° C.≦t1≦1000° C.; and
(c) sintering the powder mixture or the molded body at a temperature t2 in a temperature range of 900° C.≦t2≦1250° C.; and

the powder mixture contains the compounds of elements different from lithium in stoichiometric amounts which are selected in such a way that the lithium content of the compound is in a range of 5.5≦n≦6.875.

24. The lithium ion conductor of claim 23 , wherein the synthesis further includes pressing the powder mixture to form a molded body.

25. The lithium ion conductor of claim 24 , wherein the pressing is under a uniaxial and isostatic pressure.

26. The lithium ion conductor of claim 23 , wherein the powder mixture further includes at least one compound of an element selected from the group consisting of Al, Ga, Si and Ge.

27. The lithium ion conductor of claim 23 , wherein the powder mixture further includes at least one compound of an element selected from the group consisting of Ca, Sr, Ba, Na and K.

28. The lithium ion conductor of claim 23 , wherein the calcining temperature t1 is in a temperature range of 850° C.≦t1≦950° C.

29. The lithium ion conductor of claim 23 , wherein the lithium content of the compound is in a range of 5.9≦n≦6.6.

30. The lithium ion conductor of claim 23 , wherein the lithium content of the compound is in a range of 6.0≦n≦6.5.

31. The lithium ion conductor of claim 23 , wherein the sintering temperature t2 is in a temperature range of 1100° C.≦t2≦1200° C.

32. A lithium ion conductor, comprising:
a compound that includes a garnet-like crystal structure of the general chemical formula Li n [A (3-a′-a″) A′ (a′) A″ (a″) ][B (2-b′-b″) B′ (b′) B″ (b″) ][C′ (c′) C″ (c″) ]O 12 , wherein:
A stands for a dodecahedral position of the garnet-like crystal structure and stands for at least one element selected from the group consisting of La, Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb;
A′ stands for a dodecahedral position of the garnet-like crystal structure and stands for at least one element selected from the group consisting of Ca, Sr and Ba;
A″ stands for a dodecahedral position of the garnet-like crystal structure and s

Assignees

• Eisele Ulrich
• Koehler Thomas
• Hinderberger Stefan
• Kozinsky Boris
• Logeat Alan
• Bosch Gmbh Robert

Inventors

• Eisele Ulrich
• Koehler Thomas
• Hinderberger Stefan
• Kozinsky Boris
• Logeat Alan

Classifications

• H01M10/052

  Li-accumulators · CPC title

• C04B35/495

  based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates · CPC title

• C04B2235/3213

  Strontium oxides or oxide-forming salts thereof · CPC title

• C04B2235/3251

  Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof · CPC title

• C04B2235/3244

  Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof · CPC title