Mixed conductor, electrochemical device, and method of preparing mixed conductor

Patent metadata

Field	Value
Publication number	US-11264181-B2
Application number	US-201916595728-A
Country	US
Kind code	B2
Filing date	Oct 8, 2019
Priority date	Oct 11, 2018
Publication date	Mar 1, 2022
Grant date	Mar 1, 2022

Abstract

A mixed conductor represented by Formula 1:A4±xTi5−yGzO12−δ  Formula 1wherein, in Formula 1, A is a monovalent cation, G is at least one of a monovalent cation, a divalent cation, a trivalent cation, a tetravalent cation, a pentavalent cation, or a hexavalent cation, with the proviso that G is not Ti or Cr, wherein 0<x<2, 0.3<y<5, 0<z<5, and 0<δ≤3.

First claim

What is claimed is:

1. A mixed conductor represented by Formula 1:
A 4±x Ti 5−y G z O 12−δ   Formula 1

wherein, in Formula 1,
A is a monovalent cation,
G is at least one of a monovalent cation, a divalent cation, a trivalent cation, a tetravalent cation, a pentavalent cation, or a hexavalent cation, with the proviso that G is not Ti or Cr, and

0<x<2, 0.3<y<5, 0<z<5, and 0<δ≤3,
wherein the mixed conductor comprises a phase having a spinel-type crystal structure, and
wherein, in an X-ray diffraction spectrum of the mixed conductor, a peak intensity ratio of an intensity of a peak corresponding to a ( 111 ) crystal plane at a diffraction angle 2θ of 18°±2.5° to an intensity of a peak at a diffraction angle 2θ of 23.5°±2.5° is 0.001 to 1.

2. The mixed conductor of claim 1 , wherein
A is a monovalent alkali metal cation, and
G is at least one of a divalent cation, a trivalent cation, a tetravalent cation, a pentavalent cation, or a hexavalent cation, with the proviso that G is not Ti or Cr.

3. The mixed conductor of claim 2 , wherein A is at least one of Li, Na, or K.

4. The mixed conductor of claim 2 , wherein G is at least one of Mg, Ca, Sr, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Zr, Hf, V, Nb, Ta, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Ge, Sn, Pb, Sb, Bi, Po, As, Se, or Te.

5. The mixed conductor of claim 1 , wherein A is Li, and
G is at least one of Mg, Ca, Sr, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Zr, Hf, V, Nb, Ta, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Ge, Sn, Pb, Sb, or Bi, Po, As, Se, or Te, and
wherein 0.3<x<2, 0.3<y<2, 0.3<z<2, and 0<δ≤3.

6. The mixed conductor of claim 5 , wherein the mixed conductor comprises at least one of Li 4±x Ti 5−y Mg z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Ca z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Sr z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Sc z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Y z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y La z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Ce z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Pr z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Nd z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Sm z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Eu z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Gd z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Tb z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Dy z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Ho z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Er z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Tm z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Yb z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Lu z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3Li 4±x Ti 5−y Zr z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Hf z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y V z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Nb z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Ta z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Mo z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y W z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Mn z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Tc z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Re z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Fe z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Ru z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Os z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Co z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Rh z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Ir z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Ni z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Pd z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Pt z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Cu z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Ag z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Au z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Zn z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Cd z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Hg z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, Li 4±x Ti 5−y Al z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Ga z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y In z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Tl z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Ge z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Sn z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Pb z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Sb z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Bi z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y Po z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, Li 4±x Ti 5−y As z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, and 0<δ 4±x Ti 5−y Se z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3, or Li 4±x Ti 5−y Te z O 12−δ wherein 0.4<x≤1, 0.4<y≤1, 0.4<z≤1, and 0<δ≤3.

7. The mixed conductor of claim 1 , wherein an electronic conductivity of the mixed conductor is greater than an ionic conductivity of the mixed conductor.

8. The mixed conductor of claim 1 , wherein an electronic conductivity of the mixed conductor is 1.0×10 −6 Siemens per centimeter to 1.0 Siemens per centimeter at 25° C.

9. The mixed conductor of claim 1 , wherein an ionic conductivity of the mixed conductor is 1.0×10 −7 Siemens per centimeter to 1.0×10 −1 Siemens per centimeter at 25° C.

10. The mixed conductor of claim 1 , wherein the mixed conductor comprises a second phase which is different from a phase having a spinel-type crystal structure.

11. The mixed conductor of claim 10 , wherein the second phase comprises at least one of Li 2 TiO 3 , Gd 2 Ti 2 O 7 , GdTiO 3 , LiNbO 3 , or Nb 2 O 5 .

12. The mixed conductor of claim 1 , wherein the phase having a spinel-type crystal structure belongs to an Fd-3m space group.

13. The mixed conductor of claim 1 , wherein a band gap between a valence band and a conduction band of the mixed conductor is less than a band gap between a valence band and a conduction band of Li 4 Ti 5 O 12 .

14. The mixed conductor of claim 1 , wherein a band gap between a valence band and a conduction band of the mixed conductor is 0.001 electron volts to 2 electron volts.

15. The mixed conductor of claim 1 , wherein Ti has an oxidation number between 3 and 4.

16. The mixed conductor of claim 1 , wherein G has an oxidation number which is different from an oxidation number of Ti.

17. The mixed conductor of claim 1 , wherein A is disposed on at least one of a tetrahedral 8 a site, an oct

Assignees

• Samsung Electronics Co Ltd

Inventors

• Ma Sangbok
• Kwon Hyukjae
• Lee Hyunpyo
• Seo Donghwa
• Im Dongmin

Classifications

• C01G39/006

  Compounds containing molybdenum, with or without oxygen or hydrogen, and containing two or more other elements · CPC title

• H01M10/0525

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

• C01G45/1292

  of the type (Mn5O12)n- · CPC title

• C01G35/006

  Compounds containing tantalum, with or without oxygen or hydrogen, and containing two or more other elements · CPC title

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title