Mixed conductor, electrochemical device including the same, and method of preparing mixed conductor

Patent metadata

Field	Value
Publication number	US-11121378-B2
Application number	US-201916667996-A
Country	US
Kind code	B2
Filing date	Oct 30, 2019
Priority date	Nov 5, 2018
Publication date	Sep 14, 2021
Grant date	Sep 14, 2021

Abstract

A mixed conductor represented by Formula 1:A4+xM5-yM′yO12-δ,  Formula 1wherein, in Formula 1, A is a monovalent cation, M is at least one of a divalent cation, a trivalent cation, or a tetravalent cation, M′ is at least one of a monovalent cation, a divalent cation, a trivalent cation, a tetravalent cation, a pentavalent cation, or a hexavalent cation, M and M′ are different from each other, and 0.3≤x<3, 0.01<y<2, and 0≤δ≤1 are satisfied.

First claim

What is claimed is:

1. An electrochemical device comprising a cathode, the cathode comprising a mixed conductor represented by Formula 1:
A 4+x M 5-y M′ y O 12-δ   Formula 1

wherein, in Formula 1,
A is a first monovalent cation;
M is at least one of a divalent cation, a trivalent cation, or a tetravalent cation, provided that M is not Fe;
M′ is at least one of a second monovalent cation, a divalent cation, a trivalent cation, a tetravalent cation, a pentavalent cation, or a hexavalent cation, provided that M′ is not Fe;
M and M′ are different from each other; and
0.3≤x<3, 0.01<y<2, and 0≤δ≤1 are satisfied.

2. The electrochemical device of claim 1 , wherein the first monovalent cation is a monovalent alkali metal cation, the second monovalent cation is a monovalent alkali metal cation, or both the first monovalent cation and the second monovalent cation are both independently a monovalent alkali metal cation.

3. The electrochemical device of claim 2 , wherein the first monovalent cation comprises at least one of Li, Na, and K; the second monovalent cation comprises at least one of Li, Na, and K; or both the first monovalent cation and the second monovalent cation each independently comprises at least one of Li, Na, and K.

4. The electrochemical device of claim 1 , wherein M′ is at least one of Mg, Ca, Sr, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Ge, Sn, Pb, Sb, Bi, or Po.

5. The electrochemical device of claim 1 ,
wherein M and M′ are cations having different oxidation numbers from each other.

6. The electrochemical device of claim 1 ,
wherein M is a trivalent cation or a tetravalent cation.

7. The electrochemical device of claim 6 ,
wherein the mixed conductor is represented by Formula 2 or Formula 3:
Li 4+x Ti 5-y M1 y O 12-δ   Formula 2

Li 4+x Mn 5-y M2 y O 12-δ   Formula 3

wherein, in Formulae 2 and 3,

M1 is at least one of Mg, Ca, Sr, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Ge, Sn, Pb, Sb, Bi, or Po,
M2 is at least one of Mg, Ca, Sr, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Tc, Re, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Ge, Sn, Pb, Sb, Bi, or Po, and
0.3≤x<3, 0.01<y<2, and 0≤δ≤1 are satisfied.

8. The electrochemical device of claim 1 ,
wherein the mixed conductor includes at least one of Li 4+x Ti 5-y Ag y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+x Ti 5-y Mg y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+x Ti 5-y Ca y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+x Ti 5-y Sr y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+x Ti 5-y Mn y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+x Ti 5-y Pd y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+x Ti 5-y Pt y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+x Ti 5-y Cu y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1;
Li 4 + x Ti 5-y Zn y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+x Ti 5-y Cd y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+X Ti 5-y Hg y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+X Ti 5-y Ge y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Sn y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Pb y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Po y O 12-δ wherein 0.3≤x<3, 0.01<y<2,0≤δ≤1; Li 4+x Ti 5-y Sc y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Y y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y La y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Ce y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Pr y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Nd y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Pm y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Sm y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Eu y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Gd y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Tb y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Dy y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Ho y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Er y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Tm y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Yb y O 12-δ wherein 0.3≤x<3, 0.01<y<2,0≤δ≤1;
Li 4 + x Ti 5-y Lu y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Cr y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Ru y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Co y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Rh y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Ni y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Au y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y yAl y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Ga y O 12-δ wherein 0.3≤x<3, 0.01<y<2,0≤δ≤1; Li 4 + x Ti 5-y In y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Tl y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Sb y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Bi y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Zr y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Hf y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y V y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Nb y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Ta y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Mo y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y W y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Tc y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Re y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; Li 4+x Ti 5-y Os y O 12-δ wherein 0.3≤x<3, 0.01<y<2, 0≤δ≤1; and Li 4+x Ti 5-y Ir y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1); and Li 4+x Mn 5-y Ag y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+x Mn 5-y Au y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+x Mn 5-y Tl y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+x Mn 5-y Mg y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4 + x Mn 5-y Ca y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+x Mn 5-y Sr y O 12-δ wherein 0.3≤x<3; Li 4+x Mn 5-y Ru y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+x Mn 5-y Co y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+ Mn 5-y Ni y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+x Mn 5-y Pd y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+x Mn 5-y Pt y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1;
Li 4+x Mn 5-y Cu y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+x Mn 5-y Zn y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+x Mn 5-y Cd y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+x Mn 5-y Hg y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+x Mn 5-y Ge y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+x Mn 5-y Sn y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+x Mn 5-y Pb y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+x Mn 5-y Po y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1;
Li 4+x x Mn 5-y Sc y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+x Mn 5-y Y y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+x Mn 5-y La y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+x Mn 5-y Ce y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+x Mn 5-y Pr y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+x Mn 5-y Nd y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+x Mn 5-y Pm y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1; Li 4+x Mn 5-y Sm y O 12-δ wherein 0.3≤x<3, 0.01<y<2, and 0≤δ≤1;
Li 4+x Mn 5-y Eu y O 12-δ

Assignees

• Samsung Electronics Co Ltd

Inventors

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

Classifications

• H01M4/624

  Electric conductive fillers · CPC title

• C01G45/1292

  of the type (Mn5O12)n- · CPC title

• C01P2006/40

  Electric properties · CPC title

• C01P2002/72

  by d-values or two theta-values, e.g. as X-ray diagram · CPC title

• C01G51/64

  of the type (Mn5O12)n- · CPC title