Cathode and lithium-air battery including the cathode

Patent metadata

Field	Value
Publication number	US-11848411-B2
Application number	US-201916594821-A
Country	US
Kind code	B2
Filing date	Oct 7, 2019
Priority date	Oct 11, 2018
Publication date	Dec 19, 2023
Grant date	Dec 19, 2023

Abstract

A cathode configured to use oxygen as a cathode active material, the cathode comprising a lithium-containing metal oxide comprising at least one of:
a spinel compound represented by Formula 1

Li 1±x M 2±y O 4−δ   Formula 1

wherein, in Formula 1, M is at least one metal element belonging to Group 2 to Group 16 of the periodic table of the elements, 0<x<1, 0<y<1, 0<δ1≤1, 0<a<2, 0.3<b<5, and 0<δ≤3;
a spinel compound represented by Formula 2

Li 4±a M 5±b O 12−δ   Formula 2

wherein, in Formula 2, M is at least one metal element belonging to Group 2 to Group 16 of the periodic table of the elements, 0<x<1, 0<y<1, 0<δ1≤1, 0<a<2, 0.3<b<5, and 0<θ≤3; or
a perovskite compound represented by Formula 3

Li x A y G z O 3−δ .  Formula 3

First claim

What is claimed is:

1. A cathode configured to use oxygen as a cathode active material, the cathode comprising a lithium-containing metal oxide comprising at least one of:
a spinel compound represented by Formula 1
Li 1±x M 2±y O 4−δ   Formula 1

wherein, in Formula 1, M is at least one of Ni, Pd, Pb, Fe, Ir, Co, Rh, Cr, Ru, Re, Sn, V, Ge, W, Zr, Ti, Mo, Hf, U, Nb, Th, Ta, Bi, Li, H, Na, K, Rb, Cs, Ca, Sr, Ba, Y, La, Ce, Pr, Nd, Pm, Sm, Gd, Tb, Dy, Ho, Er, Mg, Al, Si, Sc, Zn, Ga, Rb, Ag, Cd, In, Sb, Pt, Au, or Pb, 0<x<1, 0<y<1, and 0<δ≤1;
a spinel compound represented by Formula 2
Li 4±a M 5±b O 12−δ   Formula 2

wherein, in Formula 2, M is at least one of Ni, Pd, Pb, Fe, Ir, Co, Rh, Mn, Ru, Re, Sn, V, Ge, W, Zr, Ti, Mo, Hf, U, Nb, Th, Ta, Bi, Li, H, Na, K, Rb, Cs, Ca, Sr, Ba, Y, La, Ce, Pr, Pm, Sm, Gd, Tb, Dy, Ho, Er, Mg, Al, Si, Sc, Zn, Ga, Rb, Ag, Cd, In, Sb, Pt, Au, or Pb, 0<a<2, 0.3<b<5, and 0<δ≤3; or
a perovskite compound represented by Formula 3
Li x A y G z O 3−δ   Formula 3

wherein, in Formula 3,
A is at least one of H, Na, K, Rb, Cs, Sr, Ba, Y, La, Ce, Pr, Nd, Pm, Sm, Gd, Tb, Dy, Ho, or Er,

G is at least one of Ti, Pd, Pb, Fe, Ir, Co, Rh, Mn, Cr, Ru, Re, Sn, V, Ge, W, Zr, Ti, Mo, Hf, U, Nb, Th, Ta, Bi, Li, H, Na, K, Rb, Cs, Ca, Sr, Ba, Y, La, Ce, Pr, Nd, Pm, Sm, Gd, Tb, Dy, Ho, Er, Mg, Al, Si, Sc, Zn, Ga, Rb, Ag, Cd, In, Sb, Pt, Au, or Pb, 0<x<l, 0<y<1, 0<x+y≤1, 0<z≤1.5, and 0<δ≤1.5,
wherein the cathode does not contain an electrolyte.

2. The cathode of claim 1 , wherein the lithium-containing metal oxide is a crystalline lithium-ion conductor.

3. The cathode of claim 1 , wherein the lithium-containing metal oxide further comprises at least one of a layered compound, a garnet compound, a NASICON compound of the formula Na 1+x Zr 2 Si x P 3−x O 12 wherein 0<x<3, a LISICON compound of the formula Li 2+2x Zn 1−x GeO 4 wherein 0<x<1, a phosphate compound, a tavorite compound, a triplite compound, an anti-perovskite compound, a silicate compound, or a borate compound.

4. The cathode of claim 1 , wherein the cathode comprises a spinel compound of Formula 1 and a spinel compound of Formula 2.

5. The cathode of claim 1 , wherein
M in Formula 2 is at least one of Ni, Pd, Pb, Fe, Ir, Co, Rh, Mn, Ru, Re, Sn, V, Ge, W, Zr, Ti, Mo, Hf, U, Nb, Th, Ta, Bi, Li, H, Na, K, Rb, Cs, Ca, Sr, Ba, Y, La, Ce, Pr, Pm, Sm, Gd, Tb, Dy, Ho, Mg, Al, Si, Sc, Zn, Ga, Rb, Ag, Cd, In, Sb, Pt, Au, or Pb.

6. The cathode of claim 4 , wherein the at least one spinel compound of Formula 2 is represented by Formula 4:
Li 4±a Ti 5−b M c O 12−δ   Formula 4

wherein, in Formula 4,
M is at least one of Mg, Ca, Sr, Sc, Y, La, Ce, Pr, 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, T1, Ge, Sn, Pb, Sb, Bi, Po, As, Se, or Te,
0.3<a<2, 0.3<b<2, 0.3<c<2, and 0<δ≤3.

7. The cathode of claim 4 , wherein the at least one spinel compound is 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 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 41x 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≤3, Li 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, and 0<δ≤3, 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, Li 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.

8. The cathode of claim 4 , wherein the at least one spinel compound has an electronic conductivity of about 1.x 10 −9 Siemens per centimeter to about 1.0 Siemens per centimeter, and an ionic conductivity of about 1.0×10 −8 Siemens per centimeter to about 0.1 Siemens per centimeter at 25° C.

9. The cathode of claim 1 , wherein the cathode comprises a perovskite compound represented by Formula 3.

10. The cathode of claim 9 , wherein, in Formula 3,
A is at least one of H, Na, K, Rb, Cs, Sr, Ba, Y, La, Ce, Pr, Nd, Pm, Sm, Gd, Tb, Dy, Ho, or Er,
G is at least one of Ti, Pd, Pb, Fe, Ir, Co, Rh, Mn, Cr, Ru, Re, Sn, V, Ge, W, Zr, Ti, Mo, Hf, U, Nb, Th, Ta, Bi, Li,

Assignees

• Samsung Electronics Co Ltd

Inventors

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

Classifications

• H01M10/0525 Primary

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

• H01M4/131

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

• H01M4/8652 Primary

  as mixture · CPC title

• H01M4/382

  Lithium (H01M4/405 takes precedence) · CPC title

• H01M4/8885

  Sintering or firing · CPC title