Cathode, lithium-air battery comprising the same, and method of preparing the cathode

Patent metadata

Field	Value
Publication number	US-11658306-B2
Application number	US-202017128305-A
Country	US
Kind code	B2
Filing date	Dec 21, 2020
Priority date	Feb 4, 2020
Publication date	May 23, 2023
Grant date	May 23, 2023

Abstract

A cathode configured to use oxygen as a cathode active material, the cathode including: a porous film, wherein the porous film includes a metal oxide, and wherein a surface of the porous film has root mean square (RMS) roughness (Rq) of about 0.01 micrometer to about 1 micrometer, and a porosity of the porous film is about 50 volume percent to about 99 volume percent, based on a total volume of the porous film.

First claim

What is claimed is:

1. A cathode configured to use oxygen as a cathode active material, the cathode comprising:
a porous film,
wherein the porous film comprises a metal oxide, and
wherein a surface of the porous film has a root mean square roughness of about 0.01 micrometer to about 1 micrometer, and a porosity of the porous film is about 50 volume percent to about 99 volume percent, based on a total volume of the porous film.

2. The cathode of claim 1 , wherein a mean roughness of the surface of the porous film is about 0.01 micrometer to about 1 micrometer.

3. The cathode of claim 1 , wherein a maximum roughness depth of the surface of the porous film is about 0.1 micrometer to about 10 micrometers.

4. The cathode of claim 1 , wherein the metal oxide is a lithium-containing metal oxide.

5. The cathode of claim 4 , wherein an average particle diameter of the lithium-containing metal oxide is about 10 nanometers to about 500 nanometers.

6. The cathode of claim 4 , wherein the lithium-containing metal oxide is a crystalline lithium ion conductor, and wherein the lithium-containing metal oxide has an ionic conductivity of about 1.0×10 −7 siemens per centimeter or more at 25° C.

7. The cathode of claim 4 , wherein the lithium-containing metal oxide is a crystalline electronic conductor, and wherein the lithium-containing metal oxide has an electronic conductivity of about 1.0×10 −6 siemens per centimeter or more.

8. The cathode of claim 4 , wherein the lithium-containing metal oxide is a mixed conductor, and wherein the lithium-containing metal oxide has an electronic conductivity of about 1×10 −6 siemens per centimeter or more at 25° C. and an ionic conductivity of about 1×10 −7 siemens per centimeter or more at 25° C.

9. The cathode of claim 4 , wherein the lithium-containing metal oxide comprises at least one of a perovskite compound or a spinel compound.

10. The cathode of claim 4 , wherein the lithium-containing metal oxide comprises a perovskite compound represented by Formula 1:
Li x A y G z O 3−δ   Formula 1

wherein, in Formula 1,
each A and G are independently at least one of a Group 2 to a Group 16 element, and
0<x<1, 0<y<1, 0<x+y≤1, 0<z≤1.5, and 0≤δ≤1.5.

11. The cathode of claim 10 , wherein A is at least one of H, Na, K, Rb, Cs, Ca, 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, Ni, Cr, Ru, Re, Sn, V, Ge, W, Zr, Mo, Hf, U, Nb, Th, Ta, Bi, 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, and
0.2<x≤0.7, 0<y≤0.7, 0<x+y<1, 0<z≤1.2, and 0≤δ≤1.2.

12. The cathode of claim 10 , wherein A is at least one of La, Ce, Pr, Gd, Ca, Sr, or Ba,
G is at least one of Ti, Mn, Ni, Ru, Cr, Co, Ir, Fe, Pd, Pb, Rh, Sn, V, Re, Ge, W, Zr, Mo, Nb, Ta, Hf, or Bi, and
0.2<x≤0.5, 0.4<y≤0.7, 0<x+y<1, 0.8<z≤1.2, and 0≤δ≤1.

13. The cathode of claim 10 , wherein the perovskite compound has an electronic conductivity of about 1×10 −6 siemens per centimeter or more at 25° C., and an ionic conductivity of about 2×10 −7 siemens per centimeter or more at 25° C.

14. The cathode of claim 4 , wherein the lithium-containing metal oxide comprises a spinel compound represented by at least one of Formula 2 or Formula 3:
Li 1±x M 2±y O 4−δ1   Formula 2

Li 4±a M 5±b O 12−δ2   Formula 3

wherein, in Formulae 2 and 3,
each M is independently at least one of a Group 2 to Group 16 element, and
0<x<1, 0<y<1, 0≤δ1≤1, 0<a<2, 0.3<b<5, and 0≤δ2≤3.

15. The cathode of claim 14 , wherein
each M is independently at least one of Ni, Pd, Pb, Fe, Ir, Co, Rh, Mn, Cr, Ru, Re, Sn, V, Ge, W, Zr, Ti, Mo, Hf, U, Nb, Th, Ta, Bi, 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, and
0<x<1, 0<y<1, 0≤δ1≤1, 0<a<2, 0.3<b<5, and 0≤δ2≤3.

16. The cathode of claim 14 , wherein the spinel compound 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 Cr, 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, TI, Ge, Sn, Pb, Sb, Bi, Po, As, Se, or Te, and
0.3<a<2, 0.3<b<2, 0.3<c<2, and 0≤δ≤3.

17. The cathode of claim 14 , wherein the spinel compound has an electronic conductivity of about 1×10 −6 siemens per centimeter or more at 25° C. and an ionic conductivity of about 1×10 −7 siemens per centimeter or more at 25° C.

18. The cathode of claim 4 , wherein the lithium-containing metal compound comprises at least one of a layered compound, a garnet compound, a NASICON compound, a LISICON compound, a phosphate compound, a tavorite compound, a triplite compound, an anti-perovskite compound, a silicate compound, or a borate compound.

19. The cathode of claim 4 , wherein the lithium-containing metal oxide comprises at least one of a layered compound represented by Formula 5, a NASICON compound represented by Formula 6, a LISICON compound represented by Formula 7, a garnet compound represented by Formula 8, a phosphate compound represented by Formula 9, a phosphate compound represented by Formula 10, a tavorite compound represented by Formula 11, a triplite compound represented by Formula 11, an anti-perovskite compound represented by Formula 12, a silicate compound represented by Formula 13, or a borate compound represented by Formula 14:
Li 1±x M 1±y O 2±δ   Formula 5

wherein, in Formula 5,
M in Formula 5 is at least one of a Group 2 to Group 16 elements, and
0<x<0.5, 0<y<1, and 0≤δ≤1,
Li 1+x A x M 2−x (XO 4 ) 3   Formula 6

wherein, in Formula 6,
each A and M in Formula 6 are each independently at least one of a Group 2 to a Group 16 element,
X is As, P, Mo, or S, and 0<x<1,
Li 8−c A a B′ b O 4   Formula 7

wherein, in Formula 7,
each A and B′ in Formula 7 are each independently at least one of a Group 2 to a Group 16 element,
c=ma+nb, wherein m is an oxidation number of A, n is an oxidation number of B, and 0<a≤1, and 0≤b≤1,
Li x A 3 B′ 2 O 12   Formula 8

wherein, in Formula 8,
each A and B′ in Formula 8 are each independently at least one of a Group 2 to a Group 16 element, and 3≤x≤7,
Li 1±x MPO 4   Formula 9

Li 2 MP 2 O 7   Formula 10

wherein, Formulae 9 and 10,
each M in Formulae 9 and 10 is at least one of a Group 2 to a Group 16 element, and 0≤x≤1,
Li 1±x M(TiO 4 )X′  Formula 11

wherein, in Formula 11,
M in Formula 11 is at least one of a Group 2 to a Group 16 element,
T is P or S,
X′ is F, O, or OH, and 0≤x≤1.0,
Li x M y OA  Formula 12

wherein, in Formula 12,
M in Formula 12 is at least one of a Group 2 to a Group 16 element,
A in Formula 12 is F, Cl, Br, I, S, Se, or Te, and 2≤x≤3 and 0≤y≤1,
Li 2±x MSiO 4   Formula 13

wherein, in Formula 13, M is at least one of a Group 2 to a Group 16 element, and 0≤x≤1,
Li 1±x MBO 3   Formula 14

wherein, in Formula 14,
M in Formula 14 is at least one of a Group 2 to a Group 16 element, and 0≤x≤1.

20. The cathode of claim 19 , wherein the lithium-containing metal oxide has an ionic conductivity of about 1×10 −6 siemens per centimeter or more at 25° C.

21. The cathode of claim 4 , wherein the lithium-containing metal oxide is electrochemically stable at a voltage of about 2 volts to about 4 volts, with respect to lithium metal.

22. The cathode of claim 1 , wherein the poro

Assignees

• Samsung Electronics Co Ltd

Inventors

• Lee Hyunpyo
• Kim Taeyoung
• Kim Mokwon
• Choi Wonsung

Classifications

• H01M4/8875

  Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support · CPC title

• H01M4/9016

  Oxides, hydroxides or oxygenated metallic salts · CPC title

• H01M4/8882

  Heat treatment, e.g. drying, baking · CPC title

• H01M4/8896

  Pressing, rolling, calendering (membrane electrode assemblies H01M8/1004) · CPC title

• H01M2004/8689

  Positive electrodes · CPC title