Cathode for metal-air battery, preparing method thereof, and metal-air battery comprising the same

Patent metadata

Field	Value
Publication number	US-2021126240-A1
Application number	US-202016852677-A
Country	US
Kind code	A1
Filing date	Apr 20, 2020
Priority date	Oct 23, 2019
Publication date	Apr 29, 2021
Grant date	—

Abstract

A cathode for a metal-air battery, the cathode including a mixed conductor; and first pores having a size of about 1 micrometer (μm) or greater, wherein an amount of the first pores is about 30 volume percent (volume %) or greater, with respect to a total volume of pores in the cathode, and a total porosity of the cathode is about 50% or greater, based on a total volume of the cathode.

First claim

What is claimed is:

1 . A cathode for a metal-air battery, the cathode comprising:
a mixed conductor; and first pores having a size of about 1 micrometer or greater, wherein an amount of the first pores is about 30 volume percent or greater with respect to a total volume of pores in the cathode, and a total porosity of the cathode is about 50% or greater, based on a total volume of the cathode.

2 . The cathode of claim 1 , wherein the mixed conductor has an electronic conductivity of about 1×10 −6 Siemens per centimeter or greater.

3 . The cathode of claim 1 , wherein the mixed conductor has an ionic conductivity of about 1×10 −8 Siemens per centimeter or greater.

4 . The cathode of claim 1 , wherein the mixed conductor has a particle size of about 10 nanometers to about 500 nanometers.

5 . The cathode of claim 1 , wherein the first pores have a size of about 1 micrometer to about 100 micrometers.

6 . The cathode of claim 1 , wherein an amount of the first pores is about 30 volume percent to about 95 volume percent, with respect to a total volume of pores in the cathode.

7 . The cathode of claim 1 , wherein a total porosity of the cathode is about 70% to about 95%, based on a total volume of the cathode.

8 . The cathode of claim 1 , wherein the cathode has a thickness of about 5 micrometers to about 100 micrometers.

9 . The cathode of claim 1 , wherein the mixed conductor comprises a lithium-containing metal oxide, and the lithium-containing metal oxide is at least one of a spinel compound, a perovskite compound, 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.

10 . The cathode of claim 1 , wherein the mixed conductor comprises at least one of a spinel compound represented by Formula 1, a spinel compound represented by Formula 2, or a perovskite compound represented by Formula 4:
Li 1±x M 2±y O 4−δ1   Formula 1
Li 4±a M 5±b O 12−δ2   Formula 2
wherein, in Formulae 1 and 2, M is at least one metal element belonging to Group 2 to Group 16 of the periodic table of the elements, δ1 and δ2 are oxygen vacancies, 0<x<1, 0<y<1, 0≤δ≤1≤1, 0<a<2, 0.3<b<5, and 0≤δ2≤3,
Li x A y G z O 3−δ   Formula 4

wherein, in Formula 4, A and G are each independently at least one metal element belonging to Group 2 to Group 16 of the periodic table of the elements, δ is oxygen vacancy, 0<x<1, 0<y<1, 0<x+y≤1, 0<z≤1.5, and 0≤δ≤1.5.

11 . The cathode of claim 1 , wherein the mixed conductor comprises a spinel compound represented by Formula 3:
Li 4±a Ti 5−b M′ c O 12−δ   Formula 3
wherein, in Formula 3, M′ comprises 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, δ is oxygen vacancy, 0.3<a<2, 0.3<b<2, 0.3<c<2, and 0≤δ≤3.

12 . The cathode of claim 1 , wherein the mixed conductor is a perovskite compound represented by Formula 5:
Li x A1 y G1 z O 3−δ   Formula 5

wherein, in Formula 5,
A1 is at least one of La, Ce, Pr, Gd, Ca, Sr, or Ba,
G1 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,
δ is oxygen vacancy,
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 1 , wherein the mixed conductor is at least one of Li 0.34 La 0.55 RuO 3 , Li 0.31 La 0.56 TiO 3 , Li 0.2 Ca 0.6 Mn 0.5 Ni 0.5 O 3 , Li 0.2 Ca 0.6 Mn 0.5 Ni 0.5 O 3 , LiNi 2 O 4 , LiMn 2 O 4 , LiTiNbO 4 , Li 4 Ti 5 O 12 , Li 4 Mn 5 O 12 , Li 4.5 Ti 4.5 Gd 0.5 O 12 , LiNiO 2 , LiCoO 2 , LiMnO 2 , LiNi 1−x1 Mn x1 O 2 , wherein 0<x≤1<1, LiNi 1−x2−y2 Co x2 Mn y2 O 2 , wherein 0<x≤2<0.5 and 0<y≤2≤1.5, LiNi 0.8 Co 0.1 Mn 0.1 O 2 , LiNi 1−x3−y3 Co x3 Al y3 O 2 , wherein 0<x≤3<0.5 and 0<y≤3≤0.5, Li 3 Tb 3 Te 2 O 12 , Li 4.22 Al 0.26 La 3 Zr 2 WO 12 , Li 5 La 3 Nb 2 O 12 , Li 6 BaLa 2 Ta 2 O 12 , Li 7 La 3 Zr 2 O 12 , Li 4 SiO 4 , Li 3.75 Si 0.75 P 0.25 O 4 , Li 14 Zn(GeO 4 ) 4 Li 3.4 V 0.6 Ge 0.4 O 4 , Li 3.5 V 0.5 Ti 0.5 O 4 , Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , Li 1.3 Al 0.3 Ge 1.7 (PO 4 ) 3 , Li 1.3 Al 0.3 Zr 1.7 (PO 4 ) 3 , LiFePO 4 , LiMnPO 4 , LiCoPO 4 , LiNiPO 4 , Li 2 MnP 2 O 7 , Li 2 FeP 2 O 7 , LiVO(PO 4 ), LiV(PO 4 )F, LiFe(SO 4 )F, Li 2 Fe(PO 4 )F, Li 3 OCl, Li 2 OHBr, Li 2 (OH) 0.9 F 0.1 Cl, Li 30 Cl 0.5 Br 0.5 , Li 2 MnSiO 4 , Li 2 FeSiO 4 LiFeBO 3 , or LiCoBO 3 .

14 . The cathode of claim 1 , wherein the mixed conductor has an oxidation potential that is greater than an oxidation potential of carbon and a reduction potential that is less than a reduction potential of carbon.

15 . The cathode of claim 1 , wherein the mixed conductor has a stability to being decomposed by an electrochemical reaction that is greater than a stability of carbon to being decomposed by an electrochemical reaction.

16 . A metal-air battery comprising:
a cathode according to claim 1 ; an anode; and an electrolyte disposed between the cathode and the anode.

17 . The metal-air battery of claim 16 , wherein the electrolyte comprises a solid electrolyte.

18 . The metal-air battery of claim 16 , wherein the anode comprises at least one of lithium, magnesium, iron, aluminum, or zinc, or an alloy thereof.

19 . A method of manufacturing a cathode for a metal-air battery, the method comprising:
mixing a mixed conductor, organic particles having a size of about 1 micrometer or greater, and a solvent to prepare a composition; coating the composition on a substrate to provide a coated substrate; and then thermally treating the coated substrate to manufacture the cathode.

20 . The method of claim 19 , wherein the composition further comprises a binder.

21 . The method of claim 19 , wherein the thermally treating comprises thermally treating at a temperature of about 450° C. to about 800° C.

22 . The method of claim 19 , wherein an amount of the organic particles is about 5 parts by weight to about 60 parts by weight, with respect to 100 parts by weight of the mixed conductor.

Assignees

• Samsung Electronics Co Ltd

Inventors

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

Classifications

• H01M12/08

  composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type · CPC title

• H01M4/9033

  Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites · CPC title

• H01M4/8882

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

• H01M4/8828

  Coating with slurry or ink · CPC title

• H01M4/8673

  Electrically conductive fillers · CPC title