Cathode including base-resistant compound and lithium-air battery including the same

Patent metadata

Field	Value
Publication number	US-12021244-B2
Application number	US-202017110534-A
Country	US
Kind code	B2
Filing date	Dec 3, 2020
Priority date	Jan 21, 2020
Publication date	Jun 25, 2024
Grant date	Jun 25, 2024

Abstract

A cathode for an air battery includes a porous conductive material; and a base-resistant compound on a surface of the porous conductive material, the base-resistant compound having a 0 or positive Gibbs free energy at 2 V to 4.5 V vs Li/Li+ at a pH of about 7 to about 14.

First claim

What is claimed is:

1. A cathode for an air battery, the cathode comprising:
a porous conductive material; and
a base-resistant compound on a surface of the porous conductive material, the base-resistant compound having a 0 or positive Gibbs free energy, at 2 V to 4.5 V vs Li/Li + at a pH of 7 to 14,
wherein the base-resistant compound comprises at least two or more of K, Be, Mg, Ca, Sr, Ba, Sc, Hf, Nb, Ta, W, Cd, B, Al, Ga, In, Si, Ge, Sn, P, As, Sb, Bi, O, S, Te, F, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Th, U, or Pu,
wherein the cathode comprises the base-resistant compound in an amount of 60 parts by weight and to less than 100 parts by weight, based on 100 parts by weight of the cathode.

2. The cathode of claim 1 , wherein the base-resistant compound is electrochemically stable at a pH of 9 to 14.

3. The cathode of claim 1 , wherein the base-resistant compound has a Gibbs free energy difference (ΔG) of at least 0 eV under a voltage condition of 2 V to 4.5 V vs Li/Li + .

4. The cathode of claim 1 , wherein the base-resistant compound is electrochemically stable with respect to lithium metal at a voltage of 2 V to 4.5 V vs Li/Li + at a pH of 12 to 14.

5. The cathode of claim 1 , wherein the base-resistant compound has oxidation resistance and reduction resistance with respect to lithium metal at a voltage of 2 V to 4.5 V vs Li/Li + at a pH of 12 to 14.

6. The cathode of claim 1 , wherein the base-resistant compound comprises at least one of a binary compound or a ternary compound.

7. The cathode of claim 1 , wherein the base-resistant compound is represented by Chemical Formula 1:
M1 α X1 β   Chemical Formula 1

wherein in Chemical Formula 1, M1 is at least one of K, Be, Mg, Ca, Sr, Ba, Sc, Hf, Nb, Ta, W, Cd, B, Al, Ga, In, Si, Ge, Sn, P, As, Sb, Bi, S, Te, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Th, U, or Pu,
X1 is at least one of O or F, and
0≤α≤32 and 0<β≤68.

8. The cathode of claim 1 , wherein the base-resistant compound is represented by at least one of Chemical Formula 2 or Chemical Formula 3:
M2 a1 X2 b1   Chemical Formula 2

wherein in Chemical Formula 2,
M2 is at least one of Be, Sc, Hf, Ta, In, Sn, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Th, U, or Pu,
X2 is at least one of O or F, and
0≤a12, and 0<b1≤5,
M3 a2 M4 a3 X3 b2   Chemical Formula 3

wherein in Chemical Formula 3,
each of M3 and M4 are independently at least one of K, Mg, Ca, Sr, Ba, Sc, Y, Hf, Nb, Ta, Mo, W, Cd, B, Al, Ga, In, C, Si, Ge, Sn, P, As, Sb, Bi, S, Te, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Th, or U,
X3 is at least one of O or F, and
0<a2≤29, 0≤a3≤29, and 0≤b2≤68, provided that M3 is not the same as M4.

9. The cathode of claim 1 , wherein the base-resistant compound is represented by Chemical Formula 4:
M3′ a2′ M4′ a3′ X3′ b2′   Chemical Formula 4

wherein in Chemical Formula 4,
M3′ is at least one of K, Mg, Ca, Sr, Ba, Sc, Ta, Cd, Al, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Th, or U,
M4′ is at least one of Sc, Y, Ti, Zr, Hf, Nb, Ta, Mo, W, Fe, Zn, Cd, B, Al, Ga, In, C, Si, Ge, Sn, P, As, Sb, Bi, S, Te, Ho, Tm, Th, or U,
X3′ is at least one of O or F,
0≤a2′≤29, 0≤a3′≤25, and 0≤b2′≤68.

10. The cathode of claim 9 , wherein when a3′ is 0, and X3′ comprises 0 and F.

11. A cathode for an air battery comprising:
a porous conductive material; and
a base-resistant compound on a surface of the porous conductive material, the base-resistance compound having a 0 or positive Gibbs free energy, at 2 V to 4.5 V vs Li/Li + at a pH of 7 to 14,
wherein the base-resistant compound comprises at least one of HfO 2 , Ta 2 O 5 , Nd 2 O 3 , PuO 2 , Tb 2 O 3 , Dy 2 O 3 , Gd 2 O 3 , Sm 2 O 3 , Ho 2 O 3 , Er 2 O 3 , Sc 2 O 3 , Tm 2 O 3 , Lu 2 O 3 , ThO 2 , UO 3 , Eu 2 O 3 , In 2 O 3 , BeO, SnO 2 , YbF 2 , Al 2 ZnO 4 , BaTa 2 O 6 , BaUO 4 , CaTa 2 O 6 , CaUO 4 , Cd(GaO 2 ) 2 , Cd 2 Sb 2 O 7 , CdIn 2 O 4 , CdSnO 3 , CeTh 9 O 2 O, Dy 11 Y 5 O 24 , Dy 29 Y 3 O 48 , Dy 2 CO 5 , Dy 2 GeO 5 , Dy 2 Hf 2 O 7 , Dy 2 SiO 5 , Dy 2 Sn 2 O 7 , Dy 2 Ti 2 O 7 , Dy 2 WO 6 , Dy 2 Zr 8 O 19 , Dy 3 Al 5 O 12 , Dy 3 Ga 5 O 12 , Dy 3 GaO 6 , Dy 3 Y 5 O 12 , DyAsO 4 , DyNbO 4 , DyOF, DyPO 4 , DyTaO 4 , DyY 3 O 6 , DyY 7 O 12 , Er 10 W 2 O 21 , Er 2 GeO 5 , Er 2 SiO 5 , Er 2 Sn 2 O 7 , Er 2 TiO 5 , Er 3 Al 5 O 12 , Er 3 Ga 5 O 12 , Er 4 Zr 3 O 12 , ErAsO 4 , ErBO 3 , ErNbO 4 , ErPO 4 , ErTaO 4 , Eu 2 Hf 2 O 7 , Eu 2 SiO 5 , Eu 2 Sn 2 O 7 , Eu 3 Ga 5 O 12 , Eu 3 GaO 6 , Eu 3 NbO 7 , Eu 6 WO 12 , EuOF, Gd 2 GeO 5 , Gd 2 Hf 2 O 7 , Gd 2 MoO 6 , Gd 2 SiO 5 , Gd 2 Sn 2 O 7 , Gd 2 TiO 5 , Gd 3 Al 5 O 12 , Gd 3 Ga 5 O 12 , Gd 3 GaO 6 , Gd 3 SbO 7 , Gd 3 Y 13 O 24 , Gd 3 Y 5 O 12 , Gd 5 Y 3 O 12 , Gd 6 WO 12 , GdAsO 4 , GdInO 3 , GdNbO 4 , GdOF, GdPO 4 , GdTaO 4 , Ho 2 SiO 5 , Ho 2 Sn 2 O 7 , Ho 2 Ti 2 O 7 , Ho 2 WO 6 , Ho 2 Zr 8 O 19 , Ho 3 Al 5 O 12 , Ho 3 Ga 5 O 12 , Ho 3 GaO 6 , Ho 3 ScO 6 , HoAsO 4 , HoBO 3 , HoNbO 4 , HoOF, HoPO 4 , HoTaO 4 , KTa 5 O 13 , La 2 CO 5 , La 2 GeO 5 , La 2 Hf 2 O 7 , La 2 MoO 6 , La 2 Si 2 O 7 , La 2 Sn 2 O 7 , La 2 SO 6 , La 2 TeO 6 , La 2 Th 8 O 19 , La 2 Ti 2 O 7 , La 2 UO 6 , La 2 WO 6 , La 2 Zr 2 O 7 , La 3 Ga 5 O 12 , La 4 Ga 2 O 9 , LaAlO 3 , LaAsO 4 , LaBO 3 , LaNbO 4 , LaOF, LaPO 4 , LaSbO 4 , LaScO 3 , LaTaO 4 , Lu 2 SiO 5 , Lu 2 Sn 2 O 7 , Lu 2 TiO 5 , Lu 4 Hf 3 O 12 , Lu 4 Zr 3 O 12 , Lu 6 WO 12 , Lu 6 WO 12 , LuGaO 3 , LuNbO 4 , LuSbO 4 , LuTaO 4 , Mg(GaO 2 ) 2 , MgTa 2 O 6 , MgTi 2 O 5 , Nd 2 GeO 5 , Nd 2 Hf 2 O 7 , Nd 2 MoO 6 , Nd 2 SiO 5 , Nd 2 Sn 2 O 7 , Nd 2 TeO 6 , Nd 2 Ti 2 O 7 , Nd 2 WO 6 , Nd 2 Zr 8 O 19 , Nd 3 Ga 5 O 12 , Nd 3 GaO 6 , Nd 3 U 2 O 10 , Nd 4 Ga 2 O 9 , NdAlO 3 , NdAsO 4 , NdBO 3 , NdFeO 3 , NdNbO 4 , NdOF, NdPO 4 , NdSbO 4 , NdScO 3 , NdTaO 4 , PrTaO 4 , Sc 2 Ti 2 O 7 , ScTaO 4 , Sm 27 Y 5 O 48 , Sm 2 Ge 2 O 7 , Sm 2 Hf 2 O 7 , Sm 2 MoO 6 , Sm 2 SiO 5 , Sm 2 Sn 2 O 7 , Sm 2 TeO 6 , Sm 2 Th 8 O 19 , Sm 2 TiO 5 , Sm 2 WO 6 , Sm 2 Zr 8 O 19 , Sm 3 Ga 5 O 12 , Sm 3 GaO 6 , SmAlO 3 , SmAsO 4 , SmBO 3 , SmNbO 4 , SmOF, SmPO 4 , SmSbO 4 , SmScO 3 , SmTaO 4 , SmY 15 O 24 , Sr 3 U 11 O 36 , SrTa 2 O 6 , Ta 12 MoO 33 , Ta 2 Cd 2 O 7 , Ta 2 Zn 3 O 8 , Ta 2 ZnO 6 , TaAlO 4 , TaBiO 4 , TalnO 4 , Tb 2 Ge 2 O 7 , Tb 2 SiO 5 , Tb 2 Sn 2 O 7 , Tb 2 Ti 2 O 7 , Tb 2 WO 6 , Tb 2 Zr 8 O 19 , Tb 3 Al 5 O 12 , Tb 3 Ga 5 O 12 , Tb 3 GaO 6 , TbAsO 4 , TbNbO 4 , TbOF, TbPO 4 , TbTaO 4 , Ti 3 Zn 2 O 8 , TiCdO 3 , Tm 2 Si 2 O 7 , Tm 2 Sn 2 O 7 , Tm 2 Ti 2 O 7 , Tm 2 Zr 8 O 19 , Tm 3 Al 5 O 12 , Tm 3 Ga 5 O 12 , Tm 6 WO 12 , TmNbO 4 , TmOF, TmPO 4 , TmTaO 4 , UCdO 4 , Y 11 Tm 5 O 24 , Y 13 Ho 19 O 48 , Y 13 Ho 3 O 24 , Y 13 Tm 3 O 24 , Y 15 TmO 24 , Y 2 GeO 5 , Y 2 Hf 2 O 7 , Y 2 HfO 5 , Y 2 SiO 5 , Y 2 Sn 2 O 7 , Y 2 Th 8 O 19 , Y 2 TiO 5 , Y 2 Zr 8 O 19 , Y 3 Al 5 O 12 , Y 3 Ga 5 O 12 , Y 3 GaO 6 , Y 3 SbO 7 , Y 5 Tm 11 O 24 , Y 6 WO 12 , Y 7 HoO 12 , Y 7 TmO 12 , YAsO 4 , Yb 4 Ta 25 O 68 , YbCO 3 , YBO 3 , YbTiO 3 , YNbO 4 , YOF, YPO 4 , YTaO 4 , Zn(GaO 2 ) 2 , or Zr 8 Sc 2 O 19 ,
wherein the cathode comprises the base-resistant compound in an amount of 60 parts by weight to less than 100 parts by weight, based on 100 parts by weight of the cathode.

12. The cathode of claim 1 , wherein the cathode comprises the base-resistant compound in an amount of 70 parts by weight to less than 100 parts by weight, based on 100 parts by weight of the cathode.

13. The cathode of claim 1 , wherein the air comprises between 1 volume percent to 100 volume percent of the moisture, based on a total volume of the air.

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

Assignees

• Samsung Electronics Co Ltd

Inventors

• Ma Sangbok
• Kim Mokwon
• Seo Donghwa

Classifications

• H01M2004/8689

  Positive electrodes · CPC title

• H01M2004/027

  Negative electrodes · CPC title

• H01M12/08 Primary

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

• H01M4/8605 Primary

  Porous electrodes · CPC title

• H01M4/382

  Lithium (H01M4/405 takes precedence) · CPC title