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

Patent metadata

Field	Value
Publication number	US-2021226224-A1
Application number	US-202017110534-A
Country	US
Kind code	A1
Filing date	Dec 3, 2020
Priority date	Jan 21, 2020
Publication date	Jul 22, 2021
Grant date	—

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 about 7 to about 14.

2 . The cathode of claim 1 , wherein the base-resistant compound is electrochemically stable at a pH of about 9 to about 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 about 12 to about 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 about 12 to about 14.

6 . The cathode of claim 1 , wherein the base-resistant compound comprises at least two or more of K, Be, Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, Nb, Ta, Mo, W, Fe, Zn, Cd, B, Al, Ga, In, C, Si, Ge, Sn, P, As, Sb, Bi, O, S, Te, F, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Th, U, or Pu.

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

8 . 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, 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, La, Ce, 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.

9 . 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, Y, Ti, Zr, Hf, Ta, In, Sn, Ce, 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<a1≤2, 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, Ti, Zr, Hf, Nb, Ta, Mo, W, Fe, Zn, Cd, B, Al, Ga, In, C, Si, Ge, Sn, P, As, Sb, Bi, S, Te, La, Ce, 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.

10 . 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, Y, Ti, Zr, Ta, Zn, Cd, Al, La, Ce, 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.

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

12 . The cathode of claim 1 , wherein the base-resistant compound comprises at least one of Y 2 O 3 , HfO 2 , Ta 2 O 5 , CeO 2 , ZrO 2 , 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 , TiO 2 , 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 20 , 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 16 , 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 O 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 6 , LaAlO 3 , LaAsO 4 , LaBO 3 , LaNbO 4 , LaOF, LaPO 4 , LaSbO 4 , La 5 ScO 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 UO 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 , TaInO 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 , TbTa 2 O 7 , ThTi 2 O 6 , 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 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 .

13 . The cathode of claim 1 , wherein the cathode comprises the base-resistant compound in an amount of about 1 part by weight and less than 100 parts by weight, based on 100 parts by weight of the cathode.

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

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

16 . The lithium-air battery of claim 15 , wherein the cathode is inert in the presence of a discharge product having a pH of about 9 to about 14.

17 . The lithium-air battery of claim 16 , wherein the discharge product comprises LiOH.

Assignees

• Samsung Electronics Co Ltd

Inventors

• Ma Sangbok
• Kim Mokwon
• Seo Donghwa

Classifications

• Y02E60/10

  Energy storage using batteries · CPC title

• H01M12/06

  with one metallic and one gaseous electrode · CPC title

• H01M4/8605 Primary

  Porous electrodes · CPC title

• H01M4/8647

  consisting of more than one material, e.g. consisting of composites · CPC title

• H01M4/485

  of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence) · CPC title