Oxide, method of preparing the same, solid electrolyte including the oxide, and electrochemical device including the oxide

Patent metadata

Field	Value
Publication number	US-2021043966-A1
Application number	US-202016925547-A
Country	US
Kind code	A1
Filing date	Jul 10, 2020
Priority date	Aug 5, 2019
Publication date	Feb 11, 2021
Grant date	—

Abstract

An oxide including a compound represented by Formula 1:
(Li x M1 y )(M2) 3-δ (M3) 2-ω O 12-z X z   Formula 1

wherein, in Formula 1,
6≤x≤8, 0≤y<2, −0.2≤δ≤0.2, −0.2≤ω≤0.2, and 0≤z≤2; M1 is a monovalent cation, a divalent cation, a trivalent cation, or a combination thereof; M2 is a monovalent cation, a divalent cation, a trivalent cation, or a combination thereof; M3 is a monovalent cation, a divalent cation, a trivalent cation, a tetravalent cation, a pentavalent cation, a hexavalent cation, or a combination thereof; wherein at least one of M1, M2, or M3 includes at least four elements; and X is a monovalent anion, a divalent anion, a trivalent anion, or a combination thereof.

First claim

What is claimed is:

1 . An oxide comprising a compound represented by Formula 1:
(Li x M1 y )(M2) 3-δ (M3) 2-ω O 12-z X z   Formula 1

wherein, in Formula 1,
6≤x≤8, 0≤y<2, −0.2≤δ≤0.2, −0.2≤ω≤0.2, and 0≤z≤2;
M1 is a monovalent cation, a divalent cation, a trivalent cation, or a combination thereof;
M2 is a monovalent cation, a divalent cation, a trivalent cation, or a combination thereof;
M3 is a monovalent cation, a divalent cation, a trivalent cation, a tetravalent cation, a pentavalent cation, a hexavalent cation, or a combination thereof;
wherein at least one of M1, M2, or M3 comprises at least four elements; and
X is a monovalent anion, a divalent anion, a trivalent anion, or a combination thereof.

2 . The oxide of claim 1 , wherein at least one of M1 and M2 comprises at least one element, and M3 comprises at least four elements.

3 . The oxide of claim 1 , wherein at least one of M1 or M2 comprises at least two elements, and M3 comprises at least four elements.

4 . The oxide of claim 1 , wherein M3 comprises a combination of:
four tetravalent cations; two tetravalent cations, one trivalent cation, and one pentavalent cation; two tetravalent cations, one divalent cation, and one hexavalent cation; three tetravalent cations, one trivalent cation, and one pentavalent cation; three tetravalent cations, one divalent cation, and one hexavalent cation; one tetravalent cation, two trivalent cations, and two pentavalent cations; four tetravalent cations, one trivalent cation, and one pentavalent cation; four tetravalent cations, one divalent cation, and one hexavalent cation; two tetravalent cations, two trivalent cations, and two pentavalent cations; or two tetravalent cations, two divalent cations, and two hexavalent cations.

5 . The oxide of claim 1 , wherein, in Formula 1, X is iodine, chlorine, bromine, fluorine, cyanide, cyanate, thiocyanate, azide, or a combination thereof.

6 . The oxide of claim 1 , wherein the oxide has a singlet peak at a diffraction angle of about 16 °2θ to about 20 °2θ, when analyzed by X-ray diffraction using Cu Kα radiation.

7 . The oxide of claim 1 , wherein the oxide has a garnet structure comprising a cubic phase.

8 . The oxide of claim 1 , wherein a lithium ionic conductivity of the oxide is at least about 1×10 −4 siemens per centimeter at 25° C.

9 . The oxide of claim 1 , wherein the compound represented by Formula 1 is a compound represented by Formula 2:
(Li x M1 y )(La a1 M4 a2 ) 3-δ (M5 b1 M6 b2 M7 b3 M8 b4 M9 b5 ) 2-ω O 12-z X z   Formula 2

wherein, in Formula 2,
M1 is hydrogen, iron, gallium, aluminum, boron, beryllium, or a combination thereof,
M4 is barium, calcium, strontium, yttrium, bismuth, praseodymium, neodymium, actinium, samarium, gadolinium, or a combination thereof, and
M5 to M9 are each independently zirconium, hafnium, tin, niobium , titanium, vanadium, chromium, manganese, cobalt, nickel, copper, molybdenum, tungsten, tantalum, magnesium, technetium, ruthenium, palladium, iridium, scandium, cadmium, indium, antimony, tellurium, thallium, platinum, silicon, aluminum, or a combination thereof;
6≤x≤8, 0≤y<2, −0.2≤δ≤0.2, −0.2≤ω≤0.2, and 0≤z≤2;
a1+a2=1, 0<a1≤1, and 0≤a2<1;
b1+b2+b3+b4+b5=1, 0<b1<1, 0<b2<1, 0<b3<1, 0<b4<1, and 0≤b5<1; and
X is a monovalent anion, a divalent anion, a trivalent anion, or a combination thereof, and M5 to M9 are different from each other.

10 . The oxide of claim 1 , wherein the compound represented by Formula 1 is a compound represented by Formula 3:
Li x (La a1 M10 a2 ) 3-δ (M11 b1 M12 b2 M13 b3 M14 b4 M15 b5 ) 2-ω O 12-z X z   Formula 3

wherein, in Formula 3,
M10 is barium, calcium, strontium, yttrium, bismuth, praseodymium, neodymium, actinium, samarium, gadolinium, or a combination thereof,
M11 is zirconium, hafnium, or a combination thereof, and
M12 to M15 are each independently zirconium, hafnium, tin, niobium, titanium, vanadium, chromium, manganese, cobalt, nickel, copper, molybdenum, tungsten, tantalum, magnesium, technetium, ruthenium, palladium, iridium, scandium, cadmium, indium, antimony, tellurium, thallium, platinum, silicon, aluminum, or a combination thereof;
6≤x≤8, −0.2≤δ≤0.2, −0.2≤ω≤0.2, and 0≤z≤2;
a1+a2=1, 0<a1≤1, and 0≤a2<1;
b1+b2+b3+b4+b5=1, 0<b1<1, 0<b2<1, 0<b3<1, 0<b4<1, and 0<b5<1; and
X is a monovalent anion, a divalent anion, a trivalent anion, or a combination thereof.

11 . The oxide of claim 10 , wherein, in Formula 3,
M10 is barium, M11 is zirconium, M12 is hafnium, and M13 to M15 are each independently tin, niobium, titanium, vanadium, chromium, manganese, cobalt, nickel, copper, molybdenum, tungsten, tantalum, magnesium, technetium, ruthenium, palladium, iridium, scandium, cadmium, indium, antimony, tellurium, thallium, platinum, silicon, or a combination thereof; and z is 0, or X is fluorine or chlorine.

12 . The oxide of claim 11 , wherein M13 to M15 are each independently tin, niobium, scandium, indium, or a combination thereof, and
z is 0, or X is fluorine or chlorine.

13 . The oxide of claim 1 , wherein, in Formula 1,
M2 is lanthanum, barium, or a combination thereof, M3 comprises at least four elements selected from zirconium, hafnium, tin, niobium, scandium, or indium, and z is 0, or X is fluorine.

14 . The oxide of claim 1 , wherein the oxide is
Li x La 3 Zr b1 Hf b2 Sc b3 Nb b4 Sn b5 O 12 wherein 6≤x≤8, b1+b2+b3+b4+b5=2, 0<b1<1, 0<b2<1, 0<b3<1, 0<b4<1, and 0<b5<1, Li x La 3 Zr b1 Hf b2 In b3 Nb b4 O 12 wherein 6≤x≤8, b1+b2+b3+b4=2, 0<b1<1, 0<b2<1, 0<b3<1, and 0<b4<1, Li x La 3 Zr b1 Hf b2 Sc b3 Nb b4 O 12 wherein 6≤x≤8, b1+b2+b3+b4=2, 0<b1<1, 0<b2<1, 0<b3<1, and 0<b4<1, Li x La 3 Zr b1 Hf b2 Sn b3 Ru b4 O 12 wherein 6≤x≤8, b1+b2+b3+b4=2, 0<b1<1, 0<b2<1, 0<b3<1, and 0<b4<1, Li x La a1 Ba a2 Zr b1 Hf b2 In b3 Nb b4 Sn b5 O 12 wherein 6≤x≤8, a1+a2=3, b1+b2+b3+b4+b5=2, 0<a1<3, 0<a2<3, 0<b1<1, 0<b2<1, 0<b3<1, 0<b4<1, and 0<b5<1, Li x La a1 Ba a 2 Zr b1 Hf b2 Sc b3 Nb b4 Sn b5 O 12 wherein 6≤x≤8, a1+a2=3, b1+b2+b3+b4+b5=2, 0<a1<3, 0<a2<3, 0<b1<1, 0<b2<1, 0<b3<1, 0<b4<1, and 0<b5<1, Li x La 3 Zr b1 Hf b2 Sn b3 Sc b4 Nb b5 O 12-z F z wherein 6≤x≤8, b1+b2+b3+b4+b5=2, 0<b1<1, 0<b2<1, 0<b3<1, 0<b4<1, 0<b5<1, and 0≤z≤2, Li x La 3 Zr b1 Hf b2 Sn b3 Sc b4 Nb b5 O 12-z Cl z wherein 6≤x≤8, b1+b2+b3+b4+b5=2, 0≤z≤2, 0<b1<1, 0<b2<1, 0<b3<1, 0<b4<1, and 0<b5<1, or a combination thereof.

15 . The oxide of claim 1 , wherein the oxide is
Li 7 La 3 Zr 0.4 Hf 0.4 Sc 0.4 Nb 0.4 Sn 0.4 O 12 , Li 7 La 3 Zr 0.3 Hf 0.5 Sc 0.3 Nb 0.5 Sn 0.4 O 12 , Li 7 La 3 Zr 0.5 Hf 0.3 Sc 0.5 Nb 0.3 Sn 0.4 O 12 , Li 7 La 3 Zr 0.3 Hf 0.5 Sc 0.4 Nb 0.3 Sn 0.5 O 12 , Li 7 La 3 Zr 0.5 Hf 0.3 Sc 0.4 Nb 0.5 Sn 0.3 O 12 , Li 7 La 3 Zr 0.5 Hf 0.5 In0.5Nb 0.5 O 12 , Li 7 La 3 Zr 0.4 Hf 0.6 In 0.4 Nb 0.6 O 12 , Li 7 La 3 Zr 0.6 Hf 0.4 In 0.6 Nb 0.4 O 12 , Li 7 La 3 Zr 0.4 Hf 0.4 In 0.6 Nb 0.6 O 12 , Li 7 La 3 Zr 0.6 Hf 0.6 In 0.4 Nb 0.4 O 12 , Li 7 La 3 Zr 0.5 Hf 0.5 Sc 0.5 Nb 0.5 O 12 , Li 7 La 3 Zr 0.4 Hf 0.6 Sc 0.4 Nb 0.6 O 12 , Li 7 La 3 Zr 0.6 Hf 0.4 Sc 0.6 Nb 0.4 O 12 , Li 7 La 3 Zr 0.4 Hf 0.4 Sc 0.6 Nb 0.6 O 12 , Li 7 La 3 Zr 0.6 Hf 0.6 Sc 0.4 Nb 0.4 O 12 , Li 7 La 3 Zr 0.5 Hf 0.5 Sn 0.5 Ru 0.5 O 12 , Li 7 La 3 Zr 0.4 Hf 0.6 Sn 0.4 Ru 0.6 O 12 , Li 7 La 3 Zr 0.6 Hf 0.4 Sn 0.6 Ru 0.4 O 12 , Li 7 La 3 Zr 0.4 Hf 0.4 Sn 0.6 Ru 0.6 O 12 , Li 7 La 3 Zr 0.6 Hf 0.6 Sn 0.4 Ru 0.4 O 12 , Li 7.1 La 2.9 Ba 0.1 Zr 0.4 Hf 0.4 In 0.4 Nb 0.4 Sn 0.4 O 12 , Li 7.1 La 2.9 Ba 0.1 Zr 0.3 Hf 0.5 In 0.3 Nb 0.5 Sn 0.4 O 12 , Li 7.1 La 2.9 Ba 0.1 Zr 0.5 Hf 0.3 In 0.5 Nb 0.3 Sn 0.4 O 12 , Li 7.1 La 2.9 Ba 0.1 Zr 0.

Assignees

• Samsung Electronics Co Ltd

Inventors

• Gwon Hyeokjo
• Jung Sungkyun
• Kim Ryounghee
• Kim Sewon
• Kim Jusik

Classifications

• Y02E60/10

  Energy storage using batteries · CPC title

• C01G1/02

  Oxides · CPC title

• H01M10/0562 Primary

  Solid materials · CPC title

• H01M2300/0071

  Oxides · CPC title

• H01M10/052

  Li-accumulators · CPC title