Solid conductor, preparation method thereof, solid electrolyte including the solid conductor, and electrochemical device including the solid conductor

Patent metadata

Field	Value
Publication number	US-11728510-B2
Application number	US-202016881629-A
Country	US
Kind code	B2
Filing date	May 22, 2020
Priority date	May 24, 2019
Publication date	Aug 15, 2023
Grant date	Aug 15, 2023

Abstract

A solid conductor including:a compound represented by Formula 1, a compound represented by Formula 2,or a combination thereofLi1+x+y−zTa2−xMxP1−yQyO8−zXz  Formula 1wherein, in Formula 1,M is an element having an oxidation number of +4,Q is an element having an oxidation number of +4,X is a halogen, a pseudohalogen, or a combination thereof, and0≤x≤2, 0≤y<1, and 0≤z≤2, except that cases i) x and y and z are simultaneously 0, ii) M is Hf, X is F, x is 1, y is 0, and z is 1, iii) M is Hf, X is Cl, x is 2, y is 0, and z is 2, and iv) M is Hf, X is F, x is 2, y is 0, and z is 2,Li1+x+y−zTa2−xMxP1−yQyO8·zLiX  Formula 2wherein, in Formula 2,M is an element having an oxidation number of +4,Q is an element having an oxidation number of +4,X is a halogen, a pseudohalogen, or a combination thereof, and0≤x≤2, 0≤y<1, and 0≤z2, except that cases i) x and y and z are simultaneously 0, ii) M is Hf, X is F, x is 1, y is 0, and z is 1, iii) M is Hf, X is Cl, x is 2, y is 0, and z is 2, and iv) M is Hf, X is F, x is 2, y is 0, and z is 2.

First claim

What is claimed is:

1. A solid conductor comprising:
a compound represented by Formula 1, a compound represented by Formula 2, or a combination thereof
Li 1+x+y−z Ta 2−x M x P 1−y Q y O 8−z X z   Formula 1

wherein, in Formula 1,
M is an element having an oxidation number of +4,
Q is an element having an oxidation number of +4,
X is a halogen, a pseudohalogen, or a combination thereof, and
0<x≤2, 0≤y<1, and 0≤z≤2, except for the following cases
i) x and y and z are simultaneously 0,
ii) M is Hf, X is F, x is 1, y is 0, and z is 1,
iii) M is Hf, X is Cl, x is 2, y is 0, and z is 2, and
iv) M is Hf, X is F, x is 2, y is 0, and z is 2,
Li 1+x+y−z Ta 2-−x M x P 1−y Q y O 8 ·zLiX  Formula 2

wherein, in Formula 2,
M is an element having an oxidation number of +4,
Q is an element having an oxidation number of +4,
X is a halogen, a pseudohalogen, or a combination thereof, and
0<x≤2, 0≤y<1, and 0≤z≤2, except for the following cases,
i) x and y and z are simultaneously 0,
ii) M is Hf, X is F, x is 1, y is 0, and z is 1,
iii) M is Hf, X is Cl, x is 2, y is 0, and z is 2, and
iv) M is Hf, X is F, x is 2, y is 0, and z is 2.

2. The solid conductor of claim 1 , wherein M has a coordination number of 6.

3. The solid conductor of claim 1 , wherein M in Formula 1 and M in Formula 2 are each independently hafnium, zirconium, titanium, germanium, tin, iridium, rhodium, manganese, osmium, ruthenium, platinum, or a combination thereof.

4. The solid conductor of claim 1 , wherein, in Formulae 1 and 2,
Q has a coordination number of 4, and
Q in Formula 1 and Q in Formula 2 are each independently silicon, tin, titanium, germanium, selenium, palladium, rhodium, cobalt, molybdenum, chromium, ruthenium, nickel, manganese, vanadium, niobium, or a combination thereof.

5. The solid conductor of claim 1 , wherein X in Formula 1 and X in Formula 2 are each independently chlorine, bromine, fluorine, cyanide, cyanate, thiocyanate, azide, or a combination thereof.

6. The solid conductor of claim 1 , wherein x and z in Formula 1 and x and z in Formula 2 are each independently 0<x<0.6 and 0≤z<1.

7. The solid conductor of claim 1 , wherein x, y, and z in Formula 1 and x, y, and z in Formula 2 are each independently 0<x≤0.5, 0<y≤0.5, and 0≤z≤0.3.

8. The solid conductor of claim 1 , wherein the solid conductor has a monoclinic structure.

9. The solid conductor of claim 1 , wherein the solid conductor has a peak at about 17.5°2θ, about 24.8°2θ, about 24.9°2θ, about 25.4°2θ, and about 27.8°2θ, when analyzed by X-ray diffraction using Cu Kα radiation.

10. The solid conductor of claim 1 , wherein the solid conductor has a peak at a chemical shift in a range of about −6 parts per million to about −14 parts per million, when analyzed using 31 P-nuclear magnetic resonance spectroscopy.

11. The solid conductor of claim 10 , wherein the peak has a full width at half-maximum in a range of about 2 parts per million to about 6 parts per million, when analyzed using 31 P-nuclear magnetic resonance spectroscopy.

12. The solid conductor of claim 1 , wherein the solid conductor has a peak at a chemical shift of about −15 parts per million to about −22 parts per million, when analyzed by 31 P-nuclear magnetic resonance spectroscopy.

13. The solid conductor of claim 1 , wherein the solid conductor has a lithium ionic conductivity of 1×10 −2 milliSiemens per centimeter or more at 25° C.

14. The solid conductor of claim 1 , wherein the solid conductor has electronic conductivity of 1×10 −5 milliSiemens per centimeter or less at 25° C.

15. The solid conductor of claim 1 , wherein the compound represented by Formula 1 is represented by Formula 3 or Formula 4:
Li 1+x+y−z Ta 2-−x Hf x P 1−y Si y O 8−z X z   Formula 3

wherein, in Formula 3,
X is a halogen or a pseudohalogen, and
0<x≤2, 0≤y<1, and 0≤z≤2, except for the following cases,
i) x and y and z are simultaneously 0,
ii) M is Hf, X is F, x is 1, y is 0, and z is 1,
iii) M is Hf, X is Cl, x is 2, y is 0, and z is 2, and
iv) M is Hf, X is F, x is 2, y is 0, and z is 2;
Li 1+x+y-z Ta 2-−x Zr x P 1−y Si y O 8−z X z   Formula 4

wherein, in Formula 4,
X is a halogen or a pseudohalogen, and
0<x≤2, 0≤y<1, and 0≤z≤2, except for the following cases,
i) x and y and z are simultaneously 0,
ii) M is Hf, X is F, x is 1, y is 0, and z is 1,
iii) M is Hf, X is Cl, x is 2, y is 0, and z is 2, and
iv) M is Hf, X is F, x is 2, y is 0, and z is 2.

16. The solid conductor of claim 1 , wherein, the compound represented by Formula 2 is represented by Formula 5 or Formula 6:
Li 1+x+y−z Ta 2-−x Hf x P 1−y Si y O 8 ·zLiX  Formula 5

wherein, in Formula 5,
X is a halogen atom, and
0<x≤2, 0≤y<1, and 0≤z≤2, except for the following cases,
i) x and y and z are simultaneously 0,
ii) M is Hf, X is F, x is 1, y is 0, and z is 1,
iii) M is Hf, X is Cl, x is 2, y is 0, and z is 2, and
iv) M is Hf, X is F, x is 2, y is 0, and z is 2;
Li 1+x+y-z Ta 2-−x Zr x P 1−y Si y O 8 ·zLiX  Formula 6

wherein, in Formula 6,
X is a halogen atom, and
0<x≤2, 0≤y<1, and 0≤z≤2, except for the following cases,
i) x and y and z are simultaneously 0,
ii) M is Hf, X is F, x is 1, y is 0, and z is 1,
iii) M is Hf, X is Cl, x is 2, y is 0, and z is 2, and
iv) M is Hf, X is F, x is 2, y is 0, and z is 2.

17. The solid conductor of claim 1 , wherein the solid conductor is
Li 1.025 Hf 0.025 Ta 1.975 PO 8 , Li 1.05 Hf 0.05 Ta 1.95 PO 8 , Li 1.1 Hf 0.1 Ta 1.9 PO 8 , Li 1.25 Hf 0.25 Ta 1.75 PO 8 , Li 1.125 Hf 0.125 Ta 1.875 PO 8 , Li 1.375 Hf 0.375 Ta 1.625 PO 8 , Li 1.125 Zr 0.125 Ta 1.875 PO 8 , Li 1.25 Zr 0.25 Ta 1.75 PO 8 , Li 1.375 Zr 0.375 Ta 1.625 PO 8 , Li 1.025 Zr 0.025 Ta 1.975 PO 8 , Li 1.05 Zr 0.05 Ta 1.95 PO 8 , Li 1.1 Zr 0.1 Ta 1.9 PO 8 , Li 0.9 Hf 0.05 Ta 1.95 PO 7.85 F 0.15 , Li 0.9 Hf 0.05 Ta 1.95 PO 7.85 Cl 0.15 , Li 0.8 Hf 0.05 Ta 1.95 PO 7.75 F 0.25 , Li 0.8 Hf 0.05 Ta 1.95 PO 7.75 Cl 0.25 , Li 0.875 Hf 0.025 Ta 1.975 PO 7.85 F 0.15 , Li 0.875 Hf 0.025 Ta 1.975 PO 7.85 Cl 0.15 , Li 0.775 Hf 0.025 Ta 1.975 PO 7.75 F 0.25 , Li 0.775 Hf 0.025 Ta 1.975 PO 7.75 Cl 0.25 , Li 0.95 Hf 0.1 Ta 1.9 PO 7.85 Cl 0.15 , Li 0.85 Hf 0.1 Ta 1.9 PO 7.75 F 0.25 , Li 0.85 Hf 0.1 Ta 1.9 PO 7.75 Cl 0.25 , Li 1.1 Hf 0.25 Ta 1.75 PO 7.85 Cl 0.15 , Li 1 Hf 0.25 Ta 1.75 PO 7.75 F 0.25 , Li 1 Hf 0.25 Ta 1.75 PO 7.75 Cl 0.25 , Li 0.975 Hf 0.125 Ta 1.875 PO 7.85 Cl 0.15 , Li 0.875 Hf 0.125 Ta 1.875 PO 7.75 F 0.25 , Li 0.875 Hf 0.125 Ta 1.875 PO 7.75 Cl 0.25 , Li 1.225 Hf 0.375 Ta 1.625 PO 7.85 Cl 0.15 , Li 1.125 Hf 0.375 Ta 1.625 PO 7.75 F 0.25 , Li 1.125 Hf 0.375 Ta 1.625 PO 7.75 Cl 0.25 , Li 0.975 Zr 0.125 Ta 1.875 PO 7.85 Cl 0.15 , Li 0.875 Zr 0.125 Ta 1.875 PO 7.75 F 0.25 , Li 0.875 Zr 0.125 Ta 1.875 PO 7.75 Cl 0.25 , Li 1.1 Zr 0.25 Ta 1.75 PO 7.85 Cl 0.15 , Li 1 Zr 0.25 Ta 1.75 PO 7.75 F 0.25 , Li 1 Zr 0.25 Ta 1.75 PO 7.75 Cl 0.25 , Li 1.225 Zr 0.375 Ta 1.625 PO 7.85 Cl 0.15 , Li 1.125 Zr 0.375 Ta 1.625 PO 7.75 F 0.25 , Li 1.125 Zr 0.375 Ta 1.625 PO 7.75 Cl 0.25 , Li 0.875 Zr 0.025 Ta 1.975 PO 7.85 Cl 0.15 , Li 0.775 Zr 0.025 Ta 1.975 PO 7.75 F 0.25 , Li 0.775 Zr 0.025 Ta 1.975 PO 7.75 Cl 0.25 , Li 1.05 Zr 0.05 Ta 1.95 PO 8 , Li 1.05 Zr 0.05 Ta 1.95 PO 7.85 Cl 0.15 , Li 1.05 Zr 0.05 Ta 1.95 PO 7.75 F 0.25 , Li 1.05 Zr 0.05 Ta 1.95 PO 7.75 Cl 0.25 , Li 1.1 Zr 0.1 Ta 1.9 PO 8 , Li 1.1 Zr 0.1 Ta 1.9 PO 7.85 Cl 0.15 , Li 1.1 Zr 0.1 Ta 1.9 PO 7.75 F 0.25 , Li 1.1 Zr 0.1 Ta 1.9 PO 7.75 Cl 0.25 , Li 1.05 Ta 1.975 Hf 0.025 P 0.975 Si 0.025 O 8 , Li 1.2 Ta 1.9 Hf 0.1 P 0.9 Si 0.1 O 8 , Li 1.5 Hf

Assignees

• Samsung Electronics Co Ltd
• Univ Florida State Res Found Inc

Inventors

• Kim Ryounghee
• Cho Jeongju
• Miara Lincoln
• Patel Sawankumar
• Wang Yan
• Hu yan-yan
• Gwon Hyeokjo
• Kim Sewon
• Kim Jusik
• Jung Sungkyun

Classifications

• H01M10/0562 Primary

  Solid materials · CPC title

• C01B25/45 Primary

  containing plural metal, or metal and ammonium · CPC title

• C01B25/455

  containing halogen {(completely halogenated alkali metal phosphates C01D, e.g. lithium hexafluorophosphate C01D15/005)} · CPC title

• C01B33/32

  Alkali metal silicates ({C01B33/24} , C01B33/26 take precedence) · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title