Solid electrolyte, preparation method thereof, lithium-air battery including the solid electrolyte, and electrochemical device including the solid electrolyte

Patent metadata

Field	Value
Publication number	US-11742515-B2
Application number	US-202017030571-A
Country	US
Kind code	B2
Filing date	Sep 24, 2020
Priority date	Sep 26, 2019
Publication date	Aug 29, 2023
Grant date	Aug 29, 2023

Abstract

A solid electrolyte including: a compound represented by Formula 1,

Li x M1 2−y M2 y (PO 4−z X z ) 3   Formula 1
wherein, in Formula 1, M1 is a tetravalent element, M2 is a monovalent element, a divalent element, a trivalent element, a tetravalent element, a pentavalent element, a hexavalent element, or a combination thereof, X is a halogen atom, a pseudohalogen, or a combination thereof, 0<x<8, 0≤y<1, and 0<z<4.

First claim

What is claimed is:

1. A solid electrolyte comprising:
a compound represented by Formula 1
Li x M1 2−y M2 y (PO 4−z X z ) 3   Formula 1

wherein, in Formula 1,
M1 is a tetravalent element,
M2 is aluminum, lanthanum, scandium, cerium, praseodymium, gadolinium, europium, or a combination thereof,
X is a halogen atom, a pseudohalogen, or a combination thereof, and 0<x<8
0≤y<1, and 0<z<4.

2. The solid electrolyte of claim 1 , wherein M1 is hafnium, titanium, zirconium, or a combination thereof.

3. The solid electrolyte of claim 1 , wherein M2 is lanthanum, scandium, cerium, praseodymium, gadolinium, europium, or a combination thereof.

4. The solid electrolyte of claim 1 , wherein X is chlorine, bromine, fluorine, cyanide, cyanate, thiocyanate, azide, or a combination thereof.

5. The solid electrolyte of claim 1 , wherein, in Formula 1,
X 3z is F n , Br n , Cl n , (F a Cl 1−a ) n , (F a Br 1−a ) n , or (Cl a Br 1−a ) n ,
n is 1 or less and
a is about 0.01 to about 0.99.

6. The solid electrolyte of claim 1 , wherein the solid electrolyte has a NASICON crystal structure or a crystal structure that is isostructural with the NASICON crystal structure.

7. The solid electrolyte of claim 1 , wherein, in Formula 1, x is about 0.5 to about 1.5, y is 0 to about 0.8, and z is greater than 0 and less than or equal to about 1.

8. The solid electrolyte of claim 1 , wherein the compound represented by Formula 1 is a compound represented by Formula 2, a compound represented by Formula 3, or a compound represented by Formula 4:
Li 1+y−3z Hf 2−y M2 y (PO 4−z X z ) 3   Formula 2

wherein, in Formula 2, M2 is aluminum, lanthanum, scandium, cerium, praseodymium, gadolinium, europium, or a combination thereof,
X is a halogen atom, a pseudohalogen, or a combination thereof,
0≤y<1, and 0<z<4, or
Li 1+y−3z Ti 2−y M2 y (PO 4−z X z ) 3   Formula 3

wherein, in Formula 3, M2 is aluminum, lanthanum, scandium, cerium, praseodymium, gadolinium, europium, a hexavalent element, or a combination thereof,
X is a halogen atom, a pseudohalogen, or a combination thereof,
0≤y<1, and 0<z<4, or
Li 1+y−3z Zr 2−y M2 y (PO 4−z X z ) 3   Formula 4

wherein, in Formula 4, M2 is aluminum, lanthanum, scandium, cerium, praseodymium, gadolinium, europium, or a combination thereof,
X is a halogen atom, a pseudohalogen, or a combination thereof,
0≤y<1, and 0<z<4.

9. The solid electrolyte of claim 8 , wherein, in Formulae 2 to 4, 1+y−3z is about 0.5 to about 1.5, y is 0 to about 0.8, and z is greater than 0 and equal to or less than 1.

10. The solid electrolyte of claim 1 , wherein the compound represented by Formula 1 is Li 0.8 Hf 2 P 3 O 11.8 F 0.2 , Li 0.8 Hf 2 P 3 O 11.8 Cl 0.2 , Li 0.8 Hf 2 P 3 O 11.8 Br 0.2 , Li 0.8 Hf 2 P 3 O 11.8 Br 0.1 F 0.1 , Li 0.8 Hf 2 P 3 O 11.8 Br 0.1 Cl 0.1 , Li 0.8 Ti 2 P 3 O 11.8 F 0.2 , Li 0.8 Ti 2 P 3 O 11.8 Cl 0.2 , Li 0.8 Ti 2 P 3 O 11.8 Br 0.2 , Li 0.8 Ti 2 P 3 O 11.8 Cl 0.2 , LiHf 1.9 Al 0.1 P 3 O 11.9 F 0.1 , LiHf 1.9 Al 0.1 P 3 O 11.9 Br 0.1 , LiHf 1.9 Al 0.1 P 3 O 11.9 F 0.05 Br 0.05 , LiHf 1.9 Al 0.1 P 3 O 11.9 Cl 0.1 ; LiHf 1.9 Al 0.1 P 3 O 11.9 Cl 0.05 Br 0.05 , LiHf 1.9 La 0.1 P 3 O 11.9 F 0.1 , LiHf 1.9 La 0.1 P 3 O 11.9 Br 0.1 , LiHf 1.9 La 0.1 P 3 O 11.9 F 0.05 Br 0.05 , LiHf 1.9 La 0.1 P 3 O 11.9 Cl 0.05 Br 0.05 , LiHf 1.9 La 0.1 P 3 O 11.9 Cl 0.1 , LiHf 1.9 Gd 0.1 P 3 O 11.9 F 0.1 , LiHf 1.9 Gd 0.1 P 3 O 11.9 F 0.05 Br 0.05 , LiHf 1.9 Gd 0.1 P 3 O 11.9 Cl 0.05 Br 0.05 , LiHf 1.9 Gd 0.1 P 3 O 11.9 Cl 0.1 , LiZr 1.9 Al 0.1 P 3 O 11.9 F 0.1 , LiHf 1.9 Al 0.1 P 3 O 11.9 F 0.05 Br 0.05 , LiHf 1.9 Al 0.1 P 3 O 11.9 Cl 0.05 Br 0.05 , LiZr 1.9 Al 0.1 P 3 O 11.9 Cl 0.1 , LiZr 1.9 La 0.1 P 3 O 11.9 F 0.1 , LiZr 1.9 La 0.1 P 3 O 11.9 Br 0.1 , LiZr 1.9 La 0.1 P 3 O 11.9 Br 0.05 F 0.05 , LiZr 1.9 La 0.1 P 3 O 11.9 Br 0.05 Cl 0.05 , LiZr 1.9 La 0.1 P 3 O 11.9 Cl 0.1 , LiZr 1.9 Gd 0.1 P 3 O 11.9 F 0.1 , LiZr 1.9 Gd 0.1 P 3 O 11.9 Br 0.1 , LiZr 1.9 Gd 0.1 P 3 O 11.9 Br 0.05 F 0.05 , LiZr 1.9 Gd 0.1 P 3 O 11.9 Br 0.05 Cl 0.05 , LiZr 1.9 Gd 0.1 P 3 O 11.9 Cl 0.1 , LiTi 1.9 Al 0.1 P 3 O 11.9 F 0.1 , LiTi 1.9 Gd 0.1 P 3 O 11.9 Br 0.1 , LiTi 1.9 Gd 0.1 P 3 O 11.9 Br 0.05 F 0.05 , LiTi 1.9 Gd 0.1 P 3 O 11.9 Br 0.05 Cl 0.05 , LiTi 1.9 Al 0.1 P 3 O 11.9 Cl 0.1 , LiTi 1.9 La 0.1 P 3 O 11.9 F 0.1 , LiTi 1.9 La 0.1 P 3 O 11.9 Cl 0.1 , LiTi 1.9 Gd 0.1 P 3 O 11.9 F 0.1 , LiTi 1.9 Gd 0.1 P 3 O 11.9 Br 0.1 , LiTi 1.9 Gd 0.1 P 3 O 11.9 Br 0.05 F 0.05 , LiTi 1.9 Gd 0.1 P 3 O 11.9 Br 0.05 Cl 0.05 , LiTi 1.9 Gd 0.1 P 3 O 11.9 Cl 0.1 , or a combination thereof.

11. The solid electrolyte of claim 1 , wherein the solid electrolyte has an ionic conductivity of about 1×10 −5 Siemens per centimeter or greater after being impregnated with a saturated lithium hydroxide solution.

12. The solid electrolyte of claim 1 , wherein an ionic conductivity retention of the solid electrolyte in a saturated lithium hydroxide solution is about 50% or greater.

13. The solid electrolyte of claim 1 , wherein the solid electrolyte exhibits
a first diffraction peak with a maximum point at about 19.93° 2θ to about 19.99° 2θ, and
a second diffraction peak with a maximum point at a diffraction angle of about 20.17°2θ to about 20.25° 2θ, when analyzed by X-ray diffraction using CuKα radiation.

14. The solid electrolyte of claim 13 , wherein an intensity ratio of the second diffraction peak to the first diffraction peak is less than about 1.

15. The solid electrolyte of claim 1 , wherein the solid electrolyte exhibits
a first diffraction peak with a maximum point at a diffraction angle of about 19.93° 2θ to about 19.99° 2θ, and
a second diffraction peak having a doublet peak shape, and wherein the second diffraction peak includes a peak with a first maximum point at about 20.15° 2θ to about 20.25°2θ, and a peak with a maximum point at about 20.26° 2θ to about 20.32° 2θ,
when analyzed by X-ray diffraction using CuKα radiation.

16. The solid electrolyte of claim 15 , wherein an intensity ratio of the second diffraction peak with the first maximum point at about 20.15° 2θ to about 20.25° 2θ to the first diffraction peak is greater than about 1.

17. The solid electrolyte of claim 15 , wherein an intensity ratio of the second diffraction peak with a maximum point of about 20.26° 2θ to about 20.32° 2θ to the first diffraction peak is greater than about 1.

18. The solid electrolyte of claim 1 , wherein the solid electrolyte has an ionic conductivity at 25° C. of about 1×10 −6 Siemens per centimeter, or greater.

19. A lithium-air battery comprising:
a cathode; an anode; and an electrolyte disposed between the cathode and the anode,
the electrolyte comprising the solid electrolyte according to claim 1 .

20. The lithium-air battery of claim 19 , wherein at least one of the cathode and the anode comprises the solid electrolyte comprising the compound of Formula 1:
Li x M1 2−y M2 y (PO 4−z X z ) 3   Formula 1

wherein, in Formula 1,
M1 is a tetravalent element,
M2 is aluminum, lanthanum, scandium, cerium, praseodymium, gadolinium, europium, or a combination thereof,
X is a halogen atom, a pseudohalogen, or a combination thereof,
0<x<8, 0≤y<1, and 0<z<4.

21. An electrochemical device comprising the solid electrolyte according to claim 1 .

22. The electrochemical device of claim 21 , comprising a battery, an accumulator, a supercapacitor, a fuel cell, a sensor, an electrochromic device, or a combination thereof.

23. A solid electrolyte comprising:
a compound re

Assignees

• Samsung Electronics Co Ltd

Inventors

• Ma Sangbok
• Seo Donghwa
• Lee Hyunpyo

Classifications

• H01M10/0562 Primary

  Solid materials · 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

• H01M2300/008

  Halides · CPC title

• H01M2300/0068

  inorganic · CPC title

• H01M10/0525

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