Solid electrolyte, preparation method thereof, metal air battery including the same, and electrochemical device including the same

Patent metadata

Field	Value
Publication number	US-11837696-B2
Application number	US-202016989229-A
Country	US
Kind code	B2
Filing date	Aug 10, 2020
Priority date	Dec 13, 2019
Publication date	Dec 5, 2023
Grant date	Dec 5, 2023

Abstract

A solid electrolyte including: an oxide represented by Formula 1LiyMzHfO3-x  Formula 1wherein, in Formula 1,M is a divalent element, a trivalent element, or a combination thereof, and0≤x<3, 0<y<1, and 0<z<1.

First claim

What is claimed is:

1. A solid electrolyte comprising:
an oxide represented by Formula 1,
Li y M z HfO 3-x   Formula 1

wherein, in Formula 1,
M is Sr, Ba, Ca, Mg, La, Ce, Pr, Gd, Y, Sc, or a combination thereof, and
0≤x<3, 0<y<1, and 0<z<1.

2. The solid electrolyte of claim 1 , wherein, in Formula 1, x is 0 to about 0.9.

3. The solid electrolyte of claim 1 , wherein, in Formula 1, y is about 0.1 to about 0.9.

4. The solid electrolyte of claim 1 , wherein, in Formula 1, z is about 0.1 to about 0.9.

5. The solid electrolyte of claim 1 , wherein the oxide represented by Formula 1 is at least one selected from oxides represented by Formulae 2 to 9:
Li y Ba z HfO 3-x   Formula 2

wherein, in Formula 2, 0≤x<3, 0<y<1, and 0<z<1 are satisfied;
Li y Sr z HfO 3-x   Formula 3

wherein, in Formula 3, 0≤x<3, 0<y<1, and 0<z<1 are satisfied;
Li y Ca z HfO 3-x   Formula 4

wherein, in Formula 4, 0≤x<3, 0<y<1, and 0<z<1 are satisfied;
Li y La z HfO 3-x   Formula 5

wherein, in Formula 5, 0≤x<3, 0<y<1, and 0<z<1 are satisfied;
Li y Ce z HfO 3-x   Formula 6

wherein, in Formula 6, 0≤x<3, 0<y<1, and 0<z<1 are satisfied;
Li y Pr z HfO 3-x   Formula 7

wherein, in Formula 7, 0≤x<3, 0<y<1, and 0<z<1 are satisfied;
Li y Y z HfO 3-x   Formula 8

wherein, in Formula 8, 0≤x<3, 0<y<1, and 0<z<1 are satisfied; and
Li y Sc z HfO 3-x   Formula 9

wherein, in Formula 9, 0≤x<3, 0<y<1, and 0<z<1 are satisfied.

6. The solid electrolyte of claim 5 , wherein, x is 0 to about 0.9, y is about 0.1 to about 0.9, z is about 0.1 to about 0.9, and y+z<1.

7. The solid electrolyte of claim 1 , wherein the oxide has a perovskite crystal structure.

8. The solid electrolyte of claim 7 , wherein the oxide has a crystal structure in which Li, a vacancy, and M each independently reside in an A-site in the perovskite crystal structure of ABO 3 , and hafnium resides in a B-site in the perovskite crystal structure of ABO 3 .

9. The solid electrolyte of claim 7 , wherein the oxide of Formula 1 is Li 0.3 Sr 0.6 HfO 2.75 , Li 0.3 Sr 0.4 HfO 2.55 , Li 0.3 Ba 0.6 HfO 2.75 , Li 0.3 Ba 0.4 HfO 2.55 , Li 0.3 Ca 0.6 HfO 2.75 , Li 0.3 Ca 0.4 HfO 2.55 , Li 0.10 Ca 0.80 HfO 2.85 , Li 0.20 Ca 0.80 HfO 2.7 , Li 0.25 Ca 0.50 HfO 2.625 , Li 0.40 Ca 0.20 HfO 2.7 , Li 0.10 Sr 0.60 HfO 2.85 , Li 0.20 Sr 0.60 HfO 2.7 , Li 0.25 Sr 0.50 HfO 2.625 , Li 0.40 Sr 0.20 HfO 2.7 , Li 0.10 Ba 0.40 HfO 2.75 , Li 0.20 Ba 0.60 HfO 2.7 , Li 0.25 Ba 0.50 HfO 2.625 , Li 0.40 Ba 0.20 HfO 2.7 , Li 0.34 La 0.55 HfO 3 , Li 0.34 Ce 0.55 HfO 3 , Li 0.34 Pr 0.55 HfO 3 , Li 0.34 Y 0.55 HfO 3 , Li 0.34 Sc 0.55 HfO 3 , or a combination thereof.

10. The solid electrolyte of claim 1 , wherein the solid electrolyte has an ionic conductivity of about 1×10 −6 S/cm or more at 25° C.

11. The solid electrolyte of claim 1 , wherein an intensity of a first diffraction peak at a diffraction angle of about 31.0° 2θ is greater than an intensity of a second diffraction peak at a diffraction angle of about 21.8° 20, when analyzed by X-ray diffraction using Cu Kα radiation.

12. The solid electrolyte of claim 1 , wherein a first diffraction peak has an intensity in an area where a diffraction angle is about 31.0° 2θ and a second diffraction peak in an area where a diffraction angle is about 21.8° 2θ, and wherein the intensity of the first diffraction peak is about the same as to about 25 times greater than the intensity of the second diffraction peak, when analyzed by X-ray diffraction using Cu Kα radiation.

13. The solid electrolyte of claim 1 , wherein the solid electrolyte has a pellet density of about 4 grams per cubic centimeter to about 7.5 grams per cubic centimeter.

14. A protection layer for a lithium battery, the protection layer comprising:
the solid electrolyte of claim 1 , wherein the solid electrolyte is disposed on a cathode or an anode.

15. A metal air battery comprising:
a cathode;
an anode; and
an electrolyte between the cathode and the anode,
wherein at least one of the cathode, the anode, or the electrolyte includes the solid electrolyte of claim 1 .

16. The metal air battery of claim 15 , wherein the electrolyte comprises the solid electrolyte.

17. The metal air battery of claim 15 , wherein the anode comprises lithium.

18. An electrochemical device comprising:
an anode;
a cathode; and
the solid electrolyte of claim 1 between the anode and the cathode.

19. The electrochemical device of claim 18 , wherein the electrochemical device is a battery, an accumulator, a supercapacitor, a fuel cell, a sensor, or an electrochromic device.

20. A method of preparing a solid electrolyte, the method comprising:
providing a precursor mixture comprising a lithium precursor, a hafnium precursor, and an M precursor; and
heat-treating the precursor mixture to prepare a solid electrolyte comprising an oxide represented by Formula 1,
Li y M z HfO 3-x   Formula 1

wherein in Formula 1,
M is Sr, Ba, Ca, Mg, La, Ce, Pr, Gd, Y, Sc, or a combination thereof, and
0≤x<3, 0<y<1, and 0<z<1.

21. The method of claim 20 , wherein the heat-treating comprises a primary heat-treating at about 600° C. to about 950° C. in an inert gas or in an oxidizing gas.

22. The method of claim 20 , further comprising:
pulverizing the primary heat-treated precursor mixture to obtain a pulverized product; and secondary heat-treating the pulverized product.

23. The method of claim 22 , wherein the secondary heat-treating of the pulverized product comprises heat-treating at about 900° C. to about 1300° C.

24. The method of claim 23 , wherein the secondary heat-treating comprises heat-treating in a mixed gas comprising about 1 volume percent to about 10 volume percent of a reducing gas and about 90 volume percent to 99 volume percent of an inert gas, based on a total volume of the mixed gas.

Assignees

• Samsung Electronics Co Ltd

Inventors

• Ma Sangbok
• Seo Donghwa

Classifications

• H01M10/0562 Primary

  Solid materials · CPC title

• C01G27/006

  Compounds containing hafnium, with or without oxygen or hydrogen, and containing two or more other elements · CPC title

• H01M10/0525

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

• C01P2002/34

  perovskite-type (ABO3) · CPC title

• C01P2002/72

  by d-values or two theta-values, e.g. as X-ray diagram · CPC title