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-12087906-B2
Application number	US-202318339585-A
Country	US
Kind code	B2
Filing date	Jun 22, 2023
Priority date	May 24, 2019
Publication date	Sep 10, 2024
Grant date	Sep 10, 2024

Abstract

A solid conductor including:
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 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,

Li 1+x+y-z Ta 2-x M x P 1-y Q y O 8 ·z LiX  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 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-z Ta 2 PO 8-z X z   Formula 1

wherein, in Formula 1,
X is a halogen, a pseudohalogen, or a combination thereof, and
0<z<1,
Li 1-z Ta 2 PO 8 ·zLiX  Formula 2

wherein, in Formula 2,
X is a halogen, a pseudohalogen, or a combination thereof, and
0<z<1.

2. 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.

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

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

5. 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.

6. 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.

7. The solid conductor of claim 6 , 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.

8. 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.

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

10. The solid conductor of claim 1 , wherein the solid conductor is
Li 0.9 Ta 2 PO 7.9 F 0.1 , Li 0.9 Ta 2 PO 7.9 Cl 0.15 , Li 0.85 Ta 2 PO 7.85 Cl 0.15 , Li 0.85 Ta 2 PO 7.85 F 0.15 , Li 0.8 Ta 2 PO 7.8 F 0.2 , Li 0.8 Ta 2 PO 7.8 Cl 0.2 , Li 0.975 Ta 2 PO 7.975 F 0.025 , Li 0.95 Ta 2 PO 7.95 Cl 0.05 , Li 0.975 Ta 2 PO 7.975 Cl 0.025 , Li 0.95 Ta 2 PO 7.95 F 0.05 , Li 0.875 Ta 2 PO 7.875 F 0.125 , Li 0.75 Ta 2 PO 7.75 F 0.25 , Li 0.625 Ta 2 PO 7.625 F 0.375 , Li 0.5 Ta 2 PO 7.5 F 0.5 , Li 0.375 Ta 2 PO 7.375 F 0.625 , Li 0.25 Ta 2 PO 7.25 F 0.75 , or a combination thereof.

11. A method of manufacturing a solid conductor, the method comprising:
preparing a precursor mixture comprising a precursor for forming a solid conductor; and
heat-treating the precursor mixture in an oxidizing gas to manufacture a solid conductor represented by Formula 1, Formula 2, or a combination thereof,
Li 1-z Ta 2 PO 8-z X z   Formula 1

wherein, in Formula 1,
X is a halogen, a pseudohalogen, or a combination thereof, and
0<z<1,
Li 1-z Ta 2 PO 8 ·zLiX  Formula 2

wherein, in Formula 2,
X is a halogen atom or a pseudohalogen, and
0<z<1.

12. The method of claim 11 , wherein the heat-treating comprises heat-treating at about 500° C. to about 1,200° ° C.

13. The method of claim 12 , wherein the heat-treating comprises a first heat-treatment and a second heat-treatment, wherein the second heat-treatment comprises heat-treating at a temperature greater than a temperature of the first heat-treatment, and the first heat-treatment comprises heat-treating at a temperature in a range of about 500° C. to about 1,000° C., and
the second heat-treatment comprises heat-treating at a temperature of about 600° ° C. to about 1,200° C.

14. The method of claim 11 , wherein the preparing the precursor mixture further comprises adding a lithium precursor to the precursor mixture, and the preparing the precursor mixture further comprises adding a lithium precursor containing lithium chloride, lithium fluoride, or a combination thereof to the precursor mixture.

15. A solid electrolyte comprising:
the solid conductor of claim 1 .

16. An electrochemical device comprising:
a cathode;
an anode; and
the solid conductor of claim 1 .

17. The electrochemical device of claim 16 , wherein the electrochemical device is an electrochemical battery comprising the cathode, the anode, and a solid electrolyte disposed between the cathode and the anode, the solid electrolyte comprising the solid conductor.

18. The electrochemical device of claim 17 , wherein the solid electrolyte is an electrolyte protective film, a cathode protective film, an anode protective film, or a combination thereof.

19. The electrochemical device of claim 16 , wherein the electrochemical device is an all-solid-state battery.

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

• H01M2300/0074

  Ion conductive at high temperature · CPC title

• C01P2002/86

  by NMR- or ESR-data · CPC title

• C01P2002/72

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

• C01P2002/52

  containing elements as dopants · CPC title

• C01P2006/40

  Electric properties · CPC title