Mixed conductor, method of preparing the mixed conductor, and cathode, lithium-air battery and electrochemical device each including the mixed conductor

Patent metadata

Field	Value
Publication number	US-2022359886-A1
Application number	US-202217863483-A
Country	US
Kind code	A1
Filing date	Jul 13, 2022
Priority date	Oct 24, 2018
Publication date	Nov 10, 2022
Grant date	—

Abstract

A mixed conductor, a method of preparing the same, and a cathode, a lithium-air battery, and an electrochemical device each including the mixed conductor. The mixed conductor is represented by Formula 1 and having electronic conductivity and ionic conductivity:LixMO2-δ  Formula 1wherein, in Formula 1, M is a Group 4 element, a Group 5 element, a Group 6 element, a Group 7 element, a Group 8 element, a Group 10 element, a Group 11 element, a Group 12 element, or a combination thereof, and 0<x<1 and 0≤δ≤1 are satisfied.

First claim

What is claimed is:

1 . A mixed conductor represented by Formula 1 and having electronic conductivity and ionic conductivity:
Li x MO 2-δ   Formula 1
wherein, in Formula 1, M is a Group 4 element, a Group 5 element, a Group 6 element, a Group 7 element, a Group 8 element, a Group 10 element, a Group 11 element, a Group 12 element, or a combination thereof, and 0<x<1 and 0<δ=1 are satisfied.

2 . The mixed conductor of claim 1 , wherein M is cobalt, nickel, iron, manganese, vanadium, titanium, chromium, copper, zinc, or a combination thereof.

3 . The mixed conductor of claim 1 , wherein, in Formula 1, x is from about 0.3 to about 0.5.

4 . The mixed conductor of claim 1 , wherein the mixed conductor comprises a phase having a layered crystal structure.

5 . The mixed conductor of claim 4 , wherein the mixed conductor comprises a layer of M-centered oxygen octahedra.

6 . The mixed conductor of claim 1 , wherein the mixed conductor is a compound represented by Formula 2:
Li x M 1 a M 2 b M 3 1-a-b O 2-δ   Formula 2
wherein, in Formula 2, M 1 is Ni, Co, Mn, or a combination thereof, M 2 and M 3 are each independently a Group 4 element, a Group 5 element, a Group 8 element, a Group 11 element, a Group 12 element, or a combination thereof, and 0<x<1, 0<a≤1, 0≤b<1, and 0<δ≤1 are satisfied.

7 . The mixed conductor of claim 6 , wherein M 2 and M 3 are each independently iron, vanadium, titanium, chromium, copper, zinc, or a combination thereof.

8 . The mixed conductor of claim 6 , wherein, in Formula 2, a is 1, b is 0, and M 1 has a mixed valence state and comprises metals having a plurality of a different oxidation numbers.

9 . The mixed conductor of claim 1 , wherein the mixed conductor is Li x CO a O 2-δ , Li x CO a Ni 1-a O 2-δ , Li x CO a Ni b Mn 1-a-b O 2-δ , Li x Ni a O 2-δ , Li x Mn a O 2-δ , Li x Cr a O 2-δ , Li x CO a Mn b O 2-δ , Li x Ni a Mn b O 2-δ , Li x Cr a Mn b O 2-δ , or a combination thereof, and
wherein, in each of the foregoing mixed conductors, each x is independently 0<x<1, each a is independently 0<a≤1, each b is independently 0≤b<1 and each δ is independently 0<δ≤1.

10 . The mixed conductor of claim 1 , wherein the mixed conductor is Li 0.5 CoO 2-δ , Li 0.5 Co 0.5 Ni 0.5 O 2-δ , Li 0.5 NiO 2-δ , Li 0.5 MnO 2-δ , Li 0.5 CrO 2-δ , Li 0.5 Co 0.5 Mn 0.5 O 2-δ , Li 0.5 Ni 0.5 Mn 0.5 O 2-δ , Li 0.5 Cr 0.5 Mn 0.5 O 2-δ , Li 0.4 CoO 2-δ , Li 0.4 Co 0.5 Ni 0.5 O 2-δ , Li 0.4 NiO 2-δ , Li 0.4 MnO 2-δ , Li 0.4 CrO 2-δ , Li 0.4 Co 0.5 Mn 0.5 O 2-δ , Li 0.4 Ni 0.5 Mn 0.5 O 2-δ , Li 0.4 Cr 0.5 Mn 0.5 O 2-δ , Li 0.3 CoO 2-δ , Li 0.3 Co 0.5 Ni 0.5 O 2-δ , Li 0.3 NiO 2-δ , Li 0.3 MnO 2-δ , Li 0.3 CrO 2-δ , Li 0.3 Co 0.5 Mn 0.5 O 2 O 2-δ , Li 0.3 Ni 0.5 Mn 0.5 O 2-δ , Li 0.3 Cr 0.5 Mn 0.5 O 2-δ , Li 0.5 Co 0.4 Ni 0.6 O 2-δ , Li 0.5 Co 0.4 Mn 0.6 O 2-δ , Li 0.5 Ni 0.4 Mn 0.6 O 2-δ , Li 0.5 Cr 0.4 Mn 0.6 O 2-δ , Li 0.5 Co 0.3 Ni 0.7 O 2-δ , Li 0.3 Co 0.3 Mn 0.7 O 2-δ , Li 0.5 Ni 0.3 Mn 0.7 O 2-δ , Li 0.5 Cr 0.3 Mn 0.7 O 2-δ , Li 0.5 Co 0.2 Ni 0.8 O 2-δ , Li 0.5 Ni 0.8 Mn 0.2 O 2-δ , Li 0.5 Co 0.1 Ni 0.9 O 2-δ , Li 0.5 Ni 0.9 Mn 0.1 O 2-δ , Li 0.5 Co 0.6 Ni 0.4 O 2-δ , Li 0.5 Co 0.6 Mn 0.4 O 2-δ , Li 0.5 Ni 0.6 Mn 0.4 O 2-δ , Li 0.5 Cr 0.6 Mn 0.4 O 2-δ , or a combination thereof, and 0<δ≤1 is satisfied.

11 . The mixed conductor of claim 1 , wherein an electronic conductivity of the mixed conductor is greater than an ionic conductivity thereof.

12 . The mixed conductor of claim 1 , wherein the mixed conductor has an electronic conductivity greater than 4.0×10 −9 Siemens per centimeter at 25° C.

13 . The mixed conductor of claim 1 , wherein the mixed conductor has an ionic conductivity of 1.0×10 −9 Siemens per centimeter or greater at 25° C.

14 . The mixed conductor of claim 1 , wherein an X-ray diffraction spectrum of the mixed conductor includes a first peak at a diffraction angle of about 65° 2θ and a second peak at 67° 2θ, when analyzed using Cu Kα radiation.

15 . The mixed conductor of claim 14 , wherein a maximum of the first peak is located in a range of about 65° 2θ to 66° 2θ, and
a maximum of the second peak is located in a range of about 66° 2θ to about 67° 2θ.

16 . The mixed conductor of claim 14 , wherein a height of the second peak is in a range of about 30% to about 50% of a height of the first peak.

17 . A method of preparing the mixed conductor of claim 1 , the method comprising:
mixing a lithium compound, an M-containing compound, and a solvent to obtain a mixture; first thermally treating the mixture to obtain a first thermal treatment product; pulverizing the first thermal treatment product to obtain a pulverized product; and second thermally treating the pulverized product to prepare the mixed conductor of claim 1 , wherein M in Formula 1 is a Group 4 element, a Group 5 element, a Group 6 element, a Group 7 element, a Group 8 element, a Group 10 element, a Group 11 element, a Group 12 element, or a combination thereof.

18 . The method of claim 17 , wherein the second thermally treating comprises thermally treating at a temperature which is greater than a temperature of the first thermally treating.

19 . The method of claim 17 , wherein the first thermally treating comprises treating at a temperature of about 400° C. to about 900° C.

20 . The method of claim 17 , wherein the second thermally treating comprises treating at a temperature of about 400° C. to about 1,000° C.

21 . The method of claim 17 , wherein the lithium compound is lithium oxide, lithium carbonate, lithium chloride, lithium sulfide, lithium nitrate, lithium phosphate, lithium hydroxide, or a combination thereof.

22 . The method of claim 17 , wherein the M-containing compound is an M-containing oxide, an M-containing carbonate, an M-containing chloride, an M-containing phosphate, an M-containing hydroxide, an M-containing nitrate, an M-containing hydroxide, or a combination thereof.

23 . An electrochemical device comprising the mixed conductor of claim 1 .

24 . The electrochemical device of claim 23 , wherein the electrochemical device is a battery, an accumulator, a supercapacitor, a fuel cell, a sensor, or an electrochromic device.

Assignees

• Samsung Electronics Co Ltd

Inventors

• Ma Sangbok
• Kwon Hyukjae
• Lee Hyunpyo
• Seo Donghwa
• Im Dongmin

Classifications

• H01G11/46 Primary

  Metal oxides · CPC title

• H01M2300/0071

  Oxides · CPC title

• C01G51/50

  of the type (MnO2)n-, e.g. Li(CoxMn1-x)O2 or Li(MyCoxMn1-x-y)O2 · CPC title

• H01M12/08

  composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type · CPC title

• C01P2004/62

  Submicrometer sized, i.e. from 0.1-1 micrometer · CPC title