Mixed conductor, electrochemical device including the same, and preparation method of mixed conductor

Patent metadata

Field	Value
Publication number	US-2020136217-A1
Application number	US-201916592843-A
Country	US
Kind code	A1
Filing date	Oct 4, 2019
Priority date	Oct 24, 2018
Publication date	Apr 30, 2020
Grant date	—

Abstract

A mixed ionic and electronic conductor represented by Formula 1:
T x Va y A 1-x-y M z O 3-δ ,
wherein T includes at least one monovalent cation, A includes at least one of a monovalent cation, a divalent cation, and a trivalent cation, M includes at least one of a trivalent cation, a tetravalent cation, and a pentavalent cation, M is an element other than Ti and Zr, Va is a vacancy, δ is an oxygen vacancy, 0<x, y≤0.25, 0<z<1, and 0≤δ≤1.

First claim

What is claimed is:

1 . A mixed ionic and electronic conductor represented by Formula 1:
T x Va y A 1-x-y M z O 3-δ   Formula 1

wherein, in Formula 1,
T comprises at least one monovalent cation,
A comprises at least one of a monovalent cation, a divalent cation, and a trivalent cation,
M comprises at least one of a trivalent cation, a tetravalent cation, and a pentavalent cation, and is an element other than Ti and Zr,
Va is a vacancy,
δ is an oxygen vacancy,
0<x, y≤0.25, 0<z≤1, and 0≤δ≤1.

2 . The mixed conductor of claim 1 , wherein, in Formula 1, T comprises at least one monovalent alkali metal cation.

3 . The mixed conductor of claim 1 , wherein, in Formula 1, M comprises a first cation and a second cation, and wherein an oxidation state of the first cation is different than an oxidation state of the second cation.

4 . The mixed conductor of claim 1 , wherein, in Formula 1, M comprises at least one pentavalent cation.

5 . The mixed conductor of claim 1 , wherein, in Formula 1, T comprises at least one of Li, Na, and K.

6 . The mixed conductor of claim 1 , wherein, in Formula 1, A comprises at least one of H, Na, K, Rb, Cs, Ca, Sr, Ba, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Gd, Tb, Dy, Ho, Tm, Yb, Lu, Er, and Eu.

7 . The mixed conductor of claim 1 , wherein, in Formula 1, M comprises at least one of Ni, Pd, Pb, Fe, Ir, Co, Rh, Mn, Cr, Ru, Re, Sn, V, Ge, W, Sc, Nb, Ta, and Mo.

8 . The mixed conductor of claim 1 , wherein 0<x<0.3.

9 . The mixed conductor of claim 1 , wherein δ is 0.

10 . The mixed conductor of claim 1 , wherein the mixed conductor represented by Formula 1 is represented by Formula 2:
T x Va y A 1-x-y M′ z M″ 1-z O 3-δ   Formula 2

wherein in Formula 2,
T comprises at least one monovalent cation,
A comprises at least one of a monovalent cation, a divalent cation, and a trivalent cation,
M′ and M″ each independently comprise at least one of a trivalent cation, a tetravalent cation, and a pentavalent cation,
M′ and M″ are each independently an element other than Ti and Zr,
Va is a vacancy,
δ is an oxygen vacancy,
0<x, y≤0.25, 0<z<1, and 0≤δ≤1.

11 . The mixed conductor of claim 10 , wherein M′ has an oxygen vacancy formation energy value of 2.9 electron volts, or less.

12 . The mixed conductor of claim 10 , wherein M′ comprises at least one of a trivalent cation and a tetravalent cation, and
M″ comprises at least one pentavalent cation.

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

14 . The mixed conductor of claim 1 , wherein an electronic conductivity of the mixed conductor is 4×10 −9 S/cm or greater at 25° C.

15 . The mixed conductor of claim 1 , wherein an ionic conductivity of the mixed conductor is 1×10 −6 S/cm or greater at 25° C.

16 . The mixed conductor of claim 1 , wherein the mixed conductor has a phase with a perovskite type crystal structure.

17 . The mixed conductor of claim 1 , wherein the mixed conductor has a single peak at a diffraction angle of 23°±2.5° two-theta, when analyzed by X-ray diffraction using Cu Kα radiation.

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

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 mixed conductor, the method comprising:
mixing a precursor of element T, a precursor of element A, and a precursor of element M to prepare a mixture; and heat treating the mixture to prepare the mixed conductor, wherein the mixed conductor is represented by Formula 1:
T x Va y A 1-x-y M z O 3-δ   Formula 1

wherein, in Formula 1,
T comprises at least one monovalent cation,
A comprises at least one selected from a monovalent cation, a divalent cation, and a trivalent cation,
M comprises at least one selected from a trivalent cation, a tetravalent cation, and a pentavalent cation,
M is an element other than Ti and Zr,
Va is a vacancy,
δ is an oxygen vacancy,
0<x, y≤0.25, 0<z<1, and 0≤δ≤1.

21 . The method of claim 20 , wherein the heat treating comprises a first heat treating and a second heat treating.

22 . The method of claim 20 , wherein the heat treating comprises:
drying the mixture, first heat treating the mixture in an oxidizing atmosphere to obtain a first heat treatment product, pulverizing the first heat treatment product to obtain powdered first heat treatment product, drying the powdered first heat treatment product, second heat treating the dried and powdered first heat treatment product in an oxidizing atmosphere to obtain a second heat treatment product, pulverizing the second heat treatment product, pressing the pulverized second heat treatment product to obtain a pellet, and third heat treating the pellet in an oxidizing atmosphere, in a reducing atmosphere, or in both an oxidizing atmosphere and a reducing atmosphere to prepare the mixed conductor.

23 . The method of claim 22 , wherein
the first heat treating is performed at a temperature of about 600° C. to about 1000° C. for about 3 hours to about 5 hours, the second heat treating is performed at a temperature of about 900° C. to about 1500° C. for about 4 hours to about 6 hours, and the third heat treating is performed at a temperature of about 1000° C. to about 1400° C. for 10 hours to about 24 hours.

24 . The method of claim 20 , wherein
the precursor of element T is a salt of T, an oxide of T, or carbonate of T, the precursor of element A is a salt of A, an oxide of A, or carbonate of A, and the precursor of element M is a salt of M or an oxide of M.

25 . The method of claim 20 , wherein the precursor of element M comprises a precursor of element M′ and a precursor of element M″.

Assignees

• Samsung Electronics Co Ltd

Inventors

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

Classifications

• H01G11/62

  characterised by the solute, e.g. salts, anions or cations therein · CPC title

• C01G55/002

  Compounds containing ruthenium, rhodium, palladium, osmium, iridium or platinum, with or without oxygen or hydrogen, and containing two or more other elements (C01G55/007 takes precedence) · CPC title

• C01P2006/40

  Electric properties · CPC title

• C01G51/70 Primary

  containing rare earths, e.g. LaCoO3  (C01G51/68 takes precedence) · CPC title

• C01P2002/72

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