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

Patent metadata

Field	Value
Publication number	US-11456454-B2
Application number	US-201916654611-A
Country	US
Kind code	B2
Filing date	Oct 16, 2019
Priority date	Oct 24, 2018
Publication date	Sep 27, 2022
Grant date	Sep 27, 2022

Abstract

A mixed conductor represented by Formula 1:A1±xM2±yO4−δ  Formula 1wherein, in Formula 1, A is a monovalent cation, and M is at least one of a monovalent cation, a divalent cation, a trivalent cation, a tetravalent cation, a pentavalent cation, or a hexavalent cation, 0≤x≤1, 0≤y≤2, and 0≤δ≤1, with the proviso that when M includes vanadium, 0<δ≤1, and wherein the mixed conductor has an inverse spinel crystal structure.

First claim

What is claimed is:

1. A mixed conductor represented by Formula 1:
A 1±x M 2±y O 4−δ   Formula 1

wherein, in Formula 1,
A is a monovalent cation,
M is at least one of a monovalent cation, a divalent cation, a trivalent cation, a tetravalent cation, a pentavalent cation, or a hexavalent cation,
0≤x≤1, 0≤y≤2, and
0≤δ≤1, with the proviso that when M includes vanadium, 0<δ≤1, and
wherein the mixed conductor has an inverse spinel crystal structure.

2. The mixed conductor of claim 1 , wherein A in Formula 1 is a monovalent alkali metal cation.

3. The mixed conductor of claim 2 , wherein A is at least one of Li, Na, or K.

4. The mixed conductor of claim 1 , wherein M is at least one of Co, Ni, Fe, Mn, V, Ti, Cr, Cu, Zn, Mo, Ru, Nb, Ta, Pd, Ag, Mg, Ca, Sr, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Zr, Hf, Nb, Ta, W, Tc, Re, Ru, Os, Rh, Ir, Pd, Pt, Au, Cd, Hg, Al, Ga, In, TI, Ge, Sn, Pb, Sb, Bi, Po, As, Se, or Te.

5. The mixed conductor of claim 1 , wherein in Formula 1
A is Li, and
M is at least one of Co, Ni, Fe, Mn, V, Ti, Cr, Cu, Zn, Mo, Ru, Nb, Ta, Pd, Ag, Mg, Ca, Sr, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Zr, Hf, Nb, Ta, W, Tc, Re, Ru, Os, Rh, Ir, Pd, Pt, Au, Cd, Hg, Al, Ga, In, TI, Ge, Sn, Pb, Sb, Bi, Po, As, Se, or Te.

6. The mixed conductor of claim 1 , wherein M is located in both a tetrahedral site and in an octahedral site of the inverse spinel crystal structure.

7. The mixed conductor of claim 6 , wherein the M in the tetrahedral site belongs to a high spin system including three or more unpaired electrons in a d-orbital.

8. The mixed conductor of claim 6 , wherein the M in the tetrahedral site is at least one of Fe, V, Co, Ni, Mn, Ti, Cr, Cu, Zn, Mo, Ru, Nb, Ta, Pd, or Ag.

9. The mixed conductor of claim 6 , wherein the M in the tetrahedral site and the M in the octahedral site have different oxidation numbers.

10. The mixed conductor of claim 6 , wherein the mixed conductor is at least one of:
Li 1±x Fe 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Ni 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Co 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Mn 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, L 1±x V 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Ti 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, L 1±x Cr 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Cu 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Zn 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Mo 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Ru 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Nb 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Ta 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Pd 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Ag 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Zr 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Hf 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Nb 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Ta 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x W 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Tc 2±y O 4−δ wherein 0≤x≤0.5 0≤y≤1, and 0≤δ≤0.5, Li 1±x Re 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Ru 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Os 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Rh 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Ir 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, L 1±x Pd 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Pt 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Au 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Cd 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Hg 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Al 2±4 O 4−δ wherein 0≤x≤x0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Ga 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x In 2+y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Tl 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Ge 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Sn 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Pb 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Sb 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Bi 2±y O 4−δ wherein0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x Po 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5, Li 1±x As 2±y O 4−δ wherein 0≤x≤0.5, 0≤y≤1, and 0≤δ≤0.5,
Li 1±x Fe 1±a Co 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x Fe 1±a Ni 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x Fe 1±a Mn 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x Fe 1±a V 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x Fe 1±a Ti 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x Fe 1±a Cr 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x Fe 1±a Cu 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x Fe 1±a Zn 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x Fe 1±a Mo 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x Fe 1±a Ru 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x Fe 1±a Nb 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x Fe 1±a Ta 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x Fe 1±a Pd 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x Fe 1±a Ag 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5,
Li 1±x V 1±a Fe 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x V 1±a Co 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x V 1±a Ni 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x V 1±a Mn 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x V 1±a Ti 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x V 1±a Cr 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x V 1±a Cu 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x V 1±a Zn 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x V 1±a Mo 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li a±x V 1±a Ru 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x V 1±a Nb 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x V 1±a Ta 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x V 1±a Pd 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x V 1±a Ag 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5,
Li 1±x Co 1±a Fe 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x Co 1±a Mn 1±b O 4−δ 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x Co 1±a V 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x Co 1±a Ti 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x Co 1±a Cr 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x C 1±a CU 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x Co 1±a Zn 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x Co 1±a Mo 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x Co 1±a Ru 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x Co 1±a Nb 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x Co 1±a Ta 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x Co 1±a Pd 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5, 0≤a+b≤1, and≤δ≤0.5, Li 1±x Co 1±a Ag 1±b O 4−δ wherein 0≤x≤0.5, 0≤a≤0.5, 0≤b≤0.5,

Assignees

• Samsung Electronics Co Ltd

Inventors

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

Classifications

• H01M12/08

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

• C01G49/009

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

• C01G53/42

  containing alkali metals, e.g. LiNiO2 · CPC title

• C01G49/0027 Primary

  containing one alkali metal · CPC title

• H01M10/0525

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