Solid ion conductor, solid electrolyte and electrochemical cell comprising the same, and method of preparing the solid ion conductor

Patent metadata

Field	Value
Publication number	US-11894513-B2
Application number	US-202117370032-A
Country	US
Kind code	B2
Filing date	Jul 8, 2021
Priority date	Nov 16, 2020
Publication date	Feb 6, 2024
Grant date	Feb 6, 2024

Abstract

A solid ion conductor, a solid electrolyte and electrochemical device including the same, and a method of preparing the solid ion conductor are disclosed. The solid ion conductor includes a compound represented by Formula 1:

Li a M b M′ c X d O e   Formula 1
wherein, in Formula 1, M is one or more metals selected from Lu, Ho, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Ga, In, Ce, Pr, Ti, Zr, or Hf, each having an oxidation number of +3 or +4, M′ is one or more metals selected from Na, K, Cs, Cu, or Ag, each having an oxidation number of +1, X is one or more halogens, 0<a<4, 0.5<b<1.5, 0≤c<1.5, 0<d<6.5, and 0<e<1.

First claim

What is claimed is:

1. A solid ion conductor comprising a compound represented by Formula 1:
Li a M b M′ c X d O e   Formula 1

wherein, in Formula 1,
M is one or more metals selected from Lu, Ho, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Ga, In, Ce, Pr, Ti, Zr, or Hf, each having an oxidation number of +3 or +4,
M′ is one or more metals selected from Na, K, Cs, Cu, or Ag, each having an oxidation number of +1,
X is one or more halogens,
0<a<4, 0.5<b<1.5, 0<c<1.5, 0<d<6.5, and 0<e<1,
when M is Zr, 0<c<1.5; and
when M is one or more metals selected from Lu, Ho, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Ga, In, Ce, Pr, Ti, or Hf, or when M is Zr in combination with one or more metal selected from Lu, Ho, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Ga, In, Ce, Pr, Ti, or Hf, 0≤c≤1.5.

2. The solid ion conductor of claim 1 , wherein the compound is a compound represented by Formula 2:
Li a M b M' c Cl 1 Br d2 F d3 I d4 O e
wherein, in Formula 2 ,
M is one or more metals selected from Lu, Ho, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Ga, In, Ce, Pr, Ti, Zr, or Hf, each having an oxidation number of +3 or +4,
M′ is one or more metals selected from Na, K, Cs, Cu, or Ag, each having an oxidation number of +1,
0<a<4, 0.5<b<1.5, 0<d1<6.5, 0<d2<6.5, 0<d3<6.5, 0<d4<6.5, and 0<e<1,
when M is Zr, 0<c<1.5; and
when M is one or more metals selected from Lu, Ho, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Ga, In, Ce, Pr, Ti, or Hf, or when M is Zr in combination with one or more metal selected from Lu, Ho, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Ga, In, Ce, Pr, Ti, or Hf, 0<c<1.5.

3. The solid ion conductor of claim 1 , wherein the compound is a compound represented by Formula 3:
Li a M b M' c X d O e ,
wherein, in Formula 3,
M is one or more metals selected from Lu, Ho, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Ga, In, Ce, Pr, Ti, Zr, or Hf, each having an oxidation number of +3 or +4,
M′ is one or more metals selected from Na, K, Cs, Cu, or Ag, each having an oxidation number of +1,
X is one or more selected from Cl or Br,
0<a<4, 0.5<b<1.5, 0<d1<6.5, 0<e<1, and 0<e/b <0.5,
when M is Zr, 0<c<1.5; and
when M is one or more metals selected from Lu, Ho, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Ga, In, Ce, Pr, Ti, or Hf, or when M is Zr in combination with one or more metal selected from Lu, Ho, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Ga, In, Ce, Pr, Ti, or Hf, 0≤c<1.5.

4. The solid ion conductor of claim 1 , wherein the compound is a compound represented by Formula 4:
Li a M b M' c X d O e ,
wherein, in Formula 4,
M is one or more metals selected from Lu, Ho, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Ga, In, Ce, Pr, Ti, Zr, or Hf, each having an oxidation number of +3 or +4,
M′ is one or more metals selected from Na, K, Cs, Cu, or Ag, each having an oxidation number of +1,
X is one or more selected from Cl or Br,
0<a<4, 0.5<b<1.5, 0<d1<6.5, 0<e<1, and 2<a/b <6,
when M is Zr, 0<c<1.5, and
when M is one or more metals selected from Lu, Ho, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Ga, In, Ce, Pr, Ti, or Hf, or when M is Zr in combination with one or more metal selected from Lu, Ho, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Ga, In, Ce, Pr, Ti, or Hf, 0≤c<1.5.

5. A solid ion conductor comprising a compound represented by Formula 5 or 6:
Li p M q X r-w O w   Formula 5

wherein, in Formula 5,
M is one or more metals selected from Lu, Ho, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Ga, In, Ce, Pr, Ti, Zr, or Hf, each having an oxidation number of +3,
X is one or more selected from Cl or Br,
0<p<4, 0.5<q<1.5, 0<r<6.5, 0<w<1, and 0<w/q<0.5;
Li p M q M′ z X r-w O w   Formula 6

wherein, in Formula 6,
M is one or more metals selected from Lu, Ho, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Ga, In, Ce, Pr, Ti, Zr, or Hf, each having an oxidation number of +3,
M′ is one or more metals selected from Na, K, Cs, Cu, or Ag, each having an oxidation number of +1,
X is one or more selected from Cl or Br,
0<p<4, 0.5<q<1.5, 0<z<1.5, 0<r<6.5, 0<w<1, and 2<p/q<6, 0<w/q<0.5.

6. The solid ion conductor of claim 1 , wherein the compound comprises one or more selected from:
Li 3.6 Lu 0.9 Cl 5.7 O 0.3 , Li 3.6 Lu 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.6 Ho 0.9 Cl 5.7 O 0.3 , Li 3.6 Ho 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.6 Nd 0.9 Cl 5.7 O 0.3 , Li 3.6 Nd 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.6 Sm 0.9 Cl 5.7 O 0.3 , Li 3.6 Sm 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.6 Eu 0.9 Cl 5.7 O 0.3 , Li 3.6 Eu 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.6 Gd 0.9 Cl 5.7 O 0.3 , Li 3.6 Gd 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.6 Tb 0.9 Cl 5.7 O 0.3 , Li 3.6 Tb 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.6 Dy 0.9 Cl 5.7 O 0.3 , Li 3.6 Dy 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.6 TM 0.9 Cl 5.7 O 0.3 , Li 3.6 TM 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.6 Yb 0.9 Cl 5.7 O 0.3 , Li 3.6 Yb 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.6 Ga 0.9 Cl 5.7 O 0.3 , Li 3.6 Ga 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.6 In 0.9 Cl 5.7 O 0.3 , Li 3.6 In 0.9 Cl 1.7 Br 4 O 0.3 ;
Li 3.57 Na 0.03 Lu 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Na 0.03 Ho 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Na 0.03 Nd 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Na 0.03 Sm 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Na 0.03 Eu 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Na 0.03 Gd 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Na 0.03 Tb 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Na 0.03 Dy 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Na 0.03 TM 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Na 0.03 Yb 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Na 0.03 Ga 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Na 0.03 In 0.9 Cl 1.7 Br 4 O 0.3 ;
Li 3.57 K 0.03 Lu 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 K 0.03 Ho 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 K 0.03 Nd 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 K 0.03 Sm 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 K 0.03 Eu 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 K 0.03 Gd 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 K 0.03 Tb 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 K 0.03 Dy 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 K 0.03 In 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 K 0.03 Yb 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 K 0.03 Ga 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 K 0.03 In 0.9 Cl 1.7 Br 4 O 0.3 ;
Li 3.57 Cs 0.03 Lu 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Cs 0.03 Ho 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Cs 0.03 Nd 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Cs 0.03 Sm 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Cs 0.03 Eu 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Cs 0.03 Gd 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Cs 0.03 Tb 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Cs 0.03 Dy 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Cs 0.03 Tm 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Cs 0.03 Yb 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Cs 0.03 Ga 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Cs 0.03 In 0.9 Cl 1.7 Br 4 O 0.3 ;
Li 3.57 Cu 0.03 Lu 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Cu 0.03 Ho 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Cu 0.03 Nd 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Cu 0.03 Sm 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Cu 0.03 Eu 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Cu 0.03 Gd 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Cu 0.03 Tb 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Cu 0.03 Dy 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Cu 0.03 Tm 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Cu 0.03 Yb 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Cu 0.03 Ga 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Cu 0.03 In 0.9 Cl 1.7 Br 4 O 0.3 ;
Li 3.57 Ag 0.03 Lu 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Ag 0.03 Ho 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Ag 0.03 Nd 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Ag 0.03 Sm 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Ag 0.03 Eu 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Ag 0.03 Gd 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Ag 0.03 Tb 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Ag 0.03 Dy 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Ag 0.03 Tm 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Ag 0.03 Yb 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Ag 0.03 Ga 0.9 Cl 1.7 Br 4 O 0.3 , Li 3.57 Ag 0.03 In 0.9 Cl 1.7 Br 4 O 0.3 ; or
Li 3.2 LuCl 6 O 0.1 , Li 3.2 HoCl 6 O 0.1 , Li 3.2 NdCl 6 O 0.1 , Li 3.2 SmCl 6 O 0.1 , Li 3.2 EuCl 6 O 0.1 , Li 3.2 GdCl 6 O 0.1 , Li 3.2 TbCl 6 O 0.1 , Li 3.2 DyCl 6 O 0.1 , Li 3.2 ErCl 6 O 0.1 , Li 3.2 TmCl 6 O 0.1 , Li 3.2 YbCl 6 O 0.1 , Li 3.2 GaCl 6 O 0.1 , Li 3.2 InCl 6 O 0.1 , Li 3.2 CeCl 6 O 0.1 , or Li 3.2 PrCl 6 O 0.1 .

7. The solid ion conductor of claim 1 , wherein the compoun

Assignees

• Samsung Electronics Co Ltd

Inventors

• Choi Wonsung
• Kim Jusik
• Yoon Gabin

Classifications

• H01M10/0562 Primary

  Solid materials · CPC title

• H01M4/62

  Selection of inactive substances as ingredients for active masses, e.g. binders, fillers · CPC title

• H01M10/052

  Li-accumulators · CPC title

• H01M10/0585

  of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators · CPC title

• H01M12/08 Primary

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