Metallic salt containing anion having heterocyclic aromatic structure, method of preparing the metallic salt, and electrolyte and electrochemical device each including the metallic salt

Patent metadata

Field	Value
Publication number	US-11643398-B2
Application number	US-201916571332-A
Country	US
Kind code	B2
Filing date	Sep 16, 2019
Priority date	Nov 15, 2018
Publication date	May 9, 2023
Grant date	May 9, 2023

Abstract

A metallic salt including at least one anion having a heterocyclic aromatic structure represented by one of Formulae 1 to 3; and a metallic cation:wherein, in Formulae 1 to 3, each X is independently N, P, or As, one of A1 and A2 is an electron-donating group, and the other one is an electron-withdrawing group, ring Ar1 and ring Ar2 are as defined herein, L is a linker group as defined herein, m is an integer from 1 to 5, and n is an integer from 0 to 5.

First claim

What is claimed is:

1. A metallic salt electrolyte for a battery, comprising:
at least one anion having a heterocyclic aromatic structure represented by one of Formulae 1 to 3; and
a metallic cation:

wherein, in Formulae 1 to 3,
each X is independently N, P, or As,
one of A 1 and A 2 is an electron-donating group, and the other one is an electron-withdrawing group,
ring Ar 1 and ring Ar 2 are each independently an aromatic group that is a substituted or unsubstituted C6 to C24 arylene group or a substituted or unsubstituted C4 to C24 heteroarylene group, wherein the aromatic group comprises a single aromatic ring, two or more aromatic rings which are fused together, or two or more aromatic rings which are connected covalently via a single bond, —O—, —S—, —C(═O)—, —S(═O) 2 —, —Si(R a )(R b )— wherein R a and R b are each independently a C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkylene group, or —C(═O)—NH—, and wherein Ar 1 and Ar 2 are each independently unsubstituted or substituted with at least one of an electron-donating group or an electron-withdrawing group,
L is a linker group, and is a single bond, —O—, —S—, —C(═O)—, —S(═O) 2 —, —Si(R a )(R b )— wherein R a and R b are each independently a C1 to C10 alkyl group, —C(═O)—NH—, a substituted or unsubstituted C1-C12 alkylene group, a substituted or unsubstituted C2-C12 alkenylene group, a substituted or unsubstituted C2-C12 alkynylene group, a substituted or unsubstituted C6-C12 arylene group, or a substituted or unsubstituted C4-C12 heteroarylene group, wherein the linker group is unsubstituted or substituted with at least one of an electron-donating group or an electron-withdrawing group, and wherein the linker group L is non-condensed or condensed with at least one of Ar 1 or Ar 2 ,
m is an integer from 1 to 5, and
n is an integer from 1 to 5.

2. The metallic salt electrolyte of claim 1 , wherein
the ring Ar 1 and the ring Ar 2 are each independently selected from the following formulae:

wherein
A 3 to A 15 are each independently a hydrogen atom, an electron-donating group, or an electron withdrawing group;
L′ and L″ are each independently a single bond, —O—, —S—, —C(═O)—, —S(═O) 2 —, —Si(R a )(R b )— wherein R a and R b are each independently a C1 to C10 alkyl group, —C(═O)—NH—, a C1-C12 alkylene group, a C2-C12 alkenylene group, a C2-C12 alkynylene group, a C6-C12 arylene group, or a C4-C12 heteroarylene group; and
* indicates a binding site to a neighboring atom; and
wherein, for Formula 3, at least one of A 3 to A 15 of ring An is linked to at least one of A 3 to A 15 of ring Ar 2 by the linker group L.

3. The metallic salt electrolyte of claim 1 , wherein
the heterocyclic aromatic structure of the anion is represented by one of Formulae 1a, 1b, 1c, 2a, 2b, and 3a:

wherein, in Formulae 1a to 3a,
one of A 1 and A 2 is an electron-donating group and the other one is an electron-withdrawing group;
A 3 to A 8 are each independently a hydrogen atom, an electron-donating group, or an electron-withdrawing group; and
Y is oxygen, sulfur, or nitrogen.

4. The metallic salt electrolyte of claim 1 , wherein
the electron-donating group is a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C2-C30 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C2-C30 alkoxyalkyl group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C7-C30 aryloxyalkyl group, a substituted or unsubstituted C7-C30 arylalkyl group, a substituted or unsubstituted C2-C30 heteroaryl group, a substituted or unsubstituted C2-C30 heteroaryloxy group, a substituted or unsubstituted C3-C30 heteroarylalkyl group, a substituted or unsubstituted C4-C30 carbocyclic group, a substituted or unsubstituted C5-C30 carbocyclicalkyl group, a substituted or unsubstituted C2-C30 heterocyclic group, a substituted or unsubstituted C3-C30 heterocyclicalkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted carbamoyl group, a hydroxy group, a nitro group, a cyano group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group or salt thereof, a thiol group, a phosphoric acid group or salt thereof, or a combination thereof.

5. The metallic salt electrolyte of claim 1 , wherein
the electron-donating group is —C n H 2n+1 , —OC n H 2n+1 , —NH 2 , —NH(C n H 2n+1 ), —N(C n H 2n+1 ) 2 , —OH, —NH(COC n H 2n+1 ), —N(COC n H 2n+1 ) 2 , —OCOC n H 2n+1 , —CH 2 (C n H 2n+1 ), —CH(C n H 2n+1 ) 2 , —C(C n H 2n+1 ) 3 , —SC n H 2n+1 , —N(CH 2 CH 2 ) 2 O, —P(O)(OH) 2 , —P(O)OH, a phenyl group, a vinyl group, or a combination thereof, and
wherein n is an integer from 1 to 10.

6. The metallic salt electrolyte of claim 1 , wherein
the electron-withdrawing group is a halogen atom, a cyano group, an isothiocyanate group, a thiocyanate group, a cyanato group, an isocyanato group, a fluorine-substituted C1-C30 alkyl group, a fluorine-substituted C2-C30 alkenyl group, a fluorine-substituted C2-C30 alkynyl group, a fluorine-substituted C6-C30 aryl group, a fluorine-substituted C1-C30 alkoxy group, a fluorine-substituted C2-C30 alkoxyalkyl group, a fluorine-substituted C6-C30 aryloxy group, a fluorine-substituted C7-C30 aryloxyalkyl group, a fluorine-substituted C7-C30 arylalkyl group, a fluorine-substituted C2-C30 heteroaryl group, a fluorine-substituted C2-C30 heteroaryloxy group, a fluorine-substituted C3-C30 heteroarylalkyl group, a fluorine-substituted C4-C30 carbocyclic group, a fluorine-substituted C5-C30 carbocyclicalkyl group, a fluorine-substituted C2-C30 heterocyclic group, a fluorine-substituted C3-C30 heterocyclicalkyl group, a fluorine-substituted thio group, a sulfonyl group, a sulfamoyl group, a sulfonic acid group or salt thereof, or a combination thereof.

7. The metallic salt electrolyte of claim 1 , wherein
the electron-withdrawing group is —F, —Cl, —Br, —CONH 2 , —COOC n H 2n+1 , —COCl, —COOH, —COC n H 2n+1 , —CHO, —NO 2 , —SO 3 H, —C≡N, —S—C≡N, N═C═S, —N═C═O, —C n F 2n+1 , —OC n F 2n+1 , —CH 2 C n F 2n+1 , —OC n F 2n H, —SC n F 2n+1 , —SC n F 2n H, —OCF═CF 2 , —SCF═CF 2 , —SO 2 F, and —SO 2 C n F 2n+1 , or a combination thereof, and
wherein n is an integer from 1 to 10.

8. The metallic salt electrolyte of claim 1 , wherein
at least one hydrogen atom present in Formulae 1 to 3 is substituted with a halogen atom, a C1-C30 alkyl group, a C2-C30 alkenyl group, a C2-C30 alkynyl group, a C1-C30 alkoxy group, a C2-C30 alkoxyalkyl group, a C1-C30 heteroalkyl group, a C6-C30 aryl group, a C7-C30 arylalkyl group, a C2-C30 heteroaryl group, a C3-C30 heteroarylalkyl group, a C2-C30 heteroaryloxy group, a C3-C30 heteroaryloxyalkyl group, a C6-C30 heteroarylalkoxy group, a hydroxy group, a nitro group, a cyano group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group or a salt thereof, a sulfonyl group, a sulfamoyl group, a sulfonic acid group or salt thereof, a phosphoric acid group or salt thereof, or a combination thereof.

9. The metallic salt electrolyte of claim 1 , wherein
the metallic cation is an alkali metal cation, an alkaline earth metal

Assignees

• Samsung Electronics Co Ltd
• Samsung Sdi Co Ltd

Inventors

• Lee Myungjin
• Roev Victor
• Choi Hongsoo
• Im Dongmin
• Kwak Yoonhyun
• Ma Sangbok
• Park Minsik
• Park Sungjun

Classifications

• H01M10/0568 Primary

  characterised by the solutes · CPC title

• H01M10/0569

  characterised by the solvents · CPC title

• H01M6/164

  by the solvent · CPC title

• C07D493/04

  Ortho-condensed systems · CPC title

• C07D249/18

  Benzotriazoles · CPC title