Composite electrolyte including polymeric ionic liquid and inorganic particles and lithium battery including the same

Patent metadata

Field	Value
Publication number	US-10205190-B2
Application number	US-201514834940-A
Country	US
Kind code	B2
Filing date	Aug 25, 2015
Priority date	Aug 28, 2014
Publication date	Feb 12, 2019
Grant date	Feb 12, 2019

Abstract

A composite electrolyte including a polymeric ionic liquid; a plurality of inorganic particles; and an organic electrolyte.

First claim

What is claimed is:

1. A composite electrolyte comprising:
a polymeric ionic liquid;
a plurality of inorganic particles; and
an organic electrolyte,
wherein the polymeric ionic liquid is represented by Formula 1a or Formula 1b:

wherein in Formulae 1a and 1b,

are each independently a 3 to 31 membered group comprising 2 to 30 carbon atoms and optionally at least one heteroatom in addition to X;
X is S, —N(R 5 )(R 6 ), —N(R 5 ), —P(R 6 ), or —P(R 5 )(R 6 );
R 1 to R 6 are each independently a hydrogen, an unsubstituted or substituted C1-C30 alkyl group, an unsubstituted or substituted C1-C30 heteroalkyl group, an unsubstituted or substituted C1-C30 alkoxy group, an unsubstituted or substituted C6-C30 aryl group, an unsubstituted or substituted C7-C30 arylalkyl group, an unsubstituted or substituted C6-C30 aryloxy group, an unsubstituted or substituted C6-C30 arylthio group, an unsubstituted or substituted C3-C30 heteroaryl group, an unsubstituted or substituted C4-C30 heteroarylalkyl group, an unsubstituted or substituted C3-C30 heteroaryloxy group, an unsubstituted or substituted C3-C30 heteroarylthio group, an unsubstituted or substituted C3-C30 cycloalkyl group, an unsubstituted or substituted C3-C30 cycloalkyloxy group, an unsubstituted or substituted C3-C30 heterocycloalkyl group, or an unsubstituted or substituted C2-C100 alkyleneoxide group,
wherein “substituted” refers to one substituted with a halogen atom, a C1-C20 alkyl group substituted with one or more halogen atoms, a C1-C20 alkoxy group, a C2-C20 alkoxyalkyl group, a hydroxyl group, a nitro group, a cyano group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonyl group, a sulfamoyl group, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C1-C20 heteroalkyl group, a C6-C20 aryl group, a C6-C20 arylalkyl group, a C6-C20 heteroaryl group, a C7-C20 heteroarylalkyl group, a C6-C20 heteroaryloxy group, a C6-C20 heteroaryloxyalkyl group, or a C6-C20 heteroarylalkyl group;
Y − in Formula 1a is at least one selected from BF 4 − , PF 6 − , AsF 6 − , SbF 6 − , AlCl 4 − , HSO 4 − , ClO 4 − , CH 3 SO 3 − , Cl − , Br − , I − , BF 4 − , SO 4 − , PF 6 − , ClO 4 − , CF 3 SO 3 − , CF 3 CO 2 − , (C 2 F 5 SO 2 ) 2 N − , (C 2 F 5 SO 2 )(CF 3 SO 2 )N − , and (CF 3 SO 2 ) 2 N − , and Y − in Formula 1b is an anion;
a and b are each independently an integer of 1 to 5; and
n is an integer of 500 to 2,800,
wherein a current density of the composite electrolyte due to oxidation reaction at a voltage of around 5.0 V with respect to lithium is 0.05 mA/cm 2 or less.

2. The composite electrolyte of claim 1 , wherein the inorganic particles comprise at least one selected from a metal oxide, a metal hydroxide, a metal carbonate, a metal carboxylate, a metal silicate, a metal aluminosilicate, a metal carbide, a metal nitride, a metal halide, a metal nitrate, a carbon oxide, a carbonaceous material, and an organic-inorganic composite.

3. The composite electrolyte of claim 1 , wherein the inorganic particles comprise at least one selected from Al 2 O 3 , SiO 2 , BaTiO 3 , graphite oxide, graphene oxide, metal organic framework, polyhedral oligomeric silsesquioxane, Li 2 CO 3 , Li 3 PO 4 , Li 3 N, Li 3 S 4 , Li 2 O, and montmorillonite.

4. The composite electrolyte of claim 1 , wherein a particle diameter of the inorganic particles is less than 100 nanometers.

5. The composite electrolyte of claim 1 , wherein an amount of the inorganic particles is in a range of about 1 percent by weight to about 95 percent by weight based on the total weight of the inorganic particles and the polymeric ionic liquid.

6. The composite electrolyte of claim 1 , wherein an amount of the inorganic particles is in a range of about 30 percent by weight to about 90 percent by weight based on the total weight of the inorganic particles and the polymeric ionic liquid.

7. The composite electrolyte of claim 1 , wherein the polymeric ionic liquid is at least one selected from a cationic polymeric ionic liquid, an anionic polymeric ionic liquid, and a zwitterionic polymeric ionic liquid.

8. The composite electrolyte of claim 1 , wherein

in Formula 1a is represented by Formula 2:

wherein in Formula 2,
Z denotes N, S, or P; and
R 5 and R 6 are each independently a hydrogen, an unsubstituted or substituted C1-C30 alkyl group, an unsubstituted or substituted C1-C30 heteroalkyl group, an unsubstituted or substituted C1-C30 alkoxy group, an unsubstituted or substituted C6-C30 aryl group, an unsubstituted or substituted C7-C30 arylalkyl group, an unsubstituted or substituted C6-C30 aryloxy group, an unsubstituted or substituted C6-C30 arylthio group, an unsubstituted or substituted C3-C30 heteroaryl group, an unsubstituted or substituted C4-C30 heteroarylalkyl group, an unsubstituted or substituted C3-C30 heteroaryloxy group, an unsubstituted or substituted C3-C30 heteroarylthio group, an unsubstituted or substituted C3-C30 cycloalkyl group, an unsubstituted or substituted C3-C30 cycloalkyloxy group, an unsubstituted or substituted C3-C30 heterocycloalkyl group, an unsubstituted or substituted C3-C30 alkenyl group, an unsubstituted or substituted C3-C30 alkynyl group, or an unsubstituted or substituted C2-C100 alkyleneoxide group,
wherein “substituted” refers to one substituted with a halogen atom, a C1-C20 alkyl group substituted with one or more halogen atoms, a C1-C20 alkoxy group, a C2-C20 alkoxyalkyl group, a hydroxyl group, a nitro group, a cyano group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonyl group, a sulfamoyl group, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C1-C20 heteroalkyl group, a C6-C20 aryl group, a C6-C20 arylalkyl group, a C6-C20 heteroaryl group, a C7-C20 heteroarylalkyl group, a C6-C20 heteroaryloxy group, a C6-C20 heteroaryloxyalkyl group, or a C6-C20 heteroarylalkyl group,
provided that when Z denotes S, R 5 and R 6 are absent.

9. The composite electrolyte of claim 1 , wherein the polymeric ionic liquid represented by Formula 1a is a polymeric ionic liquid represented by Formula 3:

wherein in Formula 3,
R 1 to R 8 are each independently a hydrogen, an unsubstituted or substituted C1-C30 alkyl group, an unsubstituted or substituted C1-C30 heteroalkyl group, an unsubstituted or substituted C1-C30 alkoxy group, an unsubstituted or substituted C6-C30 aryl group, an unsubstituted or substituted C7-C30 arylalkyl group, an unsubstituted or substituted C6-C30 aryloxy group, an unsubstituted or substituted C6-C30 arylthio group, an unsubstituted or substituted C3-C30 heteroaryl group, an unsubstituted or substituted C4-C30 heteroarylalkyl group, an unsubstituted or substituted C3-C30 heteroaryloxy group, an unsubstituted or substituted C3-C30 heteroarylthio group, an unsubstituted or substituted C3-C30 cycloalkyl group, an unsubstituted or s

Assignees

• Samsung Electronics Co Ltd

Inventors

• Lee Jenam
• Kim Soyeon
• Lee Seoksoo
• Kim Jusik
• Park Joungwon
• Lee Myungjin
• Lee Yonggun
• Choi Hongsoo

Classifications

• H01M10/0569

  characterised by the solvents · CPC title

• H01M2300/0082

  Organic polymers · CPC title

• H01M2300/0028

  characterised by the solvent · CPC title

• H01M2300/0085

  Immobilising or gelification of electrolyte · CPC title

• H01M10/052

  Li-accumulators · CPC title