# US 10,122,001 B2 · Polymerized ionic liquid block copolymers as battery membranes

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- Number: US 10,122,001 B2
- Document ID: US10122001B2
- Status: Granted
- Kind: B2
- Application number: 15/795,757
- Filed: 2017-10-27
- Published: 2018-03-01
- Granted: 2018-11-06
- Earliest claimed: 2012-09-12
- Assignees: Drexel University; The Trustees of the University of Pennsylvania
- Applicants: Drexel University; The Trustees of the University of Pennsylvania
- Inventors: Yossef A. Elabd; Karen I. Winey; Yuesheng Ye; Jae-Hong Choi; Tsen-Shan Sharon Sharick
- Web page: https://patentgrep.com/patent/US10122001B2

## CPC

- B01J 41/00: Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties (ion-exchange chromatography processes B01D15/36)
- B01J 41/14: obtained by reactions only involving unsaturated carbon-to-carbon bonds
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- C08F 293/005: {using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent}
- C08J 5/2231: {based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds}
- H01M 8/1018: Polymeric electrolyte materials
- H01M 8/1027: having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
- H01M 8/103: having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
- H01M 8/1032: having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
- H01M 8/1067: characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
- H01M 10/052: Li-accumulators
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 10/0565: Polymeric materials, e.g. gel-type or solid-type
- H01M 50/414: Synthetic resins, e.g. thermoplastics or thermosetting resins
- C08F 220/14: Methyl esters {, e.g. methyl (meth)acrylate}
- C08F 220/22: Esters containing halogen
- C08F 220/34: Esters containing nitrogen {, e.g. N,N-dimethylaminoethyl (meth)acrylate}
- C08F 2438/02: Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO]
- C08J 2353/00: Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- H01M 2008/1095: {Fuel cells with polymeric electrolytes}
- H01M 2300/0082: Organic polymers
- Y02E 60/10: Energy storage using batteries
- Y02E 60/50: Fuel cells
- Y10S 977/70: Nanostructure
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

## Abstract

The present invention is directed to lithium ion transport media for use in separators in lithium ion batteries, and the membranes, separators, and devices derived therefrom.

## Claims

### Claim 1

A lithium ion transport medium comprising a block copolymer comprising a first and second block, wherein
(a) the first block comprises a polymerized styrene or vinylpyridine derivative; and
(b) the second block comprises:
(i) a polymerized ionic liquid comprising a tethered ionic liquid cation and a mobile anion; and
(ii) a lithium ion salt of said mobile anion;
wherein the cation of the polymerized ionic liquid is tethered to the polymer backbone by a carboalkoxy, carboxylato, carboxyamino, or ether linkage; and wherein said block copolymer exhibits at least one region of nanophase separation.

### Claim 2 (depends on 1)

The lithium ion transport medium of claim 1 consisting essentially of a block copolymer comprising a first and second block, wherein
(a) the first block comprises a polymerized styrene or vinylpyridine derivative; and
(b) the second block comprises:
(i) a polymerized ionic liquid comprising a tethered ionic liquid cation and a mobile anion; and
(ii) a lithium ion salt of said mobile anion;
wherein the cation of the polymerized ionic liquid is tethered to the polymer backbone by a carboalkoxy, carboxylato, carboxyamino, or ether linkage and wherein said block copolymer exhibits at least one region of nanophase separation.

### Claim 3 (depends on 1)

The lithium ion transport medium of claim 1, wherein at least one region of nanophase separation comprises at least one region of a periodic nanostructured lamellar morphology with connected ion-conducting domains:
(a) which optionally extend in three-dimensions throughout the block copolymer;
(b) whose periodicity is optionally characterized by ordered domains having lattice parameter dimensions in the range of about 5 to about 50 nm, as measured by small angle X-ray scattering; or
(c) which are a combination of (a) and (b).

### Claim 4 (depends on 1)

The lithium ion transport medium of claim 1, wherein the first block comprises a polymerized styrene derivative.

### Claim 5 (depends on 1)

The lithium ion transport medium of claim 1, wherein the styrene derivative is styrene, α-methylstyrene, methylstyrene, chlorostyrene, hydroxystyrene, or vinylbenzyl chloride.

### Claim 6 (depends on 1)

The lithium ion transport medium of claim 1, wherein the styrene derivative is styrene.

### Claim 7 (depends on 1)

The lithium ion transport medium of claim 1, wherein the first block comprises a polymerized vinylpyridine derivative.

### Claim 8 (depends on 1)

The lithium ion transport medium of claim 1, wherein the first block has an average molecular weight in the range of from about 1000 to about 50000 Daltons.

### Claim 9 (depends on 1)

The lithium ion transport medium of claim 1, wherein the tethered ionic liquid cation comprises at least one optionally alkyl-substituted imidazolium, pyridinium, or pyrrolidinium cation, or combination thereof.

### Claim 10 (depends on 1)

The lithium ion transport medium of claim 1, wherein the polymerized ionic liquid comprises a C3-6 alkyl-substituted imidazolium cation.

### Claim 11 (depends on 1)

The lithium ion transport medium of claim 1, wherein the cation of the polymerized is tethered by a carboalkoxy, carboxyamino, or ether linking group.

### Claim 12 (depends on 1)

The lithium ion transport medium of claim 1, wherein the second block comprising a polymerized ionic liquid comprises a repeating unit:
where R5A, R6A, R7A, and R8A are independently H or C1-6 alkyl; and n is in a range of from 0 to 20.

### Claim 13 (depends on 12)

The lithium ion transport medium of claim 12, wherein n is about 10.

### Claim 14 (depends on 1)

The lithium ion transport medium of claim 1, wherein the block copolymer is substantially anhydrous.

### Claim 15 (depends on 1)

The lithium ion transport medium of claim 1, wherein the second block further comprises a solvent comprising ethylene carbonate, ethylene glycol, polyethylene glycol, propylene glycol, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, dipropyl carbonate, γ-butyrolactone, dimethoxyethane, diethoxyethane, or a mixture thereof.

### Claim 16 (depends on 1)

The lithium ion transport medium of claim 1, wherein the mobile anion is an alkyl phosphate, biscarbonate, bistriflimide, N(SO2C2F5)2−, N(SO2CF3)(SO2C4F9)−, carbonate, chlorate, formate, glycolate, perchlorate, hexasubstituted phosphate; tetra-substituted borate, tosylate, or triflate or combination thereof.

### Claim 17 (depends on 1)

The lithium ion transport medium of claim 1, further comprising a mobile ionic liquid comprising at least one optionally substituted imidazolium, pyridinium, pyrrolidinium cation and at least one alkyl phosphate, biscarbonate, bistriflimide, N(SO2C2F5)2−, N(SO2CF3)(SO2C4F9)−, carbonate, chlorate, formate, glycolate, perchlorate, hexasubstituted phosphate; tetra-substituted borate), tosylate, or triflate anion.

### Claim 18 (depends on 1)

The lithium ion transport medium of claim 1, wherein the polymerized ionic liquid block has a number average molecular weight in the range of from about 1000 to about 50000 Daltons.

### Claim 19 (depends on 1)

The lithium ion transport medium of claim 1, wherein the block copolymer has a number average molecular weight in a range of from about 5000 to about 25,000 Daltons, as measured by size exclusion chromatography.

### Claim 20 (depends on 1)

The lithium ion transport medium of claim 1, wherein the block copolymer has a number average molecular weight having a polydispersity in the range of about 1 to about 1.5, as measured by size exclusion chromatography.

### Claim 21 (depends on 1)

The lithium ion transport medium of claim 1, wherein the polymerized ionic liquid block is present in a range of from about 5 mole % to about 95 mole % of the total block copolymer.

### Claim 22 (depends on 1)

A lithium ion battery membrane comprising a lithium ion transport medium of claim 1.

### Claim 23 (depends on 22)

A membrane electrode assembly comprising a lithium ion battery membrane of claim 22.

### Claim 24 (depends on 22)

A lithium ion battery comprising a lithium ion battery membrane of claim 22.