# US 10,121,608 B2 · Printable ionic gel separation layer for energy storage devices

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- Number: US 10,121,608 B2
- Document ID: US10121608B2
- Status: Granted
- Kind: B2
- Application number: 14/829,243
- Filed: 2015-08-18
- Published: 2015-12-10
- Granted: 2018-11-06
- Earliest claimed: 2012-07-16
- Assignees: Printed Energy Pty Ltd
- Applicants: NthDegree Technologies Worldwide Inc.
- Inventors: Vera Nicholaevna Lockett; Mark David Lowenthal; Neil O. Shotton; William Johnstone Ray; Theodore I. Kamins
- Web page: https://patentgrep.com/patent/US10121608B2

## CPC

- H01G 11/52: Separators
- H01G 11/60: characterised by the solvent
- H01G 11/62: characterised by the solute, e.g. salts, anions or cations therein
- H01G 11/84: Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 10/056: characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M 10/0565: Polymeric materials, e.g. gel-type or solid-type
- H01M 10/0568: characterised by the solutes
- H01M 10/0569: characterised by the solvents
- H01M 50/403: Manufacturing processes of separators, membranes or diaphragms
- H01M 50/409: Separators, membranes or diaphragms characterised by the material
- H01M 50/411: Organic material
- H01M 50/414: Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M 50/426: Fluorocarbon polymers
- H01M 50/431: Inorganic material
- H01M 50/437: Glass
- H01M 50/443: Particulate material
- H01M 50/446: Composite material consisting of a mixture of organic and inorganic materials
- H01M 50/449: having a layered structure
- H01M 50/491: Porosity
- H01M 2300/0025: Organic electrolyte
- H01M 2300/0028: characterised by the solvent
- H01M 2300/0085: Immobilising or gelification of electrolyte
- Y02E 60/10: Energy storage using batteries
- Y02E 60/13: Energy storage using capacitors
- H01G: CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE (selection of specified materials as dielectric H01B3/00; capacitors having potential barriers H10D1/62, H10K10/10)
- 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

## Abstract

Representative embodiments provide a liquid or gel separator utilized to separate and space apart first and second conductors or electrodes of an energy storage device, such as a battery or a supercapacitor. A representative liquid or gel separator comprises a plurality of particles, typically having a size (in any dimension) between about 0.5 to about 50 microns; a first, ionic liquid electrolyte; and a polymer. In another representative embodiment, the plurality of particles comprise diatoms, diatomaceous frustules, and/or diatomaceous fragments or remains. Another representative embodiment further comprises a second electrolyte different from the first electrolyte; the plurality of particles are comprised of silicate glass; the first and second electrolytes comprise zinc tetrafluoroborate salt in 1-ethyl-3-methylimidalzolium tetrafluoroborate ionic liquid; and the polymer comprises polyvinyl alcohol (“PVA”) or polyvinylidene fluoride (“PVFD”). Additional components, such as additional electrolytes and solvents, may also be included.

## Claims

### Claim 1

A liquid or gel separator for separating and spacing apart at least two conductors, the liquid or gel separator comprising:
a plurality of particles arranged as one or more layers, the plurality of particles comprising silicate glass having a size between 5 microns to 15 microns and present in an amount between 40 to 75 percent of the total weight of the separator;
an ionic liquid as a first electrolyte, the ionic liquid comprising 1-ethyl-3-methylimidazolium;
a second electrolyte comprising zinc tetrafluoroborate salt, the first and second electrolytes present in an amount between 15 to 45 percent of the total weight of the separator; and
a polymer present in an amount between 0.5 to 15 percent of the total weight of the separator and comprising polyvinyl alcohol (“PVA”) or polyvinylidene fluoride (“PVFD”).

### Claim 2 (depends on 1)

The liquid or gel separator of claim 1, wherein at least some particles of the plurality of silicate glass particles are hollow.

### Claim 3 (depends on 1)

The liquid or gel separator of claim 1, further comprising at least a trace amount of N-methyl-2-pyrrolidinone.

### Claim 4 (depends on 1)

The liquid or gel separator of claim 1, wherein at least some particles of the plurality of silicate glass particles are arranged as a monolayer.

### Claim 5 (depends on 1)

The separator of claim 1, wherein the first electrolyte further comprises one or more ionic liquid cations selected from the group consisting of: butyltrimethylammonium, 1-butyl-3-methylimidazolium, 1-methyl-3-propylimidazolium, 1-hexyl-3-methylimidazolium, choline, ethylammonium, tributylmethylphosphonium, tributyl(tetradecyl)phosphonium, trihexyl(tetradecyl)phosphonium, 1-ethyl-2,3-methylimidazolium, 1-butyl-1-methylpiperidinium, diethylmethylsulfonium, 1-methyl-3-propylimidazolium, 1-methyl-1-propylpiperidinium, 1-butyl-2-methylpyridinium, 1-butyl-4-methylpyridinium, 1-butyl-1-methylpyrrolidinium, and mixtures thereof.

### Claim 6 (depends on 1)

The separator of claim 1, wherein the first electrolyte further comprises one or more ionic liquid anions selected from the group consisting of: tris(pentafluoroethyl)trifluorophosphate, trifluoromethanesulfonate, hexafluorophosphate, tetrafluoroborate, ethyl sulfate, methyl sulfate, dimethyl phosphate, trifluoromethanesulfonate, methanesulfonate, triflate, tricyanomethanide, dibutylphosphate, bis(trifluoromethylsulfonyl)imide, bis-2,4,4-(trimethylpentyl) phosphinate, iodide, chloride, bromide, nitrate, thiocyanate, and mixtures thereof.

### Claim 7 (depends on 1)

The separator of claim 1, further comprising a third electrolyte different from the first and second electrolytes, the third electrolyte comprising one or more electrolytes selected from the group consisting of: potassium hydroxide, sodium hydroxide, ammonium hydroxide, lithium hydroxide, nickel hydroxide, cadmium hydroxide, magnesium hydroxide, sulfuric acid, hydrochloric acid, fluoroboric acid, ammonium chloride, zinc chloride, zinc bis(trifluoromethanesulfonyl)imide, aluminium chloride, chromium chloride, magnesium perchloride, barium chromate, lithium chromate, lithium-thyonyl chloride, lithium perchlorate, lithium bromide, lithium triflate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis-oxalato borate, lithium bis(trifluoromethanesulfonyl)imide, lithium bisoxalatoborate, lithium iodide, lithium tetrachloroaluminate, potassium carbonate, potassium fluoride, potassium borate, silver nitride, silver tetrafluoroborate; salts of bis(trifluoromethylsulfonyl)imide, tris(pentafluoroethyl)trifluorophosphate, trifluoromethanesulfonate, hexafluorophosphate, tetrafluoroborate, ethyl sulfate, dimethyl phosphate, trifluoromethanesulfonate, triflate, tricyanomethanide, dibutylphosphate; and mixtures thereof.

### Claim 8

A method of fabricating a liquid or gel separator for separating and spacing apart at least two conductors, the method comprising:
depositing a composition over a first conductor of the at least two conductors, the composition comprising:
a plurality of particles comprising silicate glass having a size between 5 microns to 15 microns and present in an amount between 40 to 60 percent of the total weight of the composition;
an ionic liquid as a first electrolyte, the ionic liquid comprising 1-ethyl-3-methylimidazolium;
a second electrolyte comprising zinc tetrafluoroborate salt, the first and second electrolytes present in an amount between 15 to 30 percent of the total weight of the composition;
a polymer present in an amount between 0.5 to 10 percent of the total weight of the composition and comprising polyvinyl alcohol (“PVA”) or polyvinylidene fluoride (“PVFD”); and
N-methyl-2-pyrrolidinone present in an amount between 10 to 30 percent of the total weight of the composition.

### Claim 9 (depends on 8)

The method of claim 8, wherein the step of depositing comprises printing the composition.

### Claim 10 (depends on 8)

The method of claim 8, wherein at least some particles of the plurality of silicate glass particles of the composition are hollow.

### Claim 11 (depends on 8)

The method of claim 8, wherein the step of depositing further comprises arranging at least some particles of the plurality of silicate glass particles as a monolayer.

### Claim 12 (depends on 8)

The method of claim 8, wherein the first electrolyte of the composition further comprises one or more ionic liquid cations selected from the group consisting of: butyltrimethylammonium, 1-butyl-3-methylimidazolium, 1-methyl-3-propylimidazolium, 1-hexyl-3-methylimidazolium, choline, ethylammonium, tributylmethylphosphonium, tributyl(tetradecyl)phosphonium, trihexyl(tetradecyl)phosphonium, 1-ethyl-2,3-methylimidazolium, 1-butyl-1-methylpiperidinium, diethylmethylsulfonium, 1-methyl-3-propylimidazolium, 1-methyl-1-propylpiperidinium, 1-butyl-2-methylpyridinium, 1-butyl-4-methylpyridinium, 1-butyl-1-methylpyrrolidinium, and mixtures thereof.

### Claim 13 (depends on 8)

The method of claim 8, wherein the first electrolyte of the composition further comprises one or more ionic liquid anions selected from the group consisting of: tris(pentafluoroethyl)trifluorophosphate, trifluoromethanesulfonate, hexafluorophosphate, tetrafluoroborate, ethyl sulfate, methyl sulfate, dimethyl phosphate, trifluoromethanesulfonate, methanesulfonate, triflate, tricyanomethanide, dibutylphosphate, bis(trifluoromethylsulfonyl)imide, bis-2,4,4-(trimethylpentyl) phosphinate, iodide, chloride, bromide, nitrate, thiocyanate, and mixtures thereof.

### Claim 14 (depends on 8)

The method of claim 8, wherein the composition further comprises a third electrolyte different from the first and second electrolytes, the third electrolyte comprising one or more electrolytes selected from the group consisting of: potassium hydroxide, sodium hydroxide, ammonium hydroxide, lithium hydroxide, nickel hydroxide, cadmium hydroxide, magnesium hydroxide, sulfuric acid, hydrochloric acid, fluoroboric acid, ammonium chloride, zinc chloride, zinc bis(trifluoromethanesulfonyl)imide, aluminium chloride, chromium chloride, magnesium perchloride, barium chromate, lithium chromate, lithium-thyonyl chloride, lithium perchlorate, lithium bromide, lithium triflate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis-oxalato borate, lithium bis(trifluoromethanesulfonyl)imide, lithium bisoxalatoborate, lithium iodide, lithium tetrachloroaluminate, potassium carbonate, potassium fluoride, potassium borate, silver nitride, silver tetrafluoroborate; salts of bis(trifluoromethylsulfonyl)imide, tris(pentafluoroethyl)trifluorophosphate, trifluoromethanesulfonate, hexafluorophosphate, tetrafluoroborate, ethyl sulfate, dimethyl phosphate, trifluoromethanesulfonate, triflate, tricyanomethanide, dibutylphosphate; and mixtures thereof.

### Claim 15

A liquid or gel separator for separating and spacing apart at least two conductors, the liquid or gel separator comprising:
a plurality of particles comprising silicate glass having a size between 5 microns to 15 microns and present in an amount between 40 to 75 percent of the total weight of the separator, wherein at least some particles of the plurality of silicate glass particles are arranged as a monolayer;
an ionic liquid as a first electrolyte, the ionic liquid comprising 1-ethyl-3-methylimidazolium;
a second electrolyte comprising zinc tetrafluoroborate salt, the first and second electrolytes present in an amount between 15 to 45 percent of the total weight of the separator; a polymer present in an amount between 0.5 to 15 percent of the total weight of the separator and comprising polyvinyl alcohol (“PVA”) or polyvinylidene fluoride (“PVFD”); and
at least a trace amount of N-methyl-2-pyrrolidinone.

### Claim 16 (depends on 15)

The liquid or gel separator of claim 15, wherein the plurality of silicate glass particles are a mixture of solid and hollow particles.

### Claim 17 (depends on 15)

The separator of claim 15, wherein the first electrolyte further comprises one or more ionic liquid cations selected from the group consisting of: butyltrimethylammonium, 1-butyl-3-methylimidazolium, 1-methyl-3-propylimidazolium, 1-hexyl-3-methylimidazolium, choline, ethylammonium, tributylmethylphosphonium, tributyl(tetradecyl)phosphonium, trihexyl(tetradecyl)phosphonium, 1-ethyl-2,3-methylimidazolium, 1-butyl -1-methylpiperidinium, diethylmethylsulfonium, 1-methyl-3-propylimidazolium, 1-methyl-1-propylpiperidinium, 1-butyl-2-methylpyridinium, 1-butyl-4-methylpyridinium, 1-butyl-1-methylpyrrolidinium, and mixtures thereof.

### Claim 18 (depends on 15)

The separator of claim 15, wherein the first electrolyte further comprises one or more ionic liquid anions selected from the group consisting of: tris(pentafluoroethyl)trifluorophosphate, trifluoromethanesulfonate, hexafluorophosphate, tetrafluoroborate, ethyl sulfate, methyl sulfate, dimethyl phosphate, trifluoromethanesulfonate, methanesulfonate, triflate, tricyanomethanide, dibutylphosphate, bis(trifluoromethylsulfonyl)imide, bis-2,4,4-(trimethylpentyl) phosphinate, iodide, chloride, bromide, nitrate, thiocyanate, and mixtures thereof.

### Claim 19 (depends on 15)

The liquid or gel separator of claim 15, wherein the plurality of silicate glass particles are greater than 5 microns and less than 10 microns in any dimension.

### Claim 20 (depends on 15)

The liquid or gel separator of claim 15, wherein the plurality of silicate glass particles have a size of 7 microns, plus or minus 2 microns, in any dimension.