# US 10,122,044 B2 · Semi-solid electrodes with gel polymer additive

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- Number: US 10,122,044 B2
- Document ID: US10122044B2
- Status: Granted
- Kind: B2
- Application number: 14/336,119
- Filed: 2014-07-21
- Published: 2015-01-22
- Granted: 2018-11-06
- Earliest claimed: 2013-07-19
- Assignees: 24M Technologies, Inc.
- Applicants: 24M Technologies, Inc.
- Inventors: Taison Tan; Naoki Ota; Jeffry Disko
- Web page: https://patentgrep.com/patent/US10122044B2

## CPC

- H01M 10/0565: Polymeric materials, e.g. gel-type or solid-type
- H01M 4/13: Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M 4/62: Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M 4/624: {Electric conductive fillers}
- H01M 4/64: Carriers or collectors
- H01M 10/052: Li-accumulators
- H01M 10/058: Construction or manufacture
- H01M 2300/0085: Immobilising or gelification of electrolyte
- Y02E 60/10: Energy storage using batteries
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- Y10T 29/49108: Electric battery cell making
- 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
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

Embodiments described herein relate generally to electrochemical cells having semi-solid electrodes that include a gel polymer additive such that the electrodes demonstrate longer cycle life while significantly retaining the electronic performance of the electrodes and the electrochemical cells formed therefrom. In some embodiments, a semi-solid electrode can include about 20% to about 75% by volume of an active material, about 0.5% to about 25% by volume of a conductive material, and about 20% to about 70% by volume of an electrolyte. The electrolyte further includes about 0.01% to about 1.5% by weight of a polymer additive. In some embodiments, the electrolyte can include about 0.1% to about 0.7% of the polymer additive.

## Claims

### Claim 1

A semi-solid electrode, comprising:
about 20% to about 75% by volume of an active material;
about 0.5% to about 25% by volume of a conductive material; and
about 20% to about 70% by volume of an electrolyte, the electrolyte including
about 0.01% to 1.5% by weight of a polymer additive,
wherein a total polymer content in the electrolyte is less than or equal to 1.5% by weight, and
wherein the semi-solid electrode is a mixture of the active material, the conductive material and the electrolyte with the polymer additive.

### Claim 2 (depends on 1)

The semi-solid electrode of claim 1, wherein the electrolyte includes about 0.1% to about 1.25% by weight of the polymer additive.

### Claim 3 (depends on 2)

The semi-solid electrode of claim 2, wherein the electrolyte includes about 0.1% to about 1% by weight of the polymer additive.

### Claim 4 (depends on 3)

The semi-solid electrode of claim 3, wherein the electrolyte includes about 0.1% to about 0.7% by weight of the polymer additive.

### Claim 5 (depends on 4)

The semi-solid electrode of claim 4, wherein the electrolyte includes about 0.1% to about 0.5% by weight of the polymer additive.

### Claim 6 (depends on 5)

The semi-solid electrode of claim 5, wherein the electrolyte includes about 0.1% to about 0.3% by weight of the polymer additive.

### Claim 7 (depends on 1)

The semi-solid electrode of claim 1, wherein the polymer additive is a gel-polymer additive.

### Claim 8 (depends on 7)

The semi-solid electrode of claim 7, wherein the gel polymer additive includes at least one of a physically cross-linked gel polymer additive and a chemically cross-linked gel polymer additive.

### Claim 9 (depends on 7)

The semi-solid electrode of claim 7, wherein the gel polymer additive includes at least one of an acrylate group and a methacrylate group.

### Claim 10 (depends on 1)

The semi-solid electrode of claim 1, wherein the polymer additive is carboxy methyl cellulose.

### Claim 11 (depends on 1)

The semi-solid electrode of claim 1, wherein the polymer additive includes at least one of a poly(ethyleneglycol dimethacrylate), poly(ethyleneglycol diacrylate), poly(propyleneglycol dimethacrylate), poly(propyleneglycol diacrylate), and poly(methyl methacrylate) (PMMA), polyethylene glycol dimethacrylate, poly(acrylonitrile) (PAN), polyurethane (PU), poly(vinylidene difluoride) (PVdF), poly(ethylene oxide) (PEO), poly(propylene oxide) poly(ethyleneglycol dimethylether), poly(ethyleneglycol diethylether), poly[bis(methoxy ethoxyethoxide)-phosphazene], poly(dimethylsiloxane) (PDMS), polyacene, polydisulfide, polystyrene, polystyrene sulfonate, polypyrrole, polyaniline, polythiophene, polythione, polyvinyl pyridine (PVP), polyvinyl chloride (PVC), polyaniline, poly(3,4-ethylenedioxythiophene) (PEDOT), polypyrrole, polythiophene, poly(p-phenylene), poly(triphenylene), polyazulene, polyfluorene, polynaphtalene, polyanthracene, polyfuran, polycarbazole, tetrathiafulvalene-substituted polystyrene, ferrocene-substituted polyethylene, carbazole-substituted polyethylene, polyoxyphena zine, poly(heteroacene), poly[(4-styrenesulfonyl)(trifluoromethanesulfonyl)imide-co-methoxy-polyethyleneglycolacrylate] (Li[PSTFSI-co-MPEGA]), sulfonated poly(phenylene oxide) (PPO), N,N-dimethylacryl amide (DMAAm), and lithium 2-acrylamido-2-methyl-1-propane sulfonate (LiAMPS), Poly(lithium 2-Acrylamido-2-Methylpropanesulfonic Acid-Co-Vinyl Triethoxysilane), polyethyleneoxide(PEO)/poly(lithium sorbate), PEO/poly(lithium muconate), PEO/[poly(lithium sorbat)+BF3], PEO copolymer, and PEO terpolymer poly.

### Claim 12

A semi-solid electrode, comprising:
about 10% to about 75% by volume of an active material;
about 0.5% to about 20% by volume of a conductive material; and
about 20% to about 70% by volume of an electrolyte, the electrolyte including about 0.01% to 1.5% by weight of a polymer additive,
wherein a total polymer content in the electrolyte is less than or equal to 1.5% by weight, and
wherein the semi-solid electrode is a mixture of the active material, the conductive material and the electrolyte with the polymer additive.

### Claim 13 (depends on 12)

The semi-solid electrode of claim 12, wherein the semi-solid electrode further includes about 1% to about 30% by volume of a high capacity material.

### Claim 14 (depends on 12)

The semi-solid electrode of claim 12, wherein the electrolyte includes about 0.1% to about 1% by weight of the polymer additive.

### Claim 15 (depends on 12)

The semi-solid electrode of claim 12, wherein the polymer additive includes at least one of a poly(ethyleneglycol dimethacrylate), poly(ethyleneglycol diacrylate), poly(propyleneglycol dimethacrylate), poly(propyleneglycol diacrylate), and poly(methyl methacrylate) (PMMA), polyethylene glycol dimethacrylate, poly(acrylonitrile) (PAN), polyurethane (PU), poly(vinylidene difluoride) (PVdF), poly(ethylene oxide) (PEO), poly(propylene oxide) poly(ethyleneglycol dimethylether), poly(ethyleneglycol diethylether), poly[bis(methoxy ethoxyethoxide)-phosphazene], poly(dimethylsiloxane) (PDMS), polyacene, polydisulfide, polystyrene, polystyrene sulfonate, polypyrrole, polyaniline, polythiophene, polythione, polyvinyl pyridine (PVP), polyvinyl chloride (PVC), polyaniline, poly(3,4-ethylenedioxythiophene) (PEDOT), polypyrrole, polythiophene, poly(p-phenylene), poly(triphenylene), polyazulene, polyfluorene, polynaphtalene, polyanthracene, polyfuran, polycarbazole, tetrathiafulvalene-substituted polystyrene, ferrocene-substituted polyethylene, carbazole-substituted polyethylene, polyoxyphena zine, poly(heteroacene), poly[(4-styrenesulfonyl)(trifluoromethanesulfonyl)imide-co-methoxy-polyethyleneglycolacrylate] (Li[PSTFSI-co-MPEGA]), sulfonated poly(phenylene oxide) (PPO), N,N-dimethylacryl amide (DMAAm), and lithium 2-acrylamido-2-methyl-I-propane sulfonate (LiAMPS), Poly(lithium 2-Acrylamido-2-Methylpropanesulfonic Acid-Co-Vinyl Triethoxysilane), polyethyleneoxide(PEO)/poly(lithium sorbate), PEO/poly(lithium muconate), PEO/[poly(lithium sorbat)+BF3], PEO copolymer, and PEO terpolymer poly.

### Claim 16 (depends on 12)

The semi-solid electrode of claim 12, wherein the polymer additive is a gel-polymer additive.

### Claim 17

A semi-solid electrode, comprising:
an active material;
a conductive material; and
about 20% to about 70% by volume of an electrolyte, the electrolyte including about 0.01% to 1.5% by weight of a gel-polymer additive,
wherein a total polymer content in the electrolyte is less than or equal to 1.5% by weight, and
wherein the semi-solid electrode is a mixture of the active material, the conductive material and the electrolyte with the polymer additive.

### Claim 18 (depends on 17)

The semi-solid electrode of claim 17, wherein the semi-solid electrode further includes about 1% to about 30% by volume of a high capacity material.

### Claim 19 (depends on 17)

The semi-solid electrode of claim 17, wherein the electrolyte includes about 0.1% to about 1% by weight of the gel-polymer additive.

### Claim 20 (depends on 17)

The semi-solid electrode of claim 17, wherein the polymer additive includes at least one of a poly(ethyleneglycol dimethacrylate), poly(ethyleneglycol diacrylate), poly(propyleneglycol dimethacrylate), poly(propyleneglycol diacrylate), and poly(methyl methacrylate) (PMMA), polyethylene glycol dimethacrylate, poly(acrylonitrile) (PAN), polyurethane (PU), poly(vinylidene difluoride) (PVdF), poly(ethylene oxide) (PEO), poly(propylene oxide) poly(ethyleneglycol dimethylether), poly(ethyleneglycol diethylether), poly[bis(methoxy ethoxyethoxide)-phosphazene], poly(dimethylsiloxane) (PDMS), polyacene, polydisulfide, polystyrene, polystyrene sulfonate, polypyrrole, polyaniline, polythiophene, polythione, polyvinyl pyridine (PVP), polyvinyl chloride (PVC), polyaniline, poly(3,4-ethylenedioxythiophene) (PEDOT), polypyrrole, polythiophene, poly(p-phenylene), poly(triphenylene), polyazulene, polyfluorene, polynaphtalene, polyanthracene, polyfuran, polycarbazole, tetrathiafulvalene-substituted polystyrene, ferrocene-substituted polyethylene, carbazole-substituted polyethylene, polyoxyphena zine, poly(heteroacene), poly[(4-styrenesulfonyl)(trifluoromethanesulfonyl)imide-co-methoxy-polyethyleneglycolacrylate] (Li[PSTFSI-co-MPEGA]), sulfonated poly(phenylene oxide) (PPO), N,N-dimethylacryl amide (DMAAm), and lithium 2-acrylamido-2-methyl-1-propane sulfonate (LiAMPS), Poly(lithium 2-Acrylamido-2-Methylpropanesulfonic Acid-Co-Vinyl Triethoxysilane), polyethyleneoxide(PEO)/poly(lithium sorbate), PEO/poly(lithium muconate), PEO/[poly(lithium sorbat)+BF3], PEO copolymer, and PEO terpolymer poly.

### Claim 21 (depends on 17)

The semi-solid electrode of claim 17, wherein the semi-solid electrode is cured for at least 24 hours.

### Claim 22 (depends on 21)

The semi-solid electrode of claim 21, wherein the semi-solid electrode is cured at 65 degrees Celsius.