SEMI-SOLID ELECTRODES WITH GEL POLYMER ADDITIVE

• US 20150024279A1
• Filed: 07/21/2014
• Published: 01/22/2015
• Est. Priority Date: 07/19/2013
• Status: Active Grant

• Current Assignee: 24M Technologies, Inc.
• Original Assignee: 24M Technologies, Inc.
• Inventors: TAN, Taison, OTA, Naoki, DISKO, Jeffry
• Granted Patent: US 10,122,044 B2
• Time in Patent Office: Days
• US Class Current: 429/303
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0565 Polymeric materials, e.g. gel-type or solid-type
• CPC Class Codes: H01M 10/058 Construction or manufacture
• CPC Class Codes: H01M 2300/0085 Immobilising or gelification of electrolyte
• CPC Class Codes: H01M 4/13 Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
• CPC Class Codes: H01M 4/62 Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• CPC Class Codes: H01M 4/624 Electric conductive fillers
• CPC Class Codes: H01M 4/64 Carriers or collectors
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y10T 29/49108 Electric battery cell making

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

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 about 1.5% by weight of a polymer additive.

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

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

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

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

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

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

8. 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.

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

10. The semi-solid electrode of claim 7, wherein the gel polymer additive is ACG Elexcel™

.

11. The semi-solid electrode of claim 7, wherein the gel polymer additive is ERM-1 Elexcel™

.

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

13. 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), polypropylene 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, PEO terpolymer poly, and NIPPON SHOKUBAI®

polymer.

14. An energy storage device, comprising:

a positive electrode current collector, a negative electrode current collector and an ion permeable membrane disposed between the positive electrode current collector and the negative electrode current collector,

the ion permeable membrane spaced from the positive electrode current collector and at least partially defining a positive electroactive zone,

the ion permeable membrane spaced from the negative electrode current collector and at least partially defining a negative electroactive zone; and

a semi-solid electrode disposed in at least one of the positive electroactive zone and the negative electroactive zone, the semi-solid electrode including a suspension of an ion-storing solid phase material in a non-aqueous electrolyte, the non-aqueous electrolyte including about 0.01% to about 1.5% by weight of a polymer additive.

15. The energy storage device of claim 14, wherein the semi-solid electrode disposed in the positive electroactive zone is a semi-solid cathode, the semi-solid cathode comprising:

about 20% 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 about 1.5% by weight of a polymer additive.

16. The energy storage device of claim 14, wherein the semi-solid electrode disposed in the negative electroactive zone is a semi-solid anode, the semi-solid anode comprising;

about 10% to about 75% by volume of an active material;

about 0.5% to about 20% by volume of the conductive material; and

about 20% to about 70% by volume of an electrolyte, the electrolyte including about 0.01% to about 1.5% by weight of the polymer additive.

17. The energy storage device of claim 16, wherein the semi-solid anode further includes about 1% to about 30% by volume of a high capacity material.

18. A method of preparing a semi-solid electrode, the method comprising:

combining a gel polymer additive with a non-aqueous liquid electrolyte to form a polymer-electrolyte mixture;

combining an active material with the polymer-electrolyte mixture to form an intermediate material;

combining a conductive additive with the intermediate material to form a semi-solid electrode material;

forming the semi-solid electrode material into an electrode; and

optionally, curing the polymer additive.

19. The method of claim 18, wherein the polymer additive and the non-aqueous liquid electrolyte are mixed until the polymer additive dissolves in the non-aqueous liquid electrolyte.

20. The method of claim 18, wherein the weight percentage of the polymer additive in the polymer-electrolyte mixture is between about 0.01% and about 1.5%.

21. The method of claim 20, wherein the weight percentage of the polymer additive in the gel-electrolyte mixture is between about 0.1% and about 0.1%.

22. The method of claim 18, wherein the curing includes maintaining the formed electrode at room temperature for a period of at least about 24 hours.

23. The method of claim 22, wherein the curing includes maintaining the formed electrode at room temperature for a period of at least about 72 hours.

24. The method of claim 18, wherein the curing includes heating the formed electrode to a temperature of at least about 65 degrees Celsius for a period of at least about 24 hours.