Surface-stabilized anode active material particulates for lithium batteries and production method

Patent metadata

Field	Value
Publication number	US-10424810-B2
Application number	US-201715783634-A
Country	US
Kind code	B2
Filing date	Oct 13, 2017
Priority date	Oct 13, 2017
Publication date	Sep 24, 2019
Grant date	Sep 24, 2019

Abstract

Provided is a surface-stabilized anode active material particulate (for use in a lithium battery), comprising: (a) one or a plurality of prelithiated or un-prelithiated anode active material particles (with or without a coating of carbon, graphene, or ion-conducting polymer); (b) a protecting polymer layer that wraps around, embraces or encapsulates the one or plurality of anode active material particles, wherein the protecting polymer layer has a thickness from 0.5 nm to 5 μm, and a lithium ion conductivity from 10−8 S/cm to 5×10−2 S/cm at room temperature and the protecting polymer layer contains a polymer selected from poly(ethylene oxide) (PEO), polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVdF), poly bis-methoxy ethoxyethoxide-phosphazene, polyvinyl chloride, poly(vinylidene chloride), polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP), polyethylene glycol (PEG), a PEG derivative, polyethylene glycol methyl ether, polyethylene glycol dimethyl ether, a sulfonated polymer, or a combination thereof.

First claim

The invention claimed is:

1. A surface-stabilized anode active material particulate for use in a lithium battery, said particulate comprising:
(a) one or a plurality of anode active material particles capable of reversibly storing lithium ions during a charge or discharge of said battery, wherein said anode active material particles are prelithiated to contain an amount of lithium from 1% to 100% of a maximum lithium content contained in said anode active material; and
(b) a protecting polymer layer that wraps around, embraces or encapsulates said one or plurality of anode active material particles, wherein said protecting polymer layer has a thickness from 0.5 nm to 5 μm, and a lithium ion conductivity from 10 −8 S/cm to 5×10 −2 S/cm at room temperature and said protecting polymer layer contains a polymer selected from the group consisting of poly(ethylene oxide) (PEO), polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVdF), poly bis-methoxy ethoxyethoxide-phosphazene, polyvinyl chloride, poly(vinylidene chloride), polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP), polyethylene glycol (PEG), chemical derivatives of PEG, poly(ethylene glycol diacrylate) (PEGDA), polyethylene glycol methyl ether, polyethylene glycol dimethyl ether, sulfonated polymers, interpenetrating polymer networks thereof, and combinations thereof.

2. A surface-stabilized anode active material particulate for use in a lithium battery, said particulate comprising:
(a) one or a plurality of anode active material particles capable of reversibly storing lithium ions during a charge or discharge of said battery; and
(b) a protecting polymer layer that wraps around, embraces or encapsulates said one or plurality of anode active material particles, wherein said protecting polymer layer has a thickness from 0.5 nm to 5 μm, and a lithium ion conductivity from 10 −8 S/cm to 5×10 −2 S/cm at room temperature and said protecting polymer layer contains a polymer selected from poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVdF), poly bis-methoxy ethoxyethoxide-phosphazene, polyvinyl chloride, polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP), poly(ethylene glycol diacrylate) (PEGDA), an interpenetrating polymer network thereof, a sulfonated polymer, an interpenetrating polymer network of poly(ethylene oxide) (PEO), an interpenetrating polymer network of polypropylene oxide (PPO), an interpenetrating polymer network of poly(vinylidene chloride), an interpenetrating polymer network of polyethylene glycol, an interpenetrating polymer network of polyethylene glycol methyl ether, an interpenetrating polymer network of polyethylene glycol dimethyl ether, or a combination thereof.

3. A surface-stabilized anode active material particulate for use in a lithium battery, said particulate comprising:
(a) one or a plurality of anode active material particles capable of reversibly storing lithium ions during a charge or discharge of said battery, wherein said anode active material particles are coated with a layer of carbon, graphene, electron-conducting polymer, or a combination thereof to form one or a plurality of conductive material-coated particles; and
(b) a protecting polymer layer that wraps around, embraces or encapsulates said one or plurality of conductive material-coated particles of the anode active material, wherein said protecting polymer layer has a thickness from 0.5 nm to 5 μm, and a lithium ion conductivity from 10 −8 S/cm to 5×10 −2 S/cm at room temperature and said protecting polymer layer contains a polymer selected from the group consisting of poly(ethylene oxide) (PEO), polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVdF), poly bis-methoxy ethoxyethoxide-phosphazene, polyvinyl chloride, poly(vinylidene chloride), polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP), polyethylene glycol (PEG), chemical derivatives of PEG, poly(ethylene glycol diacrylate) (PEGDA), poly(ethylene glycol diacrylate) (PEGDA), polyethylene glycol methyl ether, polyethylene glycol dimethyl ether, sulfonated polymers, interpenetrating polymer networks thereof, and combinations thereof.

4. The surface-stabilized anode active material of claim 1 , claim 2 , or claim 3 , wherein said sulfonated polymer is selected from the group consisting of sulfonated polyaniline, sulfonated polypyrrole, sulfonated polythiophene, sulfonated polyfuran, a sulfonated bi-cyclic polymer, poly(perfluoro sulfonic acid), sulfonated poly (tetrafluoroethylene), sulfonated perfluoroalkoxy derivatives of polytetrafluoroethylene, sulfonated polysulfone, sulfonated poly(ether ketone), sulfonated poly (ether ether ketone), sulfonated polyimide, sulfonated styrene-butadiene copolymers, sulfonated polystyrene, sulfonated poly chloro-trifluoroethylene (PCTFE), sulfonated perfluoroethylene-propylene copolymer (FEP), sulfonated ethylene-chlorotrifluoroethylene copolymer (ECTFE), sulfonated poly vinylidenefluoride (PVDF), sulfonated copolymers of polyvinylidenefluoride with hexafluoropropene and tetrafluoroethylene, sulfonated copolymers of ethylene and tetrafluoroethylene (ETFE), sulfonated polybenzimidazole (PBI), their chemical derivatives, copolymers, blends, and combinations thereof.

5. The surface-stabilized anode active material particulate of claim 1 , claim 2 , or claim 3 , wherein said anode active material particles are selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, V, or Cd, and their mixtures, composites, or lithium-containing composites; (d) salts and hydroxides of Sn; (e) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide, ZnCo 2 O 4 ; (f) particles of graphite and carbon; and (g) combinations thereof.

6. The surface-stabilized anode active material particulate of claim 1 , claim 2 , or claim 3 , wherein said anode active material particles are in a form of nanoparticle, nanowire, nanofiber, nanotube, nanosheet, nanobelt, nanoribbon, nanodisc, nanoplatelet, or nanohorn having a thickness or diameter from 0.5 nm to 100 nm.

7. The surface-stabilized anode active material particulate of claim 1 , claim 2 or claim 3 , wherein said anode active material particles contain a sub-micron or micron particle having a dimension, diameter or thickness, from 100 nm to 30 μm.

8. The surface-stabilized anode active material particulate of claim 1 or claim 2 , wherein said anode active material particles are coated with a layer of carbon, graphene, electron-conducting polymer, ion-conducting polymer, or a combination thereof that is disposed between said particle and said protective polymer layer.

9. The surface-stabilized anode active material particulate of claim 1 or claim 2 , further comprising a layer of carbon, graphene, electron-conducting polymer, or a combination thereof that is coated on said protecting polymer layer.

10. The surface-stabilized anode active material particulate of claim 1 , claim 2 or claim 3 , wherein said protecting polymer layer comprises a lithium salt selected from lithium carbonate (Li 2 CO 3 ), lithium hydroxide (LiOH), lithium halogenide (LiF, LiCl, LiI, or Li

Assignees

• Nanotek Instruments Inc
• Global Graphene Group Inc

Inventors

• Pan Baofei
• Zhamu Aruna
• Jang Bor Z

Classifications

• H01M10/04

  Construction or manufacture in general (H01M10/058, H01M10/12, H01M10/28, H01M10/38 take precedence) · CPC title

• H01M10/0525 Primary

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M2004/027

  Negative electrodes · CPC title

• H01M4/36

  Selection of substances as active materials, active masses, active liquids · CPC title

• H01M4/04

  Processes of manufacture in general · CPC title