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

Patent metadata

Field	Value
Publication number	US-11145892-B2
Application number	US-201916580564-A
Country	US
Kind code	B2
Filing date	Sep 24, 2019
Priority date	Oct 13, 2017
Publication date	Oct 12, 2021
Grant date	Oct 12, 2021

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, embrances 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.

2. The surface-stabilized anode active material particulate of claim 1 , 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.

3. The surface-stabilized anode active material particulate of claim 1 , 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.

4. The surface-stabilized anode active material particulate of claim 1 , 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.

5. The surface-stabilized anode active material particulate of claim 1 , 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.

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

7. The surface-stabilized anode active material particulate of claim 1 , wherein said anode active material comprises silicon and said prelithiated core particle is selected from Li x Si, wherein numerical x is from 0.01 to 4.4.

8. The surface-stabilized anode active material particulate of claim 1 , wherein said anode active material particles comprise a doped semiconductor material selected from Si or Ge doped with n-type and/or p-type dopants.

9. A mass of anode active material powder comprising the surface-stabilized anode active material particulate of claim 1 .

10. An anode electrode comprising said surface-stabilized anode active material particulate of claim 1 , a conductive additive, and a binder.

11. A lithium-ion or lithium metal battery containing the anode electrode of claim 10 , a cathode electrode, and an electrolyte in ionic contact with the anode electrode and the cathode electrode.

12. A method of producing the surface-stabilized anode active material particulate of claim 1 , said method comprising:
(a) providing a plurality of particles of an anode active material; and
(b) prelithiating said particles to form prelithiated particles that each contains an amount of lithium from 1% to 100% of a maximum lithium content contained in said anode active material.

13. The method of claim 12 , 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.

14. The method of claim 12 , wherein said step of prelithiating includes electrochemical prelithiation, chemical prelithiation, physical prelithiation, or a combination thereof.

15. The method of claim 12 , wherein said anode active material comprises silicon and said prelithiated particles comprise a prelithiated silicon Li 4 Si, Li 4.4 Si, or Li x Si, wherein numerical x is from 1 to 4.4.

16. The method of claim 12 , wherein said step of providing particles of an anode active material comprises providing a doped semiconductor material selected from Si or Ge doped with n-type and/or p-type dopants.

17. The method of claim 12 , further comprising a step of coating a surface of said prelithiated particles with a thin layer of carbon, graphene, or electron-conducting polymer, having a thickness from 0.5 nm to 1 μm, prior to step (c).

18. The method of claim 17 , wherein said thin layer of carbon is obtained from pyrolization of a polymer, pitch, or organic precursor or obtained by chemical vapor deposition, physical vapor deposition, or sputtering.

19. A method of producing a lithium-ion battery comprising (A) preparing an anode from the surface-stabilized particles produced by the method of claim 12 ; and (B) combining said anode with a cathode, and an electrolyte to form said battery.

20. 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, embrances 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.

21. The surface-stabilized anode active material particulate of claim 20 , 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

Assignees

• Global Graphene Group Inc

Inventors

• Pan Baofei
• Zhamu Aruna
• Jang Bor Z

Classifications

• Y02P70/50

  Manufacturing or production processes characterised by the final manufactured product · CPC title

• H01M10/0525 Primary

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

• H01M10/04

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

• H01M4/366

  as layered products · CPC title

• H01M2004/027

  Negative electrodes · CPC title