Method of producing conducting polymer network-enabled particulates of anode active material particles for lithium-ion batteries

Patent metadata

Field	Value
Publication number	US-11735722-B2
Application number	US-201916380336-A
Country	US
Kind code	B2
Filing date	Apr 10, 2019
Priority date	Apr 10, 2019
Publication date	Aug 22, 2023
Grant date	Aug 22, 2023

Abstract

Provided is method of producing graphene-embraced anode particulates for a lithium battery, the method comprising: (A) providing anode active material-decorated carbon or graphite particles, wherein the carbon or graphite particles have a diameter or thickness from 500 nm to 50 μm and the anode active material, in a form of particles or coating having a diameter or thickness from 0.5 nm to 2 μm, is bonded to surfaces of the carbon or graphite particles; and (B) embracing the anode active material-decorated carbon or graphite particles with a shell comprising multiple graphene sheets to produce the graphene-embraced anode particulates.

First claim

The invention claimed is:

1. A method of producing multi-functional particulates of graphene-protected conducting polymer gel network-encapsulated anode particles for a lithium battery, said method comprising:
A) providing particulates of conducting polymer gel network-encapsulated anode active material particles, wherein one or a plurality of primary particles of an anode active material, having a diameter or thickness from 0.5 nm to 20 μm, is encapsulated by or embedded in an electrically and/or ionically conducting polymer gel network;
B) embracing said particulates of conducting polymer gel network-encapsulated anode active material particles with a shell of multiple graphene sheets, having a thickness from 0.5 nm to 10 μm, to produce said multi-functional particulates, having a diameter from 100 nm to 100 μm; and
C) wherein the conducting polymer gel network contains a conjugated polymer selected from Poly(isothianaphthene), Poly(2,5-dialkoxy) paraphenylene vinylene, Poly[(1,4-phenylene-1,2-diphenylvinylene)], Poly(3′,7′-dimethyloctyloxy phenylene vinylene), Polyparaphenylene sulphide, Polyheptadiyne, Poly(3-octylthiophene), Poly(3-cyclohexylthiophene), Poly(3-methyl-4-cyclohexylthiophene), Poly(2,5-dialkoxy-1,4-phenyleneethynylene), Poly(2-decyloxy-1,4-phenylene), Poly(9,9-dioctylfluorene), Polyquinoline, a derivative thereof, a copolymer thereof, a sulfonated version thereof, or a combination thereof.

2. The method of claim 1 , where said particulates of conducting polymer gel network-encapsulated anode active material particles provided in step (A) are produced by operating a procedure selected from pan-coating, air-suspension coating, centrifugal extrusion, vibration-nozzle encapsulation, spray-drying, coacervation-phase separation, interfacial polycondensation or interfacial cross-linking, in-situ polymerization, matrix polymerization, or a combination thereof.

3. The method of claim 1 , where said step (B) comprises conducting spray-drying, fluidized bed coating, or air-suspension coating to embrace or encapsulate said particulates of conducting polymer gel-encapsulated anode active material particles with multiple graphene sheets to produce said graphene-embraced anode particulates.

4. The method of claim 1 , wherein multiple graphene sheets contain single-layer or few-layer graphene, wherein said few-layer graphene sheets have 2-10 layers of stacked graphene planes having an inter-plane spacing d 002 from 0.3354 nm to 0.6 nm as measured by X-ray diffraction and said single-layer or few-layer graphene sheets contain a pristine graphene material having essentially zero % of non-carbon elements, or a non-pristine graphene material having 0.001% to 25% by weight of non-carbon elements.

5. The method of claim 4 , wherein said non-pristine graphene is selected from graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, doped graphene, chemically functionalized graphene, or a combination thereof.

6. The method of claim 1 , wherein said step (B) comprises:
i) mixing multiple particles of a graphitic material, said particulates of conducting polymer gel network-encapsulated anode active material particles, and optional milling balls or beads, to form a mixture in an impacting chamber of an energy impacting apparatus;
ii) operating said energy impacting apparatus with a frequency and an intensity for a length of time sufficient for peeling off graphene sheets from said particles of graphitic material and transferring said peeled graphene sheets to surfaces of said particulates of conducting polymer gel network-encapsulated anode active material particles to produce said multi-functional particulates; and
iii) recovering said multi-functional particulates from said impacting chamber and separating said milling balls from said multi-functional particulates.

7. The method of claim 6 , wherein said particles of ball-milling media contain milling balls selected from ceramic particles, including ZrO 2 and non-ZrO 2 metal oxide particles, metal particles, glass particles, polymer particles, or a combination thereof.

8. The method of claim 6 , wherein said energy impacting apparatus is selected from a double cone mixer, double cone blender, vibratory ball mill, planetary ball mill, high energy mill, basket mill, agitator ball mill, cryogenic ball mill, micro ball mill, tumbler ball mill, attritor, continuous ball mill, stirred ball mill, pressurized ball mill, plasma-assisted ball mill, freezer mill, vibratory sieve, bead mill, nano bead mill, ultrasonic homogenizer mill, centrifugal planetary mixer, vacuum ball mill, or resonant acoustic mixer.

9. The method of claim 6 , wherein said graphitic material is selected from natural graphite, synthetic graphite, highly oriented pyrolytic graphite, graphite fiber, graphitic nano-fiber, graphite fluoride, chemically modified graphite, meso-carbon micro-bead, partially crystalline graphite, or a combination thereof.

10. The method of claim 6 , wherein said procedure of operating said energy impacting apparatus is conducted in a continuous manner using a continuous energy impacting device.

11. The method of claim 1 , further comprising a step of pre-loading from 0.1% to 54.7% by weight of lithium ions into said primary particles of anode active material prior to step (A) or step (B), or after step (B).

12. The method of claim 1 , wherein said anode active material primary particles are selected from the group consisting of:
(A) lithiated and un-lithiated silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), niobium (Nb), and cadmium (Cd);
(B) lithiated and un-lithiated alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, Nb, or Cd with other elements;
(C) lithiated and un-lithiated oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, or Cd, and their mixtures, composites, or lithium-containing composites;
(D) lithiated and un-lithiated salts and hydroxides of Sn;
(E) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium niobium oxide, lithium transition metal oxide;
and combinations thereof.

13. The method of claim 1 , wherein said anode active material particles are porous having surface pores, internal pores, or both surface and internal pores.

14. The method of claim 1 , wherein said anode active material particles include powder, flakes, beads, pellets, spheres, wires, fibers, filaments, discs, ribbons, or rods, having a diameter or thickness from 2 nm to 100 nm.

15. The method of claim 1 , further comprising a step of incorporating said multi-functional particulates into a battery anode electrode.

Assignees

• Nanotek Instruments Inc
• Global Graphene Group Inc

Inventors

• Jang Bor Z

Classifications

• H01M4/366 Primary

  as layered products · CPC title

• H01M4/0404

  by coating on electrode collectors · CPC title

• H01M4/0466

  Electrochemical polymerisation · CPC title

• H01M4/131

  Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx · CPC title

• H01M4/133

  Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx · CPC title