Method of producing electrochemically stable elastomer-encapsulated particles of cathode active materials for lithium batteries

Patent metadata

Field	Value
Publication number	US-11239460-B2
Application number	US-201816109178-A
Country	US
Kind code	B2
Filing date	Aug 22, 2018
Priority date	Aug 22, 2018
Publication date	Feb 1, 2022
Grant date	Feb 1, 2022

Abstract

A method of producing a powder mass for a lithium battery, comprising: (a) mixing an inorganic filler and an elastomer or its precursor in a liquid medium or solvent to form a suspension; (b) dispersing a plurality of particles of a cathode active material in the suspension to form a slurry; and (c) dispensing the slurry and removing the solvent and/or polymerizing or curing the precursor to form the powder mass, wherein at least a particulate comprises one or a plurality of cathode active material particles being encapsulated by a layer of inorganic filler-reinforced elastomer having a thickness from 1 nm to 10 μm, a fully recoverable tensile strain from 2% to 500%, and a lithium ion conductivity from 10−7 S/cm to 5×10−2 S/cm and the inorganic filler has a lithium intercalation potential from 1.1 V to 4.5 V versus Li/Li+.

First claim

We claim:

1. A method of producing a powder mass of a cathode active material for a lithium battery, the method comprising: (a) mixing an inorganic filler material and an elastomer or its precursor in a liquid medium or solvent to form a suspension; (b) dispersing a plurality of particles of said cathode active material in the suspension to form a slurry; and (c) dispensing the slurry and removing the solvent and/or polymerizing or curing the precursor to form the powder mass, wherein the powder mass comprises multiple particulates of the cathode active material and at least a particulate comprises one or a plurality of particles of said cathode active material being encapsulated by a thin layer of inorganic filler-reinforced elastomer having from 0.01% to 50% by weight of an inorganic filler dispersed in an elastomeric matrix material, wherein said encapsulating thin layer of inorganic filler-reinforced elastomer has a thickness from 1 nm to 10 μm, a fully recoverable tensile strain from 2% to 500%, and a lithium ion conductivity from 10 −7 S/cm to 5×10 −2 S/cm and said inorganic filler has a lithium intercalation potential from 1.1 V to 4.5 V versus Li/Li + .

2. The method of claim 1 , wherein said inorganic filler is selected from an oxide, carbide, boride, nitride, sulfide, phosphide, or selenide of a transition metal, a lithiated version thereof, or a combination thereof.

3. The method of claim 2 , wherein said transition metal is selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Pd, Ag, Cd, La, Ta, W, Pt, Au, Hg, a combination thereof, or a combination thereof with Al, Ga, In, Sn, Pb, Sb, or Bi.

4. The method of claim 1 , wherein said inorganic filler is selected from the group consisting of nanodiscs, nanoplatelets, or nanosheets of (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) sulfide, selenide, or telluride of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, cobalt, nickel, manganese, or any transition metal; (d) boron nitride, and (e) combinations thereof, wherein said nanodiscs, nanoplatelets, or nanosheets have a thickness from 1 nm to 100 nm.

5. The method of claim 1 , wherein said elastomeric matrix material comprises a material selected from the group consisting of sulfonated or un-sulfonated versions of natural polyisoprene, synthetic polyisoprene, polybutadiene, chloroprene rubber, polychloroprene, butyl rubber, styrene-butadiene rubber, nitrile rubber, ethylene propylene rubber, ethylene propylene diene rubber, metallocene-based poly(ethylene-co-octene) elastomer, poly(ethylene-co-butene) elastomer, styrene-ethylene-butadiene-styrene elastomer, epichlorohydrin rubber, polyacrylic rubber, silicone rubber, fluorosilicone rubber, perfluoroelastomers, polyether block amides, chlorosulfonated polyethylene, ethylene-vinyl acetate, thermoplastic elastomer, protein resilin, protein elastin, ethylene oxide-epichlorohydrin copolymer, polyurethane, urethane-urea copolymer, and combinations thereof.

6. The method of claim 1 , wherein said inorganic filler-reinforced elastomer further comprises an electron-conducting filler dispersed in said elastomer matrix material wherein said electron-conducting filler is selected from the group consisting of carbon nanotube, carbon nanofiber, nano carbon particle, metal nanoparticle, metal nanowire, electron-conducting polymer, graphene, and combinations thereof, wherein said graphene is selected from sheets of pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, nitrogenated graphene, hydrogenated graphene, doped graphene, functionalized graphene, or a combination thereof and said graphene comprise single-layer graphene or few-layer graphene.

7. The method of claim 6 , wherein said electron-conducting polymer is selected from polyaniline, polypyrrole, polythiophene, polyfuran, a bi-cyclic polymer, a sulfonated derivative thereof, or a combination thereof.

8. The method of claim 6 , wherein said graphene sheets have a length or width from 5 nm to 5 μm.

9. The method of claim 1 , wherein said cathode active material is selected from an inorganic material, an organic material, a polymeric material, or a combination thereof.

10. The method of claim 9 , wherein said inorganic material is selected from a metal oxide, metal phosphate, metal silicide, metal selenide, transition metal sulfide, or a combination thereof.

11. The method of claim 9 , wherein said inorganic material is selected from the group consisting of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium vanadium oxide, lithium-mixed metal oxide, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, lithium mixed metal phosphate, lithium metal silicide, and combinations thereof.

12. The method of claim 9 , wherein said inorganic material is selected from a metal fluoride or metal chloride including the group consisting of CoF 3 , MnF 3 , FeF 3 , VF 3 , VOF 3 , TiF 3 , BiF 3 , NiF 2 , FeF 2 , CuF 2 , CuF, SnF 2 , AgF, CuCl 2 , FeCl 3 , MnCl 2 , and combinations thereof.

13. The method of claim 9 , wherein said inorganic material is selected from a lithium transition metal silicate, denoted as Li 2 MSiO 4 or Li 2 Ma x Mb y SiO 4 , wherein M and Ma are selected from Fe, Mn, Co, Ni, V, or VO; Mb is selected from Fe, Mn, Co, Ni, V, Ti, Al, B, Sn, or Bi; and x+y≤1.

14. The method of claim 9 , wherein said inorganic material is selected from a transition metal dichalcogenide, a transition metal trichalcogenide, or a combination thereof.

15. The method of claim 9 , wherein said inorganic material is selected from the group consisting of TiS 2 , TaS 2 , MoS 2 , NbSe 3 , MnO 2 , CoO 2 , an iron oxide, a vanadium oxide, and combinations thereof.

16. The method of claim 10 , wherein said metal oxide comprises a vanadium oxide selected from the group consisting of VO 2 , Li x VO 2 , V 2 O 5 , Li x V 2 O 5 , V 3 O 8 , Li x V 3 O 8 , Li x V 3 O 7 , V 4 O 9 , Li x V 4 O 9 , V 6 O 13 , Li x V 6 O 13 , their doped versions, their derivatives, and combinations thereof, wherein 0.1<x<5.

17. The method of claim 10 , wherein said metal oxide or metal phosphate is selected from a layered compound LiMO 2 , spinel compound LiM 2 O 4 , olivine compound LiMPO 4 , silicate compound Li 2 MSiO 4 , tavorite compound LiMPO 4 F, borate compound LiMBO 3 , or a combination thereof, wherein M is a transition metal or a mixture of multiple transition metals.

18. The method of claim 9 , wherein said inorganic material is selected from the group consisting of: (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) sulfide, selenide, or telluride of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, cobalt, manganese, iron, nickel, or a transition metal; (d) boron nitride, and (e) combinations thereof.

19. The method of claim 9 , wherein said organic material or polymeric material is selected from the group consisting of poly(anthraquinonyl sulfide) (PAQS), a lithium oxocarbon, 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA), poly(anthraquinonyl sulfide), pyrene-4,5,9,10-tetraone (PYT), polymer-bound PYT, quino(triazene), redox-active organic material, tetracyanoquinodimethane (TCNQ), tetracyanoethylene (TCNE), 2,3,6,7,10,11-hexamethoxytriphenylene (HMTP), poly(5-amino-1,4-dyhydroxy anthraquinone) (PADAQ), phosphazene disulfide polymer ([(NPS 2 ) 3 ]n), lithiated 1,4,5,8-naphthalenetetraol formaldehyde polymer, hexaazatrinaphtylene (HATN), hex

Assignees

• Nanotek Instruments Inc
• Global Graphene Group Inc

Inventors

• Pan Baofei
• He Hui
• Jang Bor Z

Classifications

• H01M4/624

  Electric conductive fillers · CPC title

• H01M10/0525

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

• H01M2004/028

  Positive electrodes · CPC title

• H01M4/62 Primary

  Selection of inactive substances as ingredients for active masses, e.g. binders, fillers · CPC title

• H01M4/366 Primary

  as layered products · CPC title