Electrochemically stable elastomer-encapsulated particles of cathode active materials for lithium batteries

Patent metadata

Field	Value
Publication number	US-11043662-B2
Application number	US-201816109142-A
Country	US
Kind code	B2
Filing date	Aug 22, 2018
Priority date	Aug 22, 2018
Publication date	Jun 22, 2021
Grant date	Jun 22, 2021

Abstract

Provided is a lithium battery cathode electrode comprising multiple particulates of a cathode active material, wherein at least a particulate is composed of one or a plurality of particles of a 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 based on the total weight of the inorganic filler-reinforced elastomer, wherein the 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 the inorganic filler has a lithium intercalation potential from 1.1 V to 4.5 V (preferably 1.2-2.5 V) versus Li/Li+.

First claim

We claim:

1. A cathode electrode for a lithium battery, said electrode comprising multiple particulates of a cathode active material, wherein at least a particulate is composed of 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 based on the total weight of the inorganic filler-reinforced elastomer, 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 cathode electrode of claim 1 , wherein said inorganic filler is selected from the group consisting of oxides, carbides, borides, nitrides, sulfides, phosphides, or selenides of transition metals, lithiated versions thereof, and combinations thereof.

3. The cathode electrode of claim 2 , wherein said transition metal is selected from the group consisting of 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, and combinations thereof with Al, Ga, In, Sn, Pb, Sb, or Bi.

4. The cathode electrode of claim 1 , wherein said inorganic filler is selected from 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, or (e) a combination thereof, wherein said nanodiscs, nanoplatelets, or nanosheets have a thickness from 1 nm to 100 nm.

5. The cathode electrode of claim 1 , wherein said elastomeric matrix material comprises a material selected from the group consisting 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, sulfonated versions thereof, and combinations thereof.

6. The cathode electrode 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 a carbon nanotube, carbon nanofiber, nanocarbon particle, metal nanoparticle, metal nanowire, electron-conducting polymer, graphene, or a combination thereof, wherein said graphene is selected from pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, nitrogenated graphene, hydrogenated graphene, doped graphene, functionalized graphene, and combinations thereof and wherein graphene comprises single-layer graphene or few-layer graphene.

7. The cathode electrode of claim 6 , wherein said electron-conducting polymer is selected from the group consisting of polyaniline, polypyrrole, polythiophene, polyfuran, a bi-cyclic polymer, sulfonated derivatives thereof, and combinations thereof.

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

9. The cathode electrode of claim 8 , wherein said inorganic material is selected from a metal oxide, metal phosphate, metal silicide, metal selenide, transition metal sulfide, or a combination thereof.

10. The cathode electrode of claim 8 , 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.

11. The cathode electrode of claim 8 , 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.

12. The cathode electrode of claim 8 , 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.

13. The cathode electrode of claim 8 , wherein said inorganic material is selected from a transition metal dichalcogenide, a transition metal trichalcogenide, or a combination thereof.

14. The cathode electrode of claim 8 , wherein said inorganic material is selected from TiS 2 , TaS 2 , MoS 2 , NbSe 3 , MnO 2 , CoO 2 , an iron oxide, a vanadium oxide, or a combination thereof.

15. The cathode electrode of claim 9 , wherein said metal oxide contains 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.

16. The cathode electrode of claim 9 , 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.

17. The cathode electrode of claim 8 , 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.

18. The cathode electrode of claim 8 , 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 1,4,5,8naphthalenetetraol formaldehyde polymer, hexaazatrinaphtylene (HATN), hexaazatriphenylene hexacarbonitrile (HAT(CN) 6 ), 5-benzylidene hydantoin, isatine lithium salt, pyromellitic diimide lithium salt, tetrahydroxy-p-benzoquinone derivatives (THQLi 4 ), N,N′-diphenyl-2,3,5,6-tetraketopiperazine (PHP), N,N′-diallyl-2,3,5,6-tetraketopiperazine (AP), N,N′-

Assignees

• Nanotek Instruments Inc
• Global Graphene Group Inc

Inventors

• Pan Baofei
• He Hui
• Jang Bor Z

Classifications

• H01M2004/027

  Negative electrodes · CPC title

• H01M4/622

  being polymers · CPC title

• H01M10/0525

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

• H01M4/62 Primary

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

• H01M4/137 Primary

  Electrodes based on electro-active polymers · CPC title