Method of producing protected particles of cathode active materials for lithium batteries

Patent metadata

Field	Value
Publication number	US-11223049-B2
Application number	US-201816112225-A
Country	US
Kind code	B2
Filing date	Aug 24, 2018
Priority date	Aug 24, 2018
Publication date	Jan 11, 2022
Grant date	Jan 11, 2022

Abstract

A method of producing a powder mass for a lithium battery, the method comprising: (a) providing a solution containing a sulfonated elastomer dissolved in a solvent or a precursor in a liquid form or dissolved in a solvent; (b) dispersing a plurality of particles of a cathode active material in the solution to form a slurry; and (c) dispensing the slurry and removing the solvent and/or polymerizing/curing the precursor to form the powder mass, wherein the powder mass comprises multiple particulates and at least a particulate comprises one or a plurality of particles of a cathode active material being encapsulated by a thin layer of sulfonated elastomer having a thickness from 1 nm to 10 μm, a fully recoverable tensile strain from 2% to 800%, and a lithium ion conductivity from 10−7 S/cm to 5×10−2 S/cm at room temperature.

First claim

We claim:

1. A method of producing a powder mass of a cathode active material for a lithium battery, said method comprising:
(a) providing a solution containing a sulfonated elastomer dissolved in a solvent or a precursor, a monomer or oligomer to said sulfonated elastomer in a liquid form or dissolved in a solvent, wherein said sulfonated elastomer comprises a material selected from the group consisting of sulfonated natural polyisoprene, sulfonated synthetic polyisoprene, sulfonated polybutadiene, sulfonated chloroprene rubber, sulfonated polychloroprene, sulfonated butyl rubber, sulfonated nitrile rubber, sulfonated ethylene propylene rubber, sulfonated ethylene propylene diene rubber, sulfonated metaliocene-based poly(ethylene-co-octene) elastomer, sulfonated poly(ethylene-co-butene) elastomer, sulfonated styrene-ethylene-butadiene-styrene elastomer, sulfonated epichlorohydrin rubber, sulfonated polyacrylic rubber, sulfonated silicone rubber, sulfonated fluorosilicone rubber, sulfonated perfluoroelastomers, sulfonated polyether block amides, sulfonated chlorosulfonated polyethylene, sulfonated ethylene-vinyl acetate polymer, sulfonated thermoplastic elastomer, sulfonated protein resilin, sulfonated protein elastin, sulfonated ethylene oxide-epichlorohydrin copolymer, sulfonated polyurethane, sulfonated urethane-urea copolymer, and combinations thereof;
(b) dispersing a plurality of particles of a cathode active material in said solution to form a slurry; and
(c) dispensing said slurry and removing said solvent and/or polymerizing/curing said precursor to form said powder mass, wherein said powder mass comprises multiple particulates wherein at least one of said particulates comprises one or a plurality of particles of a cathode active material being encapsulated by a thin layer of sulfonated elastomer having a thickness from 1 nm to 10 μm, a fully recoverable tensile strain from 2% to 800%, and a lithium ion conductivity from 10 −7 S/cm to 5×10 −2 S/cm at room temperature, wherein said step of dispensing said slurry and removing said solvent and/or polymerizing/curing to form said powder mass includes operating a procedure selected from pan-coating, vibration-nozzle encapsulation, interfacial polycondensation and interfacial cross-linking, or a combination thereof.

2. The method of claim 1 , wherein said step of providing said solution includes (a) sulfonating an elastomer to form said sulfonated elastomer and dissolving said sulfonated elastomer in said solvent to form said solution, or (b) sulfonating said precursor to obtain a sulfonated precursor, a sulfonated monomer or sulfonated oligomer, polymerizing said sulfonated precursor to form said sulfonated elastomer and dissolving said sulfonated elastomer in said solvent to form said solution.

3. 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.

4. The method of claim 3 , wherein said inorganic material is selected from a metal oxide, metal phosphate, metal silicide, metal selenide, transition metal sulfide, sulfur, lithium polysulfide, selenium, lithium selenide, or a combination thereof.

5. The method of claim 3 , wherein said inorganic material is selected from the group consisting of a 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.

6. The method of claim 3 , wherein said inorganic material is selected from a metal fluoride or metal chloride and combinations thereof.

7. The method of claim 3 , 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.

8. The method of claim 3 , wherein said inorganic material is selected from a transition metal dichalcogenide, a transition metal trichalcogenide, or a combination thereof.

9. The method of claim 3 , 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.

10. The method of claim 4 , 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.

11. The method of claim 4 , 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.

12. The method of claim 3 , wherein said inorganic material is selected from: (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, or (e) a combination thereof.

13. The method of claim 3 , wherein said organic material or polymeric material is selected from 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), 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′-dipropyl-2,3,5,6-tetraketopiperazine (PRP), a thioether polymer, a quinone compound, 1,4-benzoquinone, 5,7,12,14-pentacenetetrone (PT), 5-amino-2,3-dihydro-1,4-dyhydroxy anthraquinone (ADDAQ), 5-amino-1,4-dyhydroxy anthraquinone (ADAM), calixquinone, Li 4 C 6 O 6 , Li 2 C 6 O 6 , Li 6 C 6 O 6 , and combinations thereof.

14. The method of claim 13 , wherein said thioether polymer is selected from the group consisting of poly[methanetetryl-tetra(thiomethylene)] (PMTTM), poly(2,4-dithiopentanylene) (PDTP), a polymer containing poly(ethene-1,1,2,2-tetrathiol) (PETT) as a main-chain thioether polymers, a side-chain thioether polymer having a main-chain consisting of conjugating aromatic moieties, and having a thioether side chain as a pendant, poly(2-phenyl-1,3-dithiolane) (PPDT), poly(1,4-di(1,3-dithiolan-2-yl)benzene) (PDDTB), poly(tetrahydrobenzodithiophene) (PTHBDT), poly[1,2,4,5-tetrakis(propylthio)benzene] (PTKPTB, and poly[3,4(ethylenedithio)thiophene] (PEDTT).

15. The method of claim 3 , wherein said organic material comprises a phthalocyanine compound selected from the group consisting of copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, iron phthalocyanine, lead phthalocyanine, nickel phthalocyanine, vanadyl phthalocyanine, fluorochromium ph

Assignees

• Nanotek Instruments Inc
• Global Graphene Group Inc

Inventors

• Pan Baofei
• He Hui
• Jang Bor Z

Classifications

• H01M4/624

  Electric conductive fillers · CPC title

• H01M4/60

  of organic compounds · CPC title

• H01M4/5825

  Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines · CPC title

• H01M4/582

  Halogenides · CPC title

• H01M4/5815

  Sulfides · CPC title