Surface-stabilized cathode active material particles, lithium secondary batteries containing same, and method of manufacturing

Patent metadata

Field	Value
Publication number	US-12476244-B2
Application number	US-201715785351-A
Country	US
Kind code	B2
Filing date	Oct 16, 2017
Priority date	Oct 16, 2017
Publication date	Nov 18, 2025
Grant date	Nov 18, 2025

Abstract

Provided is particulate of a cathode active material for a lithium battery, comprising one or a plurality of cathode active material particles being embraced or encapsulated by a thin layer of a high-elasticity polymer having a recoverable tensile strain no less than 5%, a lithium ion conductivity no less than 10 −6 S/cm at room temperature, and a thickness from 0.5 nm to 10 μm, wherein the polymer contains an ultrahigh molecular weight (UHMW) polymer having a molecular weight from 0.5×10 6 to 9×10 6 grams/mole. The UHMW polymer is preferably selected from polyacrylonitrile, polyethylene oxide, polypropylene oxide, polyethylene glycol, polyvinyl alcohol, polyacrylamide, poly(methyl methacrylate), poly(methyl ether acrylate), a copolymer thereof, a sulfonated derivative thereof, a chemical derivative thereof, or a combination thereof.

First claim

We claim:

1 . A particulate of a cathode active material for a lithium battery, said particulate comprising one or a plurality of cathode active material particles being embraced or encapsulated by a thin layer of a protecting polymer having a molecular weight less than 0.5×10 6 g/mole, a lithium ion conductivity from 10 −8 S/cm to 5×10 −2 S/cm at room temperature, and a thickness from 0.5 nm to 10 μm, wherein said protecting polymer layer contains a polymer selected from the group consisting of derivatives of PEG, poly(ethylene glycol diacrylate) (PEGDA), polyethylene glycol methyl ether (PEG-me), polyethylene glycol dimethyl ether (PEG-de), interpenetrating polymer networks thereof, and combinations thereof, wherein said protecting polymer isolates the cathode active material from a non-aqueous electrolyte, polymer gel electrolyte, ionic liquid electrolyte, quasi-solid electrolyte, or solid-state electrolyte.

2 . The particulate of claim 1 , wherein said protecting polymer layer contains a lithium salt dispersed between chains of said protecting polymer.

3 . The particulate of claim 1 , wherein said protecting polymer layer contains an electrically conductive material dispersed therein.

4 . The particulate of claim 3 , wherein said electrically conducting material is selected from an electron-conducting polymer, a metal particle or wire, a graphene sheet, a carbon fiber, a graphite fiber, a carbon nanofiber, a graphite nanofiber, a carbon nanotube, a graphite particle, an expanded graphite flake, an acetylene black particle, or a combination thereof wherein said electrically conducting material has a thickness or diameter less than 100 nm.

5 . The particulate of claim 1 , wherein said protecting polymer layer contains a lithium salt dispersed therein wherein said lithium salt is selected from lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), lithium hexafluoroarsenide (LiAsF 6 ), lithium trifluoro-methanesulfonate (LiCF 3 SO 3 ), bis-trifluoromethyl sulfonylimide lithium (LiN(CF 3 SO 2 ) 2 ), lithium bis(oxalato) borate (LiBOB), lithium oxalyldifluoroborate (LiBF 2 C 2 O 4 ), lithium nitrate (LiNO 3 ), Li-fluoroalkyl-phosphates (LiPF 3 (CF 2 CF 3 ) 3 ), lithium bisperfluoro-ethylsulfonylimide (LiBETI), lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), an ionic liquid-based lithium salt, and combinations thereof.

6 . The particulate of claim 1 , wherein said protecting polymer layer has a thickness from 1 nm to 1 μm.

7 . The particulate of claim 1 , wherein said protecting polymer layer has a thickness less than 100 nm.

8 . The particulate of claim 1 , wherein said protecting polymer layer has a thickness less than 10 nm.

9 . The particulate of claim 1 , wherein said protecting polymer layer has a lithium ion conductivity from 10 −5 S/cm to 10 −2 S/cm.

10 . The particulate of claim 1 , wherein said cathode active material is selected from an inorganic material, an organic material, a polymeric material, or a combination thereof, and said inorganic material does not include sulfur or alkali metal polysulfide.

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

12 . The particulate of claim 10 , wherein said inorganic material is selected from 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, or a combination thereof.

13 . The particulate of claim 10 , 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.

14 . The particulate of claim 10 , 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.

15 . The particulate of claim 10 , wherein said inorganic material is selected from a transition metal dichalcogenide, a transition metal trichalcogenide, or a combination thereof.

16 . The particulate of claim 10 , 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.

17 . The particulate of claim 11 , 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<×<5.

18 . The particulate 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.

19 . The particulate of claim 10 , 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) and combinations thereof.

20 . The particulate of claim 10 , 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 (ADAQ), calixquinone, Li 4 C 6 O 6 , Li 2 C 6 O 6 , Li 6 C 6 O 6 , or a combination thereof, wherein said thioether polymer is selected from 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-y

Assignees

• Nanotek Instruments Inc
• Honeycomb Battery Company

Inventors

• Zhamu Aruna
• Jang Bor Z

Classifications

• H01M4/5815

  Sulfides · CPC title

• H01M2004/021

  Physical characteristics, e.g. porosity, surface area · CPC title

• H01M10/052

  Li-accumulators · 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