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WO2020041559A1 - Particules encapsulées dans un élastomère électrochimiquement stable de matériaux actifs de cathode destinés à des batteries au lithium - Google Patents

Particules encapsulées dans un élastomère électrochimiquement stable de matériaux actifs de cathode destinés à des batteries au lithium Download PDF

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Publication number
WO2020041559A1
WO2020041559A1 PCT/US2019/047642 US2019047642W WO2020041559A1 WO 2020041559 A1 WO2020041559 A1 WO 2020041559A1 US 2019047642 W US2019047642 W US 2019047642W WO 2020041559 A1 WO2020041559 A1 WO 2020041559A1
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Prior art keywords
lithium
graphene
elastomer
poly
oxide
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PCT/US2019/047642
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English (en)
Inventor
Baofei Pan
Hui He
Bor Z. Jang
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Global Graphene Group Inc
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Global Graphene Group Inc
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Priority claimed from US16/109,178 external-priority patent/US11239460B2/en
Priority claimed from US16/109,142 external-priority patent/US11043662B2/en
Application filed by Global Graphene Group Inc filed Critical Global Graphene Group Inc
Publication of WO2020041559A1 publication Critical patent/WO2020041559A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates generally to the field of rechargeable lithium battery and, more particularly, to the cathode active materials in the form of particulates containing transition metal oxide-filled elastomer-encapsulated cathode active material particles and the method of producing same.
  • a unit cell or building block of a lithium-ion battery is typically composed of an anode current collector, an anode or negative electrode layer (containing an anode active material responsible for storing lithium therein, a conductive additive, and a resin binder), an electrolyte and porous separator, a cathode or positive electrode layer (containing a cathode active material responsible for storing lithium therein, a conductive additive, and a resin binder), and a separate cathode current collector.
  • the electrolyte is in ionic contact with both the anode active material and the cathode active material.
  • a porous separator is not required if the electrolyte is a solid- state electrolyte.
  • the binder in the anode layer is used to bond the anode active material (e.g. graphite or Si particles) and a conductive filler (e.g. carbon black particles or carbon nanotube) together to form an anode layer of structural integrity, and to bond the anode layer to a separate anode current collector, which acts to collect electrons from the anode active material when the battery is discharged.
  • anode active material e.g. graphite or Si particles
  • a conductive filler e.g. carbon black particles or carbon nanotube
  • PVDF polyvinylidine fluoride
  • SBR styrene-butadiene rubber
  • anode current collector typically a sheet of Cu foil.
  • a binder resin e.g. PVDF or PTFE
  • the same resin binder also acts to bond this cathode active layer to a cathode current collector (e.g. Al foil).
  • lithium-ion batteries actually evolved from rechargeable“lithium metal batteries” that use lithium (Li) metal as the anode and a Li intercalation compound (e.g. MoS 2 ) as the cathode.
  • Li metal is an ideal anode material due to its light weight (the lightest metal), high electronegativity (-3.04 V vs. the standard hydrogen electrode), and high theoretical capacity (3,860 mAh/g). Based on these outstanding properties, lithium metal batteries were proposed 40 years ago as an ideal system for high energy-density applications.
  • prelithiated cathodes e.g. lithium cobalt oxide, as opposed to cobalt oxide
  • cathode active materials e.g. lithium transition metal oxides
  • a transition metal e.g. Fe, Mn, Co, Ni, etc.
  • These cathode active materials also contain a high oxygen content that could assist in the progression of thermal runaway and provide oxygen for electrolyte oxidation, increasing the danger of explosion or fire hazard. This is a serious problem that has hampered the widespread implementation of electric vehicles.
  • phosphate and lithium transition metal oxides has been limited to the range of 150-250 mAh/g and, in most cases, less than 200 mAh/g. Additionally, emerging high-capacity cathode active materials (e.g. FeF 3 ) still cannot deliver a long battery cycle life.
  • emerging high-capacity cathode active materials e.g. FeF 3
  • High-capacity cathode active materials such as metal fluoride, metal chloride, and lithium transition metal silicide, can undergo large volume expansion and shrinkage during the discharge and charge of a lithium battery. These repeated volume changes lead to structural instability of the cathode, breakage of the normally weak bond between the binder resin and the active material, fragmentation of active material particles, delamination between the cathode active material layer and the current collector, and interruption of electron-conducting pathways.
  • These high-capacity cathodes include 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 , etc.
  • High-capacity cathode active materials also include a lithium transition metal silicate, Li 2 MSi0 4 or Li 2 Ma x Mb y Si0 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.
  • a lithium transition metal silicate Li 2 MSi0 4 or Li 2 Ma x Mb y Si0 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.
  • cathode active material layer or electrode for a lithium battery that contains a very unique class of cathode active materials.
  • the cathode active material is in a form of particulates, wherein at least a particulate contains one or a plurality of particles of a cathode active material being embraced or encapsulated by a thin layer of an inorganic filler-reinforced elastomer.
  • This new class of material is capable of overcoming the cathode-induced rapid capacity decay problem commonly associated with a rechargeable lithium battery.
  • the cathode electrode comprises multiple particulates of a cathode active material, wherein at least a particulate is composed of one or a plurality of the cathode active material particles that are 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 mih, a fully recoverable tensile strain from 2% to 500%, and a lithium ion conductivity from 10 S/cm to 5 x _2
  • the inorganic filler has a lithium intercalation potential no less than 1.1 V versus Li/Li + (preferably from 1.1 V to 4.5 V, more preferably from 1.1 to 3.5 V, and most preferably from 1.1 to 2.5 V).
  • the inorganic filler is preferably selected from an oxide, carbide, boride, nitride, sulfide, phosphide, or selenide of a transition metal, a lithiated version thereof, or a combination thereof.
  • the 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.
  • particles of this inorganic filler are in a form of nanoparticle, nanowire, nanofiber, nanotube, nanosheet, nanobelt, nanoribbon, nanodisc, nanoplatelet, or nanohorn having a dimension (diameter, thickness, or width, etc.) less than 100 nm, preferably less than 10 nm.
  • the encapsulating thin layer of inorganic filler-reinforced elastomer has a fully recoverable tensile strain from 2% to 500% (more typically from 5% to 300% and most typically from 10% to 150%), a thickness from 1 nm to 10 pm, and a lithium ion conductivity from 10
  • this thin encapsulating layer also has an electrical conductivity from 10 -7 S/cm to 100 S/cm (more typically from 10 -3 S/cm to 10 S/cm when an electron-conducting additive is added into the elastomer matrix material).
  • the elastomeric matrix material contains a sulfonated or non-sulfonated version of an elastomer selected from 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) (POE) elastomer, po!y(eihy!ene-co-butene) (PBE) elastomer, styrene- ethylene-butadiene-styrene (SEES) elastomer, epichlorohydrin rubber, polyacrylic rubber, silicone rubber, fluoro silicone rubber, perfluoroelastomers, polyether block amides,
  • chlorosulfonated polyethylene ethylene-vinyl acetate, thermoplastic elastomer, protein resilin, protein elastin, ethylene oxide-epichlorohydrin copolymer, polyurethane, urethane-urea copolymer, or a combination thereof.
  • These sulfonated elastomers or rubbers when present without graphene sheets, exhibit a high elasticity (having a fully recoverable tensile strain from 2% to 800%). In other words, they can be stretched up to 800% (8 times of the original length when under tension) and, upon release of the tensile stress, they can fully recover back to the original dimension.
  • the fully recoverable tensile strains are typically reduced down to 2%-500% (more typically from 5% to 300% and most typically from 10% to 150%).
  • the inorganic filler-reinforced elastomer further contains an electron-conducting filler dispersed in the elastomer matrix material wherein the electron-conducting filler is selected from a carbon nanotube, carbon nanofiber, nanocarbon particle, metal nanoparticle, metal nanowire, electron-conducting polymer, graphene, or a combination thereof.
  • the graphene may be preferably selected from pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, nitrogenated graphene, hydrogenated graphene, doped graphene, functionalized graphene, or a combination thereof and the graphene preferably comprises single-layer graphene or few-layer graphene, wherein the few-layer graphene is defined as a graphene platelet formed of less than 10 graphene planes.
  • the electron-conducting polymer is preferably selected from (but not limited to) polyaniline, polypyrrole, polythiophene, polyfuran, a bi-cyclic polymer, a sulfonated derivative thereof, or a combination thereof.
  • the graphene sheets have a lateral dimension (length or width) from 5 nm to 5 pm, more preferably from 10 nm to 1 pm, and most preferably from 10 nm to 300 nm. Shorter graphene sheets allow for easier encapsulation and enable faster lithium ion transport through the inorganic filler-reinforced elastomer-based encapsulating layer.
  • the particulates are substantially or essentially spherical or ellipsoidal in shape.
  • the particulate have a diameter or thickness smaller than 30 pm, more preferably smaller than 20 pm, and most preferably smaller than 10 pm.
  • the cathode active material particulate may contain a cathode active material selected from an inorganic material, an organic material, a polymeric material, or a combination thereof.
  • the inorganic material may be selected from a metal oxide, metal phosphate, metal silicide, metal selenide, transition metal sulfide, or a combination thereof.
  • the inorganic material may be 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.
  • the 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.
  • 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.
  • the inorganic material is selected from a lithium transition metal silicate, denoted as Li 2 MSi0 4 or Li 2 Ma x Mb y Si0 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.
  • Li 2 MSi0 4 Li 2 Ma x Mb y Si0 4
  • 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
  • the inorganic material is selected from a transition metal dichalcogenide, a transition metal trichalcogenide, or a combination thereof.
  • the inorganic material is selected from TiS 2 , TaS 2 , MoS 2 , NbSe 3 , Mn0 2 , Co0 2 , an iron oxide, a vanadium oxide, or a combination thereof.
  • the cathode active material layer may contain a metal oxide containing vanadium oxide selected from the group consisting of V0 2 , Li x V0 2 , V 2 Os, Li x V 2 Os, V 3 0 8 , Li x V 3 0 8 , Li x V 3 0 7 , V 4 Oy, Li x V 4 0 9 , V 6 0i 3 , ⁇ c n 60i3, their doped versions, their derivatives, and combinations thereof, wherein 0.1 ⁇ x ⁇ 5.
  • the cathode active material layer may contain a metal oxide or metal phosphate, selected from a layered compound LiM0 2 , spinel compound LiM 2 0 4 , olivine compound LiMP0 4 , silicate compound Li 2 MSi0 4 , tavorite compound LiMP0 4 F, borate compound LiMB0 3 , or a
  • M is a transition metal or a mixture of multiple transition metals.
  • the 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.
  • the cathode active material layer may contain an organic material or polymeric material 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-l,4-dyhydroxy anthraquinone) (PADAQ), phosphazene disulfide polymer ([(NPS 2 ) 3 ]H), lithiated l,4,5,8-naphthalenet
  • the thioether polymer is selected from poly[methanetetryl-tetra(thiomethylene)] (PMTTM), poly(2,4-dithiopentanylene) (PDTP), a polymer containing poly(ethene-l,l,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(l,4-di(l,3-dithiolan-2-yl)benzene) (PDDTB), poly(tetrahydrobenzodithiophene) (PTHBDT), poly[l,2,4,5- tetrakis(propylthio)benzene] (PTKPTB, or poly[3,4(ethylenedithio)
  • the cathode active material layer contains an organic material selected from a phthalocyanine compound, such as copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, iron phthalocyanine, lead phthalocyanine, nickel phthalocyanine, vanadyl phthalocyanine, fluorochromium phthalocyanine, magnesium phthalocyanine, manganous phthalocyanine, dilithium phthalocyanine, aluminum phthalocyanine chloride, cadmium phthalocyanine, chlorogallium phthalocyanine, cobalt phthalocyanine, silver phthalocyanine, a metal-free phthalocyanine, a chemical derivative thereof, or a combination thereof.
  • a phthalocyanine compound such as copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, iron phthalocyanine, lead phthalocyanine, nickel phthalocyanine, vanadyl phthalocyanine, fluorochrom
  • the cathode active material is preferably in a form of nanoparticle (spherical, ellipsoidal, and irregular shape), nanowire, nanofiber, nanotube, nanosheet, nanobelt, nanoribbon, nanodisc, nanoplatelet, or nanohorn having a thickness or diameter less than 100 nm. These shapes can be collectively referred to as“particles” unless otherwise specified or unless a specific type among the above species is desired. Further preferably, the cathode active material has a dimension less than 50 nm, even more preferably less than 20 nm, and most preferably less than 10 nm.
  • one particle or a cluster of particles may be coated with or embraced by a layer of carbon disposed between the active material particle(s) and the protecting polymer layer (the encapsulating shell).
  • a carbon layer may be deposited to embrace the encapsulated particle or the encapsulated cluster of multiple cathode active material particles.
  • the particulate may further contain a graphite or carbon material mixed with the active material particles, which are all encapsulated by the encapsulating shell (but not dispersed within this thin layer of inorganic filler-reinforced elastomer).
  • the carbon or graphite material is selected from polymeric carbon, amorphous carbon, chemical vapor deposition carbon, coal tar pitch, petroleum pitch, mesophase pitch, carbon black, coke, acetylene black, activated carbon, fine expanded graphite particle with a dimension smaller than 100 nm, artificial graphite particle, natural graphite particle, or a combination thereof.
  • the cathode active material particles may be coated with or embraced by a conductive protective coating (selected from a carbon material, electronically conductive polymer, conductive metal oxide, or conductive metal coating) prior to being encapsulated by the inorganic filler-reinforced elastomer shell.
  • a conductive protective coating selected from a carbon material, electronically conductive polymer, conductive metal oxide, or conductive metal coating
  • the inorganic filler-reinforced elastomer has a lithium ion conductivity no less than 10 6 S/cm, more preferably no less than 5xl0 5 S/cm.
  • the inorganic filler-reinforced elastomer further contains from 0.1% to 40% by weight (preferably from 1% to 30% by weight) of a lithium ion-conducting additive dispersed in the elastomer matrix material.
  • the elastomeric matrix material contains a material selected from a sulfonated or non-sulfonated version of natural polyisoprene (e.g. cis-l,4-polyisoprene natural rubber (NR) and trans-l,4-polyisoprene gutta-percha), synthetic polyisoprene (IR for isoprene rubber), polybutadiene (BR for butadiene rubber), chloroprene rubber (CR), polychloroprene (e.g.
  • natural polyisoprene e.g. cis-l,4-polyisoprene natural rubber (NR) and trans-l,4-polyisoprene gutta-percha
  • synthetic polyisoprene IR for isoprene rubber
  • BR polybutadiene
  • CR chloroprene rubber
  • polychloroprene e.g.
  • Neoprene, Baypren etc. butyl rubber (copolymer of isobutylene and isoprene, HR), including halogenated butyl rubbers (chloro butyl rubber (CIIR) and bromo butyl rubber (BUR), styrene-butadiene rubber (copolymer of styrene and butadiene, SBR), nitrile rubber (copolymer of butadiene and acrylonitrile, NBR), EPM (ethylene propylene rubber, a copolymer of ethylene and propylene), EPDM rubber (ethylene propylene diene rubber, a terpolymer of ethylene, propylene and a diene-component), metallocene -based poly(ethylene-co-octene) (POE) elastomer, poly(ethylene-co-butene) (PBE) elastomer, styrene-ethylene-butadiene-styrene (
  • Hypalon and ethylene-vinyl acetate (EVA), thermoplastic elastomers (TPE), protein resilin, protein elastin, ethylene oxide-epichlorohydrin copolymer, polyurethane, urethane-urea copolymer, and combinations thereof. Sulfonation imparts higher lithium ion conductivity to the elastomer.
  • R a hydrocarbon group, 0 ⁇ x ⁇ 1 and 1 ⁇ y ⁇ 4.
  • the inorganic filler-reinforced elastomer further contains a lithium ion-conducting additive dispersed in a sulfonated elastomer matrix material, wherein the lithium ion-conducting additive contains a lithium salt selected from lithium perchlorate (LiQ0 4) , lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), lithium hexafluoroarsenide (LiAsF 6 ), lithium trifluoro-methanesulfonate (L1CF 3 SO 3 ), bis-trifluoromethyl sulfonylimide lithium (LiN(CF 3 S0 2 ) 2 ), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF 2 C 2 0 4 ), lithium nitrate (L1NO 3 ), Li-fluoroalkyl-phosphat
  • the proportion of this lithium ion-conducing additive is preferably from 0.1% to 40% by weight, but more preferably from 1% to 25% by weight.
  • the sum of this additive and graphene sheets preferably occupies from 1% to 40% by weight, more preferably from 3% to 35% by weight, and most preferably from 5% to 25% by weight of the resulting composite weight (the elastomer matrix, electron-conducting additive, and lithium ion-conducting additive combined).
  • the elastomeric matrix material may contain a mixture or blend of a sulfonated elastomer and an electron- conducting polymer selected from
  • this electron-conducting polymer is preferably from 0.1% to 20% by weight.
  • the elastomeric matrix material contains a mixture or blend of a sulfonated elastomer and a lithium ion-conducting polymer selected from poly(ethylene oxide) (PEO), polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVDF), poly bis-methoxy ethoxyethoxide-phosphazene, polyvinyl chloride, polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP), a sulfonated derivative thereof, or a combination thereof.
  • a lithium ion-conducting polymer selected from poly(ethylene oxide) (PEO), polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (P
  • Sulfonation is herein found to impart improved lithium ion conductivity to a polymer.
  • the proportion of this lithium ion-conducting polymer is preferably from 0.1% to 20% by weight.
  • Mixing or dispersion of an additive or reinforcement species in an elastomer or rubber may be conducted using solution mixing or melt mixing.
  • the present disclosure also provides a powder mass of cathode active material for a lithium battery.
  • the powder mass comprises multiple particulates of a cathode active material, wherein at least one particulate is composed of one or a plurality of the cathode active material particles that are 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
  • the encapsulating thin layer of inorganic filler-reinforced elastomer has a thickness from 1 nm to 10 pm, a fully recoverable tensile strain from 2% to 500%, and a lithium ion conductivity from 10 S/cm to 5 x _2
  • the inorganic filler is preferably selected from an oxide, carbide, boride, nitride, sulfide, phosphide, or selenide of a transition metal, a lithiated version thereof, or a combination thereof.
  • the transition metal is selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb,
  • the particles of this inorganic filler are preferably in a form of nanoparticle, nanowire, nanofiber, nanotube, nanosheet, nanobelt, nanoribbon, nanodisc, nanoplatelet, or nanohorn having a dimension (diameter, thickness, or width, etc.) less than 100 nm, preferably less than 10 nm.
  • the 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 the nanodiscs, nanoplatelets, or nanosheets have a thickness from 1 nm to 100 nm.
  • the present disclosure also provides a cathode electrode that contains the presently invented inorganic filler-reinforced elastomer-encapsulated cathode material particles, an optional conductive additive (e.g. expanded graphite flakes, carbon black, acetylene black, or carbon nanotube), and an optional resin binder (typically required).
  • an optional conductive additive e.g. expanded graphite flakes, carbon black, acetylene black, or carbon nanotube
  • an optional resin binder typically required
  • the present disclosure also provides a lithium battery containing an optional cathode current collector (e.g. Al foil), the presently invented cathode electrode as described above, an anode active material layer or anode electrode, an optional anode current collector (e.g. Cu foil), an electrolyte in ionic contact with the anode active material layer and the cathode active material layer and an optional porous separator.
  • an optional cathode current collector e.g. Al foil
  • an anode current collector e.g. Cu foil
  • electrolyte in ionic contact with the anode active material layer and the cathode active material layer and an optional porous separator.
  • the anode active material may be selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti,
  • Ni, Co, or Cd with other elements oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, V, or Cd, and their mixtures, composites, or lithium-containing composites; (d) salts and hydroxides of Sn; (e) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide; (f) prelithiated versions thereof; (g) particles and foil of Li, Li alloy, or surface-stabilized Li particles having at least 60% by weight of lithium element therein; and (h) combinations thereof.
  • the lithium battery may be a lithium-ion battery, lithium metal battery (containing lithium metal or lithium alloy as the main anode active material and containing no intercalation- based anode active material), lithium- sulfur battery, lithium-selenium battery, or lithium-air battery.
  • the disclosure also provides a method of producing a powder mass of a cathode active material for a lithium battery, the method comprising: (a) mixing particles of an inorganic filler (optionally along with an electron-conducting filler and/or a lithium ion-conducting filler) and an elastomer or its precursor (e.g.
  • the powder mass comprises multiple particulates of the cathode active material, wherein at least one of the particulates is composed of one or a plurality of the cathode active material particles which are encapsulated by a thin layer of inorganic filler-reinforced elastomer having from 0.01% to 50% by weight of particles of an inorganic filler dispersed in an elastomeric matrix material and the encapsulating thin layer of inorganic filler-reinforced elastomer has a thickness from 1 nm to 10 pm (preferably from 1 nm to 100 nm), a fully recoverable tensile strain from 2% to 500%
  • the step of mixing the inorganic filler particles and the elastomer (sulfonated or non-sulfonated) or its precursor (monomer and/or oligomer) preferably includes a procedure of chemically bonding the elastomer or its precursor to the inorganic filler particles. There can be several different sequences of operations.
  • a chemical reaction may be optionally but preferably initiated between inorganic filler particles and the monomer/oligomer at this stage or later.
  • Cathode active material particles are then dispersed in the suspension to form a slurry.
  • a micro-encapsulation procedure e.g. spray drying
  • the resulting particulate is then subjected to a polymerization/curing treatment (e.g. via heating and/or UV curing, etc.). If the starting monomer/oligomer already had sulfonate groups or were already sulfonated, the resulting reinforced elastomer shell would be a sulfonated elastomer composite. Otherwise, the resulting mass of particulates may be subsequently subjected to a sulfonating treatment, if so desired. Alternatively, one may dissolve a linear or branched chain polymer (but uncured or un- crosslinked) in a solvent to form a polymer solution.
  • a polymerization/curing treatment e.g. via heating and/or UV curing, etc.
  • Such a polymer can be a sulfonated polymer to begin with, or can be sulfonated during any subsequent stage (e.g. after the particulates are formed).
  • Inorganic filler particles (optionally along with an electron-conducting additive and/or a lithium ion-conducting additive) are then added into the polymer solution to form a suspension; particles of the cathode active material can be added concurrently or sequentially.
  • the suspension is then subjected to a micro-encapsulation treatment to form particulates. Curing or cross-linking of the elastomer/graphene composite is then allowed to proceed.
  • the step of providing the solution and suspension may include (a) sulfonating an elastomer to form a sulfonated elastomer and dissolving the sulfonated elastomer in a solvent to form a polymer solution, or (b) sulfonating the precursor (monomer or oligomer) to obtain a sulfonated precursor (sulfonated monomer or sulfonated oligomer), polymerizing the sulfonated precursor to form a sulfonated elastomer and dissolving the sulfonated elastomer in a solvent to form a solution.
  • Inorganic filler particles optionally along with an electron-conducting additive and/or a lithium ion-conducting additive
  • cathode active material particles are concurrently or sequentially added into the solution to form a suspension.
  • the step of dispensing the slurry and removing the solvent and/or polymerizing/curing the precursor to form the powder mass includes operating a procedure (e.g. micro-encapsulation) selected from pan-coating, air-suspension coating, centrifugal extrusion, vibration-nozzle encapsulation, spray-drying, coacervation-phase separation, interfacial polycondensation and interfacial cross-linking, in-situ polymerization, matrix polymerization, or a combination thereof.
  • a procedure e.g. micro-encapsulation
  • a procedure selected from pan-coating, air-suspension coating, centrifugal extrusion, vibration-nozzle encapsulation, spray-drying, coacervation-phase separation, interfacial polycondensation and interfacial cross-linking, in-situ polymerization, matrix polymerization, or a combination thereof.
  • the step of mixing the inorganic filler particles and elastomer or its precursor may include dissolving or dispersing from 0.1% to 40% by weight of a lithium ion conducting additive in the liquid medium or solvent.
  • the lithium ion- conducting additive contains a lithium salt selected from lithium perchlorate (LiCl0 4) , lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), lithium hexafluoroarsenide (LiAsF 6 ), lithium trifluoro-methanesulfonate (L1CF 3 SO 3 ), bis-trifluoromethyl sulfonylimide lithium
  • LiN(CF 3 S0 2 ) 2 lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF 2 C 2 0 4 ), lithium nitrate (L1NO 3 ), Li-fluoroalkyl-phosphate (LiPF 3 (CF 2 CF 3 ) 3 ), lithium bisperfluoro- ethylsulfonylimide (LiBETI), lithium bis(trifluoromethanesulfonyl)imide, lithium
  • LiTFSI lithium trifluoromethanesulfonimide
  • the slurry further contains an electron-conducting polymer selected from polyaniline, polypyrrole, polythiophene, polyfuran, a bi-cyclic polymer, a sulfonated derivative thereof, or a combination thereof.
  • an electron-conducting polymer selected from polyaniline, polypyrrole, polythiophene, polyfuran, a bi-cyclic polymer, a sulfonated derivative thereof, or a combination thereof.
  • the slurry further contains a lithium ion-conducting polymer selected from poly(ethylene oxide) (PEO), polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVDF), poly bis-methoxy ethoxyethoxide-phosphazene, polyvinyl chloride, polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP), a sulfonated derivative thereof, or a combination thereof.
  • a lithium ion-conducting polymer selected from poly(ethylene oxide) (PEO), polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVDF), poly bis-methoxy ethoxyethoxide-phosphazene
  • the method may further comprise mixing multiple particulates of the aforementioned cathode active material, a binder resin, and an optional conductive additive to form a cathode electrode, which is optionally coated on a cathode current collector (e.g. Al foil).
  • the method may further comprise combining an anode electrode, the presently invented cathode electrode (positive electrode), an electrolyte, and an optional porous separator into a lithium battery cell.
  • the encapsulating material is of high strength and stiffness so that it can help to refrain the electrode active material particles, when lithiated, from expanding to an excessive extent.
  • the protective inorganic filler-reinforced elastomer shell having both high elasticity and high strength, has a high fracture toughness and high resistance to crack formation to avoid disintegration during repeated cycling.
  • the inorganic filler-reinforced elastomer shell is relatively inert (inactive) with respect to the electrolyte. Further, since there is no direct contact between the cathode active material particles and liquid electrolyte, there is no opportunity for the transition metal in the cathode active material to catalyze the decomposition of electrolyte, which otherwise could generate undesirable chemical species (e.g. volatile molecules) inside the battery cell.
  • the inorganic filler-reinforced elastomer shell material can be both lithium ion
  • FIG. 1(A) Schematic of a prior art lithium battery cell, wherein the anode layer is a thin Li foil and the cathode is composed of particles of a cathode active material, a conductive additive (not shown) and a resin binder (not shown).
  • FIG. 1(B) Schematic of a prior art lithium-ion battery; the anode layer being composed of
  • particles of an anode active material a conductive additive (not shown) and a resin binder (not shown).
  • FIG. 2(A) Schematic illustrating the notion that expansion/shrinkage of electrode active material particles, upon lithium insertion and de-insertion during discharge/charge of a prior art lithium-ion battery, can lead to detachment of resin binder from the particles, interruption of the conductive paths formed by the conductive additive, and loss of contact with the current collector;
  • FIG. 2(B) Several different types of particulates containing filled elastomer-encapsulated
  • FIG. 3 The specific intercalation capacity curves of four lithium cells: cathode containing un encapsulated V O particles, cathode containing un-encapsulated but graphene-embraced V2O5 particles, cathode containing filled elastomer-encapsulated V2O5 particles, and cathode containing filled elastomer-encapsulated graphene-embraced V2O5 particles.
  • FIG. 4 The specific capacity values of two lithium battery cells having a cathode active material featuring (1) filled elastomer-encapsulated carbon-coated LiFeP0 particles and (2) carbon-coated LiFeP0 particles without filled elastomer encapsulation, respectively.
  • FIG. 5 The discharge capacity curves of two coin cells having two different types of cathode active materials: (1) filled elastomer-encapsulated metal fluoride particles and (2) non- encapsulated metal fluorides.
  • FIG. 6 Specific capacities of two lithium-FePc (organic) cells, each having Li foil as an anode active material and FePc/RGO mixture particles as the cathode active material (one cell containing un-encapsulated particles and the other containing particles encapsulated by an elastomer composite).
  • This disclosure is directed at a cathode active material layer (positive electrode layer, not including the cathode current collector) for a lithium secondary battery.
  • This positive electrode comprises a cathode active material that is in a form of an elastomer composite shell-protected particulate.
  • the battery is preferably a secondary battery based on a non-aqueous electrolyte, a polymer gel electrolyte, an ionic liquid electrolyte, a quasi-solid electrolyte, or a solid-state electrolyte.
  • the shape of a lithium secondary battery can be cylindrical, square, button-like, etc.
  • the present disclosure is not limited to any battery shape or configuration or any type of electrolyte.
  • a lithium-ion battery cell is typically composed of an anode current collector (e.g. Cu foil), an anode or negative electrode active material layer (i.e. anode layer typically containing particles of an anode active material, conductive additive, and binder), a porous separator and/or an electrolyte component, a cathode or positive electrode active material layer (containing a cathode active material, conductive additive, and resin binder), and a cathode current collector (e.g. Al foil). More specifically, the cathode layer comprises particles of a cathode active material, a conductive additive (e.g. carbon black particles), and a resin binder (e.g. SBR or PVDF). This cathode layer is typically 50-300 pm thick (more typically 100- 200 pm) to give rise to a sufficient amount of current per unit electrode area.
  • anode current collector e.g. Cu foil
  • an anode or negative electrode active material layer i.e. anode layer typically
  • the anode active material is a lithium metal foil or a layer of packed Li particles supported on an anode current collector, such as a sheet of copper foil.
  • an anode current collector such as a sheet of copper foil.
  • This can be a lithium meal secondary battery, lithium- sulfur battery, lithium-selenium battery, etc.
  • the anode in FIG. 1(B) can be designed to contain higher-capacity anode active materials having a composition formula of Li a A (A is a metal or semiconductor element, such as Al and Si, and "a" satisfies 0 ⁇ a ⁇ 5).
  • Li 4 Si (3,829 mAh/g)
  • Li 4.4 Si (4,200 mAh/g)
  • Li 4.4 Ge (1,623 mAh/g)
  • Li 4.4 Sn 993 mAh/g
  • Li 3 Cd 715 mAh/g
  • Li 3 Sb 660 mAh/g
  • Li 44 Pb 569 mAh/g
  • LiZn 410 mAh/g
  • Li 3 Bi 385 mAh/g
  • one major problem in the current lithium battery is the notion that active material particles can get fragmented and the binder resin can detach from both the active material particles and conductive additive particles due to repeated volume expansion/shrinkage of the active material particles during the charge and discharge cycles. These binder detachment and particle fragmentation phenomena lead to loss of contacts between active material particles and conductive additives and loss of contacts between the active material and its current collector. These adverse effects result in a significantly shortened charge-discharge cycle life.
  • the cathode active material layer comprises multiple cathode active material particles that are fully embraced or encapsulated by an elastomer composite having a recoverable (elastic) tensile strain no less than 2% under uniaxial tension and a lithium ion conductivity no less than
  • the elastomer composite comprises an elastomer matrix which is reinforced with an inorganic filler.
  • the present disclosure provides four major types of particulates of elastomer composite-encapsulated cathode active material particles.
  • the first one is a single-particle particulate containing a cathode active material core 10 encapsulated by a high-elasticity composite elastomer shell 12.
  • the second is a multiple-particle particulate containing multiple cathode active material particles 14 (e.g. FeF 3 particles), optionally along with other conductive materials (e.g. particles of graphite or hard carbon, not shown), which are encapsulated by an elastomer composite 16.
  • multiple cathode active material particles 14 e.g. FeF 3 particles
  • other conductive materials e.g. particles of graphite or hard carbon, not shown
  • the third is a single-particle particulate containing a cathode active material core 18 coated by a carbon or graphene layer 20 (or other conductive material) further encapsulated by an elastomer composite 22.
  • the fourth is a multiple-particle particulate containing multiple cathode active material particles 24 (e.g. FeF 3 particles) coated with a conductive protection layer 26 (carbon, graphene, etc.), optionally along with other active materials or conductive additive, which are encapsulated by an elastomer composite shell 28.
  • the elastomer refers to a polymer, typically a lightly cross-linked polymer, which exhibits an elastic deformation that is at least 5% when measured (without an additive or reinforcement in the polymer) under uniaxial tension.
  • the“elastic deformation” is defined as a deformation of a material (when being mechanically stressed) that is essentially fully recoverable and the recovery is essentially instantaneous upon release of the load.
  • the elastic deformation is preferably greater than 5%, more preferably greater than 10%, further more preferably greater than 50%, still more preferably greater than 100%, and most preferably greater than 200%.
  • the preferred types of elastomer composites will be discussed later.
  • the application of the presently invented elastomer composite encapsulation approach is not limited to any particular class of cathode active materials.
  • the cathode active material layer may contain a cathode active material selected from an inorganic material, an organic material, a polymeric material, or a combination thereof.
  • the inorganic material may be selected from a metal oxide, metal phosphate, metal silicide, metal selenide, transition metal sulfide, or a combination thereof.
  • the inorganic material as a cathode active material, may be 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.
  • the inorganic filler for reinforcing the elastomer may be selected from an oxide, carbide, boride, nitride, sulfide, phosphide, or selenide of a transition metal, a lithiated version thereof, or a combination thereof.
  • the 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.
  • These inorganic fillers for reinforcing the elastomer shell are preferably selected to have an intercalation potential (the electrochemical potential at which lithium intercalates into these materials) higher than the intercalation potential of the active material encapsulated in the particulate.
  • an intercalation potential the electrochemical potential at which lithium intercalates into these materials
  • the lithium titanate may be considered as a lithiated version of titanium oxide (Ti0 2 ), which has a lithium intercalation potential > 2.5 V.
  • the inorganic filler must have a lithium intercalation potential higher than 1.1 V versus Li/Li + , preferably higher than 1.2 V, more preferably higher than 1.4 V, and most preferably higher than 1.5 V.
  • metal oxide examples include Nb0 2 and its lithiated version and titanium-niobium composite oxide (e.g. represented by a general formula TiNb 2 0 7 ) and its lithiated versions. They typically have a lithium intercalation potential higher than 1.1 V versus Li/Li + .
  • the niobium-containing composite metal oxide for use as an inorganic filler in the encapsulating elastomer shell may be selected from the group consisting of TiNb 2 0 7 ,
  • niobium oxide typically forms the main framework or backbone of the crystal structure, along with at least a transition metal oxide.
  • Transition metal oxide is but one of the many suitable inorganic filler materials for reinforcing the elastomer matrix.
  • the inorganic filler may be selected from an oxide, carbide, boride, nitride, sulfide, phosphide, or selenide of a transition metal, a lithiated version thereof, or a combination thereof.
  • these and other inorganic fillers are in a form of nanoparticle, nanowire, nanofiber, nanotube, nanosheet, nanobelt, nanoribbon, nanodisc, nanoplatelet, or nanohom having a dimension (diameter, thickness, or width, etc.) less than 100 nm, preferably less than 10 nm.
  • These inorganic filler materials typically have a lithium intercalation potential from 1.1 V to 4.5 V versus Li/Li + , and more typically and preferably from 1.1 V to 3.5 V, and most preferably from 1.1 V to 1.5 V.
  • the lithium intercalation potential of a filler dispersed in the elastomeric matrix material may be higher than the lithium intercalation potential of the active material encapsulated by the filled elastomer.
  • the inorganic filler material for reinforcing an elastomer matrix material may also be selected from nanodiscs, nanoplatelets, or nanosheets (having a thickness from 1 nm to 100 nm) of: (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or
  • nanodiscs, nanoplatelets, or nanosheets preferably have a thickness less than 20 nm, more preferably from 1 nm to 10 nm.
  • the inorganic filler-reinforced elastomer further contains an electron-conducting filler dispersed in the elastomer matrix material wherein the electron-conducting filler is selected from a carbon nanotube, carbon nanofiber, nanocarbon particle, metal nanoparticle, metal nanowire, electron-conducting polymer, graphene, or a combination thereof.
  • the graphene may be preferably selected from pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, nitrogenated graphene, hydrogenated graphene, doped graphene, functionalized graphene, or a combination thereof and the graphene preferably comprises single-layer graphene or few-layer graphene, wherein the few-layer graphene is defined as a graphene platelet formed of 2-10 graphene planes. More preferably, the graphene sheets contain 1-5 graphene planes, most preferably 1-3 graphene planes (i.e. single-layer, double-layer, or triple-layer graphene).
  • the electron-conducting polymer is preferably selected from (but not limited to) polyaniline, polypyrrole, polythiophene, polyfuran, a bi-cyclic polymer, a sulfonated derivative thereof, or a combination thereof.
  • the inorganic filler reinforced elastomer has a lithium ion conductivity from 10 -7 S/cm to 5x 10 -2 S/cm, more preferably and typically greater than 10 -5
  • the composite further contains from 0.1% to 40%
  • the inorganic filler-reinforced elastomer must have a high elasticity (high elastic deformation value).
  • an elastic deformation is a deformation that is fully recoverable upon release of the mechanical stress and the recovery process is essentially instantaneous (no significant time delay).
  • An elastomer such as a vulcanized natural rubber, can exhibit a tensile elastic deformation from 2% up to 1,000% (10 times of its original length). Sulfonation of the rubber reduces the elasticity to 800%.
  • 0.0l%-50% of inorganic filler particles and/or conductive filler e.g.
  • the tensile elastic deformation of a sulfonated elastomer/rubber is reduced to typically from 2% to 500%. It may be noted that although a metal typically has a high ductility (i.e. can be extended to a large extent without breakage), the majority of the deformation is plastic deformation (non- recoverable) and elastic deformation occurs to only a small extent (typically ⁇ 1% and more typically ⁇ 0.2%).
  • a broad array of inorganic filler reinforced elastomers can be used to encapsulate a cathode active material particle or multiple particles. Encapsulation means substantially fully embracing the particle(s) without allowing the particle to be in direct contact with electrolyte in the battery.
  • the elastomeric matrix material may be selected from a sulfonated or non-sulfonated version of natural polyisoprene (e.g.
  • Neoprene, Baypren etc. butyl rubber (copolymer of isobutylene and isoprene, HR), including halogenated butyl rubbers (chloro butyl rubber (CIIR) and bromo butyl rubber (BUR), styrene-butadiene rubber (copolymer of styrene and butadiene, SBR), nitrile rubber (copolymer of butadiene and acrylonitrile, NBR), EPM (ethylene propylene rubber, a copolymer of ethylene and propylene), EPDM rubber (ethylene propylene diene rubber, a terpolymer of ethylene, propylene and a diene-component), metallocene-based poly(ethylene-co-octene) (POE) elastomer, poly(ethylene-co-butene) (PBE) elastomer, styrene-ethylene-butadiene-styrene (SE
  • Hypalon and ethylene-vinyl acetate (EVA), thermoplastic elastomers (TPE), protein resilin, protein elastin, ethylene oxide-epichlorohydrin copolymer, polyurethane, urethane-urea copolymer, and combinations thereof.
  • TPE thermoplastic elastomers
  • protein resilin protein resilin
  • protein elastin ethylene oxide-epichlorohydrin copolymer
  • polyurethane urethane-urea copolymer
  • the urethane-urea copolymer film usually consists of two types of domains, soft domains and hard domains. Entangled linear backbone chains consisting of poly(tetramethylene ether) glycol (PTMEG) units constitute the soft domains, while repeated methylene diphenyl diisocyanate (MDI) and ethylene diamine (EDA) units constitute the hard domains.
  • PTMEG poly(tetramethylene ether) glycol
  • MDI methylene diphenyl diisocyanate
  • EDA ethylene diamine
  • the lithium ion-conducting additive can be incorporated in the soft domains or other more amorphous zones.
  • the electron-conducting filler may be selected from a carbon nanotube (CNT), carbon nanofiber, graphene, nanocarbon particles, metal nanowires, etc.
  • CNT carbon nanotube
  • carbon nanofiber carbon nanofiber
  • graphene nanocarbon particles
  • metal nanowires metal nanowires
  • nanographene platelet composed of one basal plane (graphene plane) or multiple basal planes stacked together in the thickness direction.
  • graphene plane carbon atoms occupy a 2- D hexagonal lattice in which carbon atoms are bonded together through strong in-plane covalent bonds.
  • these graphene planes may be weakly bonded together through van der Waals forces.
  • An NGP can have a platelet thickness from less than 0.34 nm (single layer) to 100 nm (multi-layer).
  • the preferred thickness is ⁇ 10 nm, more preferably ⁇ 3 nm (or ⁇ 10 layers), and most preferably single-layer graphene.
  • the presently invented sulfonated elastomer/graphene composite shell preferably contains mostly single-layer graphene, but could make use of some few-layer graphene (less than 10 layers or 10 graphene planes).
  • the graphene sheet may contain a small amount (typically ⁇ 25% by weight) of non-carbon elements, such as hydrogen, nitrogen, fluorine, and oxygen, which are attached to an edge or surface of the graphene plane.
  • Graphene sheets may be oxidized to various extents during their preparation, resulting in graphite oxide (GO) or graphene oxide.
  • graphene preferably or primarily refers to those graphene sheets containing no or low oxygen content; but, they can include GO of various oxygen contents.
  • graphene may be fluorinated to a controlled extent to obtain graphite fluoride, or can be doped using various dopants, such as boron and nitrogen.
  • Graphite oxide may be prepared by dispersing or immersing a laminar graphite material (e.g., powder of natural flake graphite or synthetic graphite) in an oxidizing agent, typically a mixture of an intercalant (e.g., concentrated sulfuric acid) and an oxidant (e.g., nitric acid, hydrogen peroxide, sodium perchlorate, potassium permanganate) at a desired temperature (typically 0-70°C) for a sufficient length of time (typically 30 minutes to 5 days).
  • an intercalant e.g., concentrated sulfuric acid
  • an oxidant e.g., nitric acid, hydrogen peroxide, sodium perchlorate, potassium permanganate
  • GIC graphite intercalation compound
  • the GIC particles are then exposed to a thermal shock, preferably in a temperature range of 600-l,l00°C for typically 15 to 60 seconds to obtain exfoliated graphite or graphite worms, which are optionally (but preferably) subjected to mechanical shearing (e.g. using a mechanical shearing machine or an ultrasonicator) to break up the graphite flakes that constitute a graphite worm.
  • mechanical shearing e.g. using a mechanical shearing machine or an ultrasonicator
  • the un-broken graphite worms or individual graphite flakes are then re-dispersed in water, acid, or organic solvent and ultrasonicated to obtain a graphene polymer solution or suspension.
  • the pristine graphene material is preferably produced by one of the following three processes: (A) Intercalating the graphitic material with a non-oxidizing agent, followed by a thermal or chemical exfoliation treatment in a non-oxidizing environment; (B) Subjecting the graphitic material to a supercritical fluid environment for inter-graphene layer penetration and exfoliation; or (C) Dispersing the graphitic material in a powder form to an aqueous solution containing a surfactant or dispersing agent to obtain a suspension and subjecting the suspension to direct ultrasonication.
  • a particularly preferred step comprises (i) intercalating the graphitic material with a non-oxidizing agent, selected from an alkali metal (e.g., potassium, sodium, lithium, or cesium), alkaline earth metal, or an alloy, mixture, or eutectic of an alkali or alkaline metal; and (ii) a chemical exfoliation treatment (e.g., by immersing potassium-intercalated graphite in ethanol solution).
  • a non-oxidizing agent selected from an alkali metal (e.g., potassium, sodium, lithium, or cesium), alkaline earth metal, or an alloy, mixture, or eutectic of an alkali or alkaline metal
  • a chemical exfoliation treatment e.g., by immersing potassium-intercalated graphite in ethanol solution.
  • a preferred step comprises immersing the graphitic material to a supercritical fluid, such as carbon dioxide (e.g., at temperature T > 3l°C and pressure P > 7.4 MPa) and water (e.g., at T > 374°C and P > 22.1 MPa), for a period of time sufficient for inter graphene layer penetration (tentative intercalation).
  • a supercritical fluid such as carbon dioxide (e.g., at temperature T > 3l°C and pressure P > 7.4 MPa) and water (e.g., at T > 374°C and P > 22.1 MPa)
  • a sudden de pressurization to exfoliate individual graphene layers.
  • suitable supercritical fluids include methane, ethane, ethylene, hydrogen peroxide, ozone, water oxidation (water containing a high concentration of dissolved oxygen), or a mixture thereof.
  • a preferred step comprises (a) dispersing particles of a graphitic material in a liquid medium containing therein a surfactant or dispersing agent to obtain a suspension or slurry; and (b) exposing the suspension or slurry to ultrasonic waves (a process commonly referred to as ultrasonication) at an energy level for a sufficient length of time to produce the separated nanoscaled platelets, which are pristine, non-oxidized NGPs.
  • ultrasonic waves a process commonly referred to as ultrasonication
  • Reduced graphene oxide can be produced with an oxygen content no greater than 25% by weight, preferably below 20% by weight, further preferably below 5%. Typically, the oxygen content is between 5% and 20% by weight.
  • the oxygen content can be determined using chemical elemental analysis and/or X-ray photoelectron spectroscopy (XPS).
  • the laminar graphite materials used in the prior art processes for the production of the GIC, graphite oxide, and subsequently made exfoliated graphite, flexible graphite sheets, and graphene platelets are, in most cases, natural graphite.
  • the starting material may be selected from the group consisting of natural graphite, artificial graphite (e.g., highly oriented pyrolytic graphite, HOPG), graphite oxide, graphite fluoride, graphite fiber, carbon fiber, carbon nanofiber, carbon nanotube, mesophase carbon microbead (MCMB) or carbonaceous micro-sphere (CMS), soft carbon, hard carbon, and combinations thereof.
  • All of these materials contain graphite crystallites that are composed of layers of graphene planes stacked or bonded together via van der Waals forces.
  • graphite multiple stacks of graphene planes, with the graphene plane orientation varying from stack to stack, are clustered together.
  • carbon fibers the graphene planes are usually oriented along a preferred direction.
  • soft carbons are carbonaceous materials obtained from carbonization of liquid-state, aromatic molecules. Their aromatic ring or graphene structures are more or less parallel to one another, enabling further graphitization.
  • Hard carbons are carbonaceous materials obtained from aromatic solid materials (e.g., polymers, such as phenolic resin and polyfurfuryl alcohol). Their graphene structures are relatively randomly oriented and, hence, further graphitization is difficult to achieve even at a temperature higher than 2,500°C. But, graphene sheets do exist in these carbons.
  • Graphene sheets may be oxidized to various extents during their preparation, resulting in graphite oxide or graphene oxide (GO).
  • graphene preferably or primarily refers to those graphene sheets containing no or low oxygen content; but, they can include GO of various oxygen contents.
  • graphene may be fluorinated to a controlled extent to obtain graphene fluoride.
  • Pristine graphene may be produced by direct ultrasonication (also known as liquid phase production) or supercritical fluid exfoliation of graphite particles. These processes are well- known in the art. Multiple pristine graphene sheets may be dispersed in water or other liquid medium with the assistance of a surfactant to form a suspension.
  • Fluorinated graphene or graphene fluoride is herein used as an example of the halogenated graphene material group.
  • fluorination of pre- synthesized graphene This approach entails treating graphene prepared by mechanical exfoliation or by CVD growth with fluorinating agent such as XeF 2 , or F-based plasmas;
  • Exfoliation of multilayered graphite fluorides Both mechanical exfoliation and liquid phase exfoliation of graphite fluoride can be readily accomplished [F. Karlicky, et al.“ Halogenated Graphenes: Rapidly Growing Family of Graphene Derivatives” ACS Nano, 2013, 7 (8), pp 6434-6464].
  • the nitrogenation of graphene can be conducted by exposing a graphene material, such as graphene oxide, to ammonia at high temperatures (200-400°C). Nitrogenated graphene could also be formed at lower temperatures by a hydrothermal method; e.g. by sealing GO and ammonia in an autoclave and then increased the temperature to l50-250°C. Other methods to synthesize nitrogen doped graphene include nitrogen plasma treatment on graphene, arc- discharge between graphite electrodes in the presence of ammonia, ammonolysis of graphene oxide under CVD conditions, and hydrothermal treatment of graphene oxide and urea at different temperatures.
  • a graphene material such as graphene oxide
  • Nitrogenated graphene could also be formed at lower temperatures by a hydrothermal method; e.g. by sealing GO and ammonia in an autoclave and then increased the temperature to l50-250°C.
  • Other methods to synthesize nitrogen doped graphene include nitrogen plasma treatment on graph
  • the inorganic filler-reinforced elastomer further contains a lithium ion-conducting additive dispersed in an elastomer matrix material.
  • the lithium ion-conducting additive may contain a lithium salt selected from lithium perchlorate (LiCl0 4) , lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), lithium hexafluoroarsenide (LiAsF 6 ), lithium trifluoro-methanesulfonate (L1CF3SO3), bis-trifluoromethyl sulfonylimide lithium (LiN(CF3S0 2 ) 2 ), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF 2 C 2 0 4 ), lithium nitrate (L1NO3), Li-fluoroalkyl-phosphate (LiPF3(CF 2 CF3)3), lithium bisperfluoro-ethylsulfonylimide (LiBETI), lithium
  • LiTFSI trifluoromethanesulfonimide
  • ionic liquid-based lithium salt an ionic liquid-based lithium salt, or a combination thereof.
  • the lithium ion-conducting additive or filler is a lithium ion conducting polymer selected from poly(ethylene oxide) (PEO), polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVDF), poly bis-methoxy ethoxyethoxide-phosphazene, polyvinyl chloride,
  • PVDF-HFP poly(vinylidene fluoride)-hexafluoropropylene
  • the elastomeric matrix material may contain an electron-conducting polymer selected from polyaniline, polypyrrole, polythiophene, polyfuran, a bi-cyclic polymer, derivatives thereof (e.g. sulfonated versions), or a combination thereof.
  • Some elastomers are originally in an unsaturated chemical state (unsaturated rubbers) that can be cured by sulfur vulcanization to form a cross-linked polymer that is highly elastic (hence, an elastomer). Prior to vulcanization, these polymers or oligomers are soluble in an organic solvent to form a polymer solution.
  • Graphene sheets can be chemically functionalized to contain functional groups (e.g. -OH, -COOH, NH 2 , etc.) that can react with the polymer or its oligomer. The graphene-bonded oligomer or polymer may then be dispersed in a liquid medium (e.g. a solvent) to form a solution or suspension.
  • Particles of a cathode active material can be dispersed in this polymer solution or suspension to form a slurry of an active material particle-polymer mixture.
  • This suspension can then be subjected to a solvent removal treatment while individual particles remain substantially separated from one another.
  • the graphene-bonded polymer precipitates out to deposit on surfaces of these active material particles. This can be accomplished, for instance, via spray drying.
  • Unsaturated rubbers that can be vulcanized to become elastomer include natural polyisoprene (e.g. cis-l,4-polyisoprene natural rubber (NR) and trans-l,4-polyisoprene gutta percha), synthetic polyisoprene (IR for isoprene rubber), polybutadiene (BR for butadiene rubber), chloroprene rubber (CR), polychloroprene (e.g.
  • natural polyisoprene e.g. cis-l,4-polyisoprene natural rubber (NR) and trans-l,4-polyisoprene gutta percha
  • synthetic polyisoprene IR for isoprene rubber
  • BR polybutadiene
  • CR chloroprene rubber
  • polychloroprene e.g.
  • Neoprene, Baypren etc. butyl rubber (copolymer of isobutylene and isoprene, HR), including halogenated butyl rubbers (chloro butyl rubber (CIIR) and bromo butyl rubber (BUR), styrene-butadiene rubber (copolymer of styrene and butadiene, SBR), nitrile rubber (copolymer of butadiene and acrylonitrile, NBR),
  • Some elastomers are saturated rubbers that cannot be cured by sulfur vulcanization; they are made into a rubbery or elastomeric material via different means: e.g. by having a copolymer domain that holds other linear chains together.
  • Graphene sheets can be solution- or melt- dispersed into the elastomer to form a graphene/elastomer composite.
  • graphene/elastomer composites can be used to encapsulate particles of an active material by one of several means: melt mixing (followed by pelletizing and ball-milling, for instance), solution mixing (dissolving the active material particles in an uncured polymer, monomer, or oligomer, with or without an organic solvent) followed by drying (e.g. spray drying), interfacial polymerization, or in situ polymerization of elastomer in the presence of active material particles.
  • Saturated rubbers and related elastomers in this category include EPM (ethylene propylene rubber, a copolymer of ethylene and propylene), EPDM rubber (ethylene propylene diene rubber, a terpolymer of ethylene, propylene and a diene-component), epichlorohydrin rubber (ECO), polyacrylic rubber (ACM, ABR), silicone rubber (SI, Q, VMQ), fluoro silicone rubber (FVMQ), fluoroelastomers (FKM, and FEPM; such as Viton, Tecnoflon, Fluorel, Aflas and Dai-El), perfluoroelastomers (FFKM: Tecnoflon PFR, Kalrez, Chemraz, Perlast), polyether block amides (PEBA), chlorosulfonated polyethylene (CSM; e.g.
  • CSM chlorosulfonated polyethylene
  • Hypalon and ethylene-vinyl acetate (EVA), thermoplastic elastomers (TPE), protein resilin, and protein elastin.
  • TPE thermoplastic elastomers
  • Polyurethane and its copolymers are particularly useful elastomeric shell materials for encapsulating active material particles.
  • Rubbers and their solvents are polybutadiene (2- methyl pentane + n-hexane or 2,3-dimethylbutane), styrene-butadiene rubber (toluene, benzene, etc.), butyl rubber (n-hexane, toluene, cyclohexane), etc.
  • the SBR can be vulcanized with different amounts of sulfur and accelerator at 433° K in order to obtain different network structures and crosslink densities.
  • Butyl rubber (HR) is a copolymer of isobutylene and a small amount of isoprene (e.g.
  • the physical methods include pan coating, air-suspension coating, centrifugal extrusion, vibration nozzle, and spray-drying methods.
  • the physico-chemical methods include ionotropic gelation and coacervation-phase separation methods.
  • the chemical methods include interfacial polycondensation, interfacial cross-linking, in-situ polymerization, and matrix polymerization.
  • Pan-coating method The pan coating process involves tumbling the active material particles in a pan or a similar device while the encapsulating material (e.g. elastomer monomer/oligomer, elastomer melt, elastomer/solvent solution) is applied slowly until a desired encapsulating shell thickness is attained.
  • the encapsulating material e.g. elastomer monomer/oligomer, elastomer melt, elastomer/solvent solution
  • Air-suspension coating method In the air suspension coating process, the solid particles (core material) are dispersed into the supporting air stream in an encapsulating chamber. A controlled stream of a polymer- solvent solution (elastomer or its monomer or oligomer dissolved in a solvent; or its monomer or oligomer alone in a liquid state) is concurrently introduced into this chamber, allowing the solution to hit and coat the suspended particles. These suspended particles are encapsulated (fully coated) with polymers while the volatile solvent is removed, leaving a very thin layer of polymer (elastomer or its precursor, which is cured/hardened subsequently) on surfaces of these particles. This process may be repeated several times until the required parameters, such as full-coating thickness (i.e. encapsulating shell or wall thickness), are achieved. The air stream which supports the particles also helps to dry them, and the rate of drying is directly proportional to the temperature of the air stream, which can be adjusted for optimized shell thickness.
  • a polymer- solvent solution elastomer or its
  • the particles in the encapsulating zone portion may be subjected to re-circulation for repeated coating.
  • the encapsulating chamber is arranged such that the particles pass upwards through the encapsulating zone, then are dispersed into slower moving air and sink back to the base of the encapsulating chamber, enabling repeated passes of the particles through the encapsulating zone until the desired encapsulating shell thickness is achieved.
  • Centrifugal extrusion Active material particles may be encapsulated using a rotating extrusion head containing concentric nozzles.
  • a stream of core fluid slurry containing particles of an active material dispersed in a solvent
  • the device rotates and the stream moves through the air it breaks, due to Rayleigh instability, into droplets of core, each coated with the shell solution.
  • the molten shell may be hardened or the solvent may be evaporated from the shell solution.
  • the capsules can be hardened after formation by catching them in a hardening bath. Since the drops are formed by the breakup of a liquid stream, the process is only suitable for liquid or slurry. A high production rate can be achieved. Up to 22.5 kg of microcapsules can be produced per nozzle per hour and extrusion heads containing 16 nozzles are readily available.
  • Vibrational nozzle encapsulation method Core-shell encapsulation or matrix- encapsulation of an active material can be conducted using a laminar flow through a nozzle and vibration of the nozzle or the liquid. The vibration has to be done in resonance with the Rayleigh instability, leading to very uniform droplets.
  • the liquid can consist of any liquids with limited viscosities (1-50,000 mPa-s): emulsions, suspensions or slurry containing the active material.
  • the solidification can be done according to the used gelation system with an internal gelation (e.g. sol-gel processing, melt) or an external (additional binder system, e.g. in a slurry).
  • an internal gelation e.g. sol-gel processing, melt
  • an external binder system e.g. in a slurry
  • Spray drying may be used to encapsulate particles of an active material when the active material is dissolved or suspended in a melt or polymer solution.
  • the liquid feed solution or suspension
  • the liquid feed is atomized to form droplets which, upon contacts with hot gas, allow solvent to get vaporized and thin polymer shell to fully embrace the solid particles of the active material.
  • Coacervation-phase separation This process consists of three steps carried out under continuous agitation:
  • the core material is dispersed in a solution of the encapsulating polymer (elastomer or its monomer or oligomer).
  • the encapsulating material phase which is an immiscible polymer in liquid state, is formed by (i) changing temperature in polymer solution, (ii) addition of salt, (iii) addition of non-solvent, or (iv) addition of an incompatible polymer in the polymer solution.
  • encapsulating shell material shell material being immiscible in vehicle phase and made rigid via thermal, cross-linking, or dissolution techniques.
  • Interfacial polycondensation and interfacial cross-linking Interfacial polycondensation entails introducing the two reactants to meet at the interface where they react with each other. This is based on the concept of the Schotten-Baumann reaction between an acid chloride and a compound containing an active hydrogen atom (such as an amine or alcohol), polyester, polyurea, polyurethane, or urea-urethane condensation. Under proper conditions, thin flexible encapsulating shell (wall) forms rapidly at the interface.
  • an active hydrogen atom such as an amine or alcohol
  • a solution of the active material and a diacid chloride are emulsified in water and an aqueous solution containing an amine and a polyfunctional isocyanate is added.
  • a base may be added to neutralize the acid formed during the reaction.
  • Condensed polymer shells form instantaneously at the interface of the emulsion droplets.
  • Interfacial cross-linking is derived from interfacial polycondensation, wherein cross- linking occurs between growing polymer chains and a multi-functional chemical groups to form an elastomer shell material.
  • In-situ polymerization In some micro-encapsulation processes, active materials particles are fully coated with a monomer or oligomer first. Then, direct polymerization of the monomer or oligomer is carried out on the surfaces of these material particles.
  • Matrix polymerization This method involves dispersing and embedding a core material in a polymeric matrix during formation of the particles. This can be accomplished via spray drying, in which the particles are formed by evaporation of the solvent from the matrix material. Another possible route is the notion that the solidification of the matrix is caused by a chemical change.
  • a variety of synthetic methods may be used to sulfonate an elastomer or rubber: (i) exposure to sulfur trioxide in vapor phase or in solution, possibly in presence of Lewis bases such as triethyl phosphate, tetrahydrofuran, dioxane, or amines; (ii) chloro sulfonic acid in diethyl ether; (iii) concentrated sulfuric acid or mixtures of sulfuric acid with alkyl hypochlorite; (iv) bisulfites combined to dioxygen, hydrogen peroxide, metallic catalysts, or peroxo derivates; and (v) acetyl sulfate.
  • Lewis bases such as triethyl phosphate, tetrahydrofuran, dioxane, or amines
  • chloro sulfonic acid in diethyl ether (iii) concentrated sulfuric acid or mixtures of sulfuric acid with alkyl hypochlorite; (iv) bisulf
  • Sulfonation of an elastomer or rubber may be conducted before, during, or after curing of the elastomer or rubber. Further, sulfonation of the elastomer or rubber may be conducted before or after the particles of an electrode active material are embraced or encapsulated by the elastomer/rubber or its precursor (monomer or oligomer). Sulfonation of an elastomer or rubber may be accomplished by exposing the elastomer/rubber to a sulfonation agent in a solution state or melt state, in a batch manner or in a continuous process.
  • the sulfonating agent may be selected from sulfuric acid, sulfonic acid, sulfur trioxide, chlorosulfonic acid, a bisulfate, a sulfate (e.g. zinc sulfate, acetyl sulfate, etc.), a mixture thereof, or a mixture thereof with another chemical species (e.g. acetic anhydride, thiolacetic acid, or other types of acids, etc.).
  • a sulfate e.g. zinc sulfate, acetyl sulfate, etc.
  • another chemical species e.g. acetic anhydride, thiolacetic acid, or other types of acids, etc.
  • metal sulfates that may be used as a sulfonating agent; e.g. those sulfates containing Mg, Ca, Co, Li, Ba, Na, Pb, Ni, Fe, Mn, K, Hg, Cr, and other transition metal
  • a triblock copolymer poly(styrene-isobutylene-styrene) or SIBS
  • sulfonated may be performed in solution with acetyl sulfate as the sulfonating agent.
  • acetic anhydride reacts with sulfuric acid to form acetyl sulfate (a sulfonating agent) and acetic acid (a by product).
  • SIBS is then mixed with the mixture of acetyl sulfate and acetic acid.
  • Such a sulfonation reaction produces sulfonic acid substituted to the para-position of the aromatic ring in the styrene block of the polymer.
  • Elastomers having an aromatic ring may be sulfonated in a similar manner.
  • a sulfonated elastomer also may be synthesized by copolymerization of a low level of functionalized (i.e. sulfonated) monomer with an unsaturated monomer (e.g. olefinic monomer, isoprene monomer or oligomer, butadiene monomer or oligomer, etc.).
  • a low level of functionalized (i.e. sulfonated) monomer with an unsaturated monomer (e.g. olefinic monomer, isoprene monomer or oligomer, butadiene monomer or oligomer, etc.).
  • EXAMPLE 1 Sol-Gel Process for Producing Li x TiNb 2 0 7 (TNO) as a Reinforcement or Filler for the Elastomer Shell
  • the synthesis method involves precipitating the precursor to niobium-based composite metal oxide nanoparticles from a solution reactant mixture of Nb(OH)s (dissolved in citric acid) and water-ethanol solution containing Ti(OC 3 H 7 )4.
  • Nb 2 Os was dissolved in hydrofluoric acid to form a transparent solution.
  • ammonia was added to obtain a white Nb(OH)s precipitate.
  • the Nb(OH)s was dissolved in citric acid to form a Nb(V)-citrate solution.
  • a water-ethanol solution containing Ti(OC 3 H 7 )4 was added to this solution while the pH value of the solution was adjusted using ammonia.
  • This final mixture containing Nb(V) and Ti(IV) ions was then stirred at 90°C to form a citric gel.
  • This gel was then heated to l40°C to obtain a precursor, which was annealed at 900°C and at l350°C to obtain the Li x TiNb 2 0 7 (TNO) powder.
  • the powder was ball-milled in a high-intensity ball mill to obtain nanoparticles of TNO, which were then dispersed in monomers/oligomers of several different elastomers (e.g.
  • polyurethane, polybutadine, etc. to form reacting suspensions.
  • the monomers/oligomers were then polymerized to a controlled extent without allowing for any significant cross-linking of chains. This procedure often enables chemical bonding between the composite metal oxide particles and other inorganic filler species (particles of transition metal carbide, sulfide, selenide, phosphide, nitride, boride, etc.).
  • These non-cured or non-crosslinked polymers were then each separately dissolved in an organic solvent to form a suspension (polymer- solvent solution plus bonded metal oxide particles).
  • Particles of cathode active materials were then dispersed into this suspension to form a slurry. The slurry was then spray-dried to form particulates containing cathode active material particles being embraced by an encapsulating shell of metal oxide- reinforced elastomer.
  • EXAMPLE 2 Preparation of TiNb 2 0 7 , TiMoNb0 7 , and TiFeo .3 Nbi .7 0 7 as a Reinforcement or Filler for the Elastomer Shell
  • a niobium-titanium composite oxide represented by the general formula TiNb 2 0 7 was synthesized, by following the following procedure: Commercially available niobium oxide (Nb 2 Os) and a titanate proton compound were used as starting materials.
  • the titanate proton compound was prepared by immersing potassium titanate in hydrochloric acid at 25°C for 72 hours. In the process, 1M hydrochloric acid was replaced with a 1M of fresh acid every 24 hours. As a result, potassium ions were exchanged for protons to obtain the titanate proton compound.
  • the niobium oxide (Nb 2 Os) and the titanate proton compound were weighed such that the molar ratio of niobium to titanium in the synthesized compound was 3.
  • the mixture was dispersed in 100 ml of pure water, followed by vigorous mixing.
  • the obtained mixture was placed in a heat resistant container and was subjected to hydrothermal synthesis under conditions of l80°C for a total of 24 hours.
  • the obtained sample was washed in pure water three times, and then dried.
  • the sample was then subjected to a heat treatment at l,l00°C for 24 hours to obtain TiNb 2 0 7 .
  • niobium-molybdenum-titanium composite oxide was synthesized in the same manner as above except that niobium oxide (Nb 2 Os), molybdenum oxide (Mo 2 Os), and a titanate proton compound were weighed such that the molar ratio of niobium to titanium and that of molybdenum to titanium in the synthesized compound was 1.5 and 1.5, respectively.
  • niobium-molybdenum-titanium composite oxide TiMoNb0 7
  • niobium-iron-titanium composite oxide was synthesized in the same manner as above except that niobium oxide (Nb 2 Os), a titanate proton compound, and iron oxide (Fe 2 0 3 ) were weighed such that the molar ratio of niobium to titanium and of iron to titanium in the synthesized compound was 3 and 0.3, respectively.
  • niobium oxide Nb 2 Os
  • TiOs titanate proton compound
  • Fe 2 0 3 iron oxide
  • niobium-containing composite metal oxide powders TiNb 2 0 7 , TiMoNb0 7 , and TiFeo .3 Nbi 7 0 7 ) were separately added into a monomer of synthetic polyisoprene and a mixture of monomers for urethane-urea copolymer, respectively. Polymerization of the respective reacting mass was initiated and proceeded to obtain linear chains without crosslinking. This step was found to create some bonding between the composite metal oxide particles.
  • substantially linear chains were dissolved in a solvent (e.g. benzene and DMAc) to form a solution and particles of selected cathode active materials (V 2 Os, lithium iron phosphate, LiCo0 2 , etc.) were dispersed in the solution to form a slurry.
  • a solvent e.g. benzene and DMAc
  • particles of selected cathode active materials V 2 Os, lithium iron phosphate, LiCo0 2 , etc.
  • the paste was transferred into a Teflon container having a 90-mL capacity, which was then placed in an autoclave.
  • the paste was then heated up to 220°C for 5 hours with a heating and cooling ramp of 2 and 5 degrees C/min, respectively.
  • the paste was then washed with distilled water by centrifugation until a pH between 6 and 7 was obtained.
  • the resulting compound was heated at 60°C for 12 hours and then ball-milled for 30 min at 500 rpm
  • the paste was transferred into a Teflon container having a 90-mL capacity, which was then placed in an autoclave.
  • the paste was then heated up to 220°C for 5 hours with a heating and cooling ramp of 2 and 5 degrees C/min, respectively.
  • the paste was then washed with distilled water by centrifugation until a pH between 6 and 7 was obtained.
  • the compound was heated at 60°C for 12 hours and then ball-milled for 30 min at 500 rpm in hexane. After evaporation of hexane, the powder was calcinated at 950°C for 1 hour with a heating/cooling ramp of 3 degrees C/min to obtain Feo .i Tio .8 Nb 2.i 0 7 crystals.
  • a sequence of steps can be utilized to form nanoplatelets from many different types of layered compounds: (a) dispersion of a layered compound in a low surface tension solvent or a mixture of water and surfactant, (b) ultrasonication, and (c) an optional mechanical shear treatment.
  • dichalcogenides MoSe 2
  • MoSe 2 consisting of Se— Mo— Se layers held together by weak van der Waals forces can be exfoliated via the direct ultrasonication process invented by our research group.
  • Intercalation can be achieved by dispersing MoSe 2 powder in a silicon oil beaker, with the resulting suspension subjected to ultrasonication at 120 W for two hours.
  • the resulting MoSe 2 platelets were found to have a thickness in the range from approximately 1.4 nm to 13.5 nm with most of the platelets being mono-layers or double layers.
  • zirconium chloride (ZrCl 4 ) precursor 1.5 mmol
  • oleylamine 5.0 g, 18.7 mmol
  • the reaction mixture was first heated to 300°C at a heating rate of 5°C/min under argon flow and subsequently CS 2 (0.3 mL, 5.0 mmol) was injected. After 1 h, the reaction was stopped and cooled down to room temperature. After addition of excess butanol and hexane mixtures (1:1 by volume), 18 nm ZrS 2 nanodiscs (-100 mg) were obtained by centrifugation. Larger sized nanodiscs ZrS 2 of 32 nm and 55 nm were obtained by changing reaction time to 3 h and 6 h, respectively otherwise under identical conditions.
  • EXAMPLE 7 Preparation of Boron Nitride Nanosheets as a Nanofiller for the Elastomer Shell
  • the BN nanosheets obtained were from 1 nm thick ( ⁇ 3 atomic layers) up to 7 nm thick.
  • EXAMPLE 8 Sulfonation of triblock copolymer poly(styrene-isobutylene-styrene) or SIBS
  • An example of the sulfonation procedure used in this study is summarized as follows: a 10% (w/v) solution of SIBS (50 g) and a desired amount of graphene oxide sheets (0.15 TO 405 by wt.) in methylene chloride (500 ml) was prepared. The solution was stirred and refluxed at approximately 40 8C, while a specified amount of acetyl sulfate in methylene chloride was slowly added to begin the sulfonation reaction.
  • Acetyl sulfate in methylene chloride was prepared prior to this reaction by cooling 150 ml of methylene chloride in an ice bath for approximately 10 min. A specified amount of acetic anhydride and sulfuric acid was then added to the chilled methylene chloride under stirring conditions. Sulfuric acid was added
  • the S-SIBS samples were dissolved in a mixed solvent of toluene/hexanol (85/15, w/w) to form solutions having polymer concentrations ranging from 5 to 2.5% (w/v). Desired amounts of transition metal oxides prepared in Examples 1-4 were added into these solutions and the resulting slurries were ultrasonicated for 0.5- 1.5 hours. Particles of a desired cathode active material, along with a desired amount of conducting additive (e.g. graphene sheets or CNTs) were then added into the slurry samples. The slurry samples were separately spray-dried to form transition metal oxide-reinforced sulfonated elastomer-embraced particles. Alternatively, sulfonation may be conducted on the reinforced elastomer layer after this encapsulating layer is form. (e.g. after the active material particle(s) is/are encapsulated.
  • a desired cathode active material along with a desired amount of conducting additive (e.g
  • BZP Benzophenone
  • TAA 1,3-bis(trimethoxysilyl)
  • a desired amount of inorganic filler particles 0.l%-40% by wt.
  • PB-TA inorganic material-reinforced thioacetylated polybutadiene
  • inorganic filler material particles may be added at different stages of the procedure: before, during or after BZP is added or before/during/after the cathode active material particles are added.
  • SBS Sulfonated styrene-butadiene- styrene triblock copolymer
  • SBS concentration 11 g/lOO mL
  • HCOOH cyclohexane solution
  • H 2 0 2 solution 1 g/lOO mL
  • the molar ratio of H 2 0 2 /HC00H was 1.
  • the product (ESBS) was precipitated and washed several times with ethanol, followed by drying in a vacuum dryer at 60°C.
  • ESBS was first dissolved in toluene to form a solution with a concentration of 10 g/lOO mL, into which was added 5 wt% TEAB/ESBS as a phase transfer catalyst and 5 wt% DMA/ESBS as a ring-opening catalyst.
  • TEAB tetraethyl ammonium bromide
  • DMA N,N-dimethyl aniline.
  • reaction is autocatalytic and strongly exothermic! Particles of the desired cathode active materials were added before or after this reaction.
  • the resulting slurry was stirred for 1 h, and then most of the solvent was distilled off in vacuum at 35°C.
  • the slurry containing the sulfonated elastomer was coagulated in a plenty of acetonitrile, isolated by filtration, washed with fresh acetonitrile, and dried in vacuum at 35°C to obtain sulfonated elastomers.
  • elastomers e.g. polyisoprene, EPDM, EPR, polyurethane, etc.
  • all the rubbers or elastomers can be directly immersed in a solution of sulfuric acid, a mixture of sulfuric acid and acetyl sulfate, or other sulfonating agent discussed above to produce sulfonated elastomers/rubbers.
  • both the inorganic filler material and cathode active material particles may be added at various stages of the procedure. However, the inorganic filler material is preferably added before or immediately after addition of TAA and the cathode active material particles are added at a later stage.
  • EXAMPLE 12 Graphene Oxide from Sulfuric Acid Intercalation and Exfoliation of MCMBs
  • MCMB meocarbon microbeads
  • This material has a density of about 2.24 g/cm with a median particle size of about 16 pm.
  • MCMBs (10 grams) were intercalated with an acid solution (sulfuric acid, nitric acid, and potassium permanganate at a ratio of 4:1:0.05) for 48 hours. Upon completion of the reaction, the mixture was poured into deionized water and filtered. The intercalated MCMBs were repeatedly washed in a 5% solution of HC1 to remove most of the sulfate ions. The sample was then washed repeatedly with deionized water until the pH of the filtrate was neutral.
  • the slurry was dried and stored in a vacuum oven at 60°C for 24 hours.
  • the dried powder sample was placed in a quartz tube and inserted into a horizontal tube furnace pre-set at a desired temperature, 800°C-l,l00°C for 30-90 seconds to obtain graphene samples.
  • a small quantity of graphene was mixed with water and ultrasonicated at 60-W power for 10 minutes to obtain a suspension.
  • a small amount was sampled out, dried, and investigated with TEM, which indicated that most of the NGPs were between 1 and 10 layers.
  • the oxygen content of the graphene powders (GO or RGO) produced was from 0.1% to approximately 25%, depending upon the exfoliation temperature and time.
  • Graphite oxide was prepared by oxidation of graphite flakes with sulfuric acid, sodium nitrate, and potassium permanganate at a ratio of 4:1:0.05 at 30°C for 48 hours, according to the method of Hummers [US Pat. No. 2,798,878, July 9, 1957]. Upon completion of the reaction, the mixture was poured into deionized water and filtered. The sample was then washed with 5% HC1 solution to remove most of the sulfate ions and residual salt and then repeatedly rinsed with deionized water until the pH of the filtrate was approximately 4. The intent was to remove all sulfuric and nitric acid residue out of graphite interstices. The slurry was dried and stored in a vacuum oven at 60°C for 24 hours.
  • the dried, intercalated (oxidized) compound was exfoliated by placing the sample in a quartz tube that was inserted into a horizontal tube furnace pre-set at l,050°C to obtain highly exfoliated graphite.
  • the exfoliated graphite was dispersed in water along with a 1% surfactant at 45°C in a flat-bottomed flask and the resulting graphene oxide (GO) suspension was subjected to ultrasonication for a period of 15 minutes to obtain a homogeneous graphene-water suspension.
  • EXAMPLE 14 Preparation of Pristine Graphene Sheets Pristine graphene sheets were produced by using the direct ultrasonic ation or liquid-phase exfoliation process. In a typical procedure, five grams of graphite flakes, ground to
  • HEG highly exfoliated graphite
  • FHEG fluorinated highly exfoliated graphite
  • a pre-cooled Teflon reactor was filled with 20-30 mL of liquid pre-cooled ClF 3 , and then the reactor was closed and cooled to liquid nitrogen temperature. Subsequently, no more than 1 g of HEG was put in a container with holes for ClF gas to access the reactor. After 7-10 days, a gray-beige product with approximate formula C 2 F was formed. GF sheets were then dispersed in halogenated solvents to form suspensions.
  • Graphene oxide (GO), synthesized in Example 12, was finely ground with different proportions of urea and the pelletized mixture heated in a microwave reactor (900 W) for 30 s. The product was washed several times with deionized water and vacuum dried. In this method graphene oxide gets simultaneously reduced and doped with nitrogen.
  • the products obtained with graphene/urea mass ratios of 1/0.5, 1/1 and 1/2 are designated as N-l, N-2 and N-3 respectively and the nitrogen contents of these samples were 14.7, 18.2 and 17.5 wt.%
  • EXAMPLE 17 Cathode Particulates Containing V O Particles Encapsulated by a Shell of Elastomer Composite
  • Cathode active material layers were prepared from V2O5 particles and graphene- embraced V2O5 particles, respectively.
  • V2O5 particles were commercially available.
  • Graphene- embraced V2O5 particles were prepared in-house.
  • vanadium pentoxide gels were obtained by mixing V2O5 in a LiCl aqueous solution.
  • the Li + -exchanged gels obtained by interaction with LiCl solution (the Li:V molar ratio was kept as 1:1) was mixed with a GO suspension and then placed in a Teflon-lined stainless steel 35 ml autoclave, sealed, and heated up to l80°C for 12 h. After such a hydrothermal treatment, the green solids were collected, thoroughly washed, ultrasonicated for 2 minutes, and dried at 70°C for 12 h followed by mixing with another 0.1% GO in water, ultrasonicating to break down nanobelt sizes, and then spray drying at 200°C to obtain graphene-embraced V2O5 composite particulates.
  • the working electrodes were prepared by mixing 85 wt. % active material (elastomer composite encapsulated or non-encapsulated particulates of V2O5, separately), 7 wt. % acetylene black (Super-P), and 8 wt. % polyvinylidene fluoride (PVDF) binder dissolved in N-methyl-2-pyrrolidinoe (NMP) to form a slurry of 5 wt. % total solid content. After coating the slurries on A1 foil, the electrodes were dried at 120°C in vacuum for 2 h to remove the solvent before pressing.
  • active material elastomer composite encapsulated or non-encapsulated particulates of V2O5, separately
  • Super-P acetylene black
  • PVDF polyvinylidene fluoride
  • NMP N-methyl-2-pyrrolidinoe
  • Electrochemical measurements were carried out using CR2032 (3 V) coin-type cells with lithium metal as the counter/reference electrode, Celgard 2400 membrane as separator, and 1 M LiPF 6 electrolyte solution dissolved in a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC) (EC-DEC, 1:1 v/v).
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • the cell assembly was performed in an argon-filled glove-box.
  • the CV measurements were carried out using a CH-6 electrochemical workstation at a scanning rate of 1 mV/s.
  • the electrochemical performance of the particulates of nano LUTisO ⁇ -reinforced sulfonated elastomer-encapsulated V2O5 particles and that of non-protected V2O5 were evaluated by galvanostatic charge/discharge cycling at a current density of 50 mA/g, using a LAND electrochemical workstation.
  • the protecting elastomer composite encapsulation shell appears to be capable of reversibly deforming to a great extent without breakage when the active material particles expand and shrink.
  • the elastomer also remains chemically bonded to the binder resin when the encapsulated particles expand or shrink.
  • the PVDF binder is broken or detached from some of the non-encapsulated active material particles.
  • LFP lithium iron phosphate
  • the battery cells from the TiNb 2 0 7 reinforced elastomer-encapsulated LFP particles and non-coated LFP particles were prepared using a procedure described in Example 1.
  • FIG. 4 shows that the cathode prepared according to the presently invented inorganic filler reinforced elastomer-encapsulated particulate approach offers a significantly more stable and higher reversible capacity compared to the un-coated LFP particle-based.
  • the high-elasticity elastomer is more capable of holding the active material particles and conductive additive together, significantly improving the structural integrity of the active material electrode.
  • the high- elasticity elastomer also acts to isolate the electrolyte from the active material yet still allowing for easy diffusion of lithium ions.
  • EXAMPLE 19 Metal Fluoride and Metal Chloride Particles Encapsulated by a MoSe 2 - Reinforced Sulfonated Styrene-Butadiene Rubber (SBR)/Graphene Composite
  • nanoparticles from the same batch were also investigated to determine and compare the cycling behaviors of the lithium-ion batteries containing these particles as the cathode active material.
  • FIG. 5 Shown in FIG. 5 are the discharge capacity curves of two coin cells having two different types of cathode active materials: (1) elastomer composite-encapsulated metal fluoride particles and (2) non-encapsulated metal fluorides.
  • the high-elasticity elastomer composite appears to be capable of reversibly deforming without breakage when the cathode active material particles expand and shrink.
  • the elastomer also remains chemically bonded to the binder resin when the active particles expand or shrink.
  • both SBR and PVDF the two conventional binder resins, are broken or detached from some of the non-encapsulated active material particles.
  • the high-elasticity elastomer has contributed to the structural stability of the electrode layer. These were observed by using SEM to examine the surfaces of the electrodes recovered from the battery cells after some numbers of charge-discharge cycles.
  • EXAMPLE 20 Metal Naphthalocyanine-Reduced Graphene Oxide (FePc/RGO) Hybrid Particulates Encapsulated by a High-Elasticity ZrS 2 -Filled Elastomer
  • lithium ion-conducting additives were added to several different sulfonated elastomer composites to prepare encapsulation shell materials for protecting core particles of active material.
  • these filled elastomer materials are suitable encapsulation shell materials provided that their lithium ion conductivity at room temperature is no less than 10 S/cm. With these materials, lithium ions appear to be capable of readily diffusing in and out of the encapsulation shell having a thickness no greater than 1 pm. For thicker shells (e.g. 10 pm), a lithium ion conductivity at room temperature no less than 10 4 S/cm would be required.
  • Table 1 Lithium ion conductivity of various sulfonated elastomer composite compositions as a shell material for protecting active material particles.
  • the inorganic filler reinforced elastomer encapsulation strategy is surprisingly effective in alleviating the cathode expansion/shrinkage-induced capacity decay problems.
  • This encapsulation elastomer strategy reduces or eliminates direct contact between the catalytic transition metal element (e.g. Fe, Mn, Ni, Co, etc.) commonly used in a cathode active material and the electrolyte, thereby reducing/eliminating catalytic decomposition of the electrolyte.
  • the catalytic transition metal element e.g. Fe, Mn, Ni, Co, etc.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne une électrode de cathode de batterie au lithium comprenant de multiples particules constituées d'un matériau actif de cathode, au moins une particule étant composée d'une ou de plusieurs particules constituées d'un matériau actif de cathode étant encapsulées par une couche mince constituée d'élastomère renforcé par une charge inorganique comportant de 0,01 % à 50 % en poids d'une charge inorganique dispersée dans un matériau matriciel élastomère sur la base du poids total de l'élastomère renforcé par une charge inorganique, la couche mince d'encapsulation d'élastomère renforcé par une charge inorganique présentant une épaisseur de 1 nm à 10 µm, un allongement en traction complètement récupérable de 2 % à 500 %, et une conductivité des ions lithium de 10-7 S/cm à 5x10-2 S/cm et la charge inorganique présentant un potentiel d'intercalation du lithium de 1,1 V à 4,5 V (de préférence de 1,2 à 2,5 V) par rapport à Li/Li+. L'invention concerne également un procédé de production d'une masse pulvérulente destinée à une batterie au lithium.
PCT/US2019/047642 2018-08-22 2019-08-22 Particules encapsulées dans un élastomère électrochimiquement stable de matériaux actifs de cathode destinés à des batteries au lithium Ceased WO2020041559A1 (fr)

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US16/109,142 2018-08-22
US16/109,178 2018-08-22
US16/109,178 US11239460B2 (en) 2018-08-22 2018-08-22 Method of producing electrochemically stable elastomer-encapsulated particles of cathode active materials for lithium batteries
US16/109,142 US11043662B2 (en) 2018-08-22 2018-08-22 Electrochemically stable elastomer-encapsulated particles of cathode active materials for lithium batteries

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CN111952561A (zh) * 2020-08-03 2020-11-17 扬州大学 自模板法合成的CoIn2S4@CPAN微球复合材料及其方法
CN114023960A (zh) * 2021-10-20 2022-02-08 上海大学(浙江·嘉兴)新兴产业研究院 一种金属配位聚合物有机正极材料及其制备方法
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CN116093252A (zh) * 2023-04-06 2023-05-09 宁德新能源科技有限公司 负极极片、以及包含其的电化学装置及电子装置

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CN116093252A (zh) * 2023-04-06 2023-05-09 宁德新能源科技有限公司 负极极片、以及包含其的电化学装置及电子装置

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