WO2018125641A1 - Batteries en métal alcalin en forme de corde souples et à forme conforme - Google Patents

Batteries en métal alcalin en forme de corde souples et à forme conforme Download PDF

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Publication number
WO2018125641A1
WO2018125641A1 PCT/US2017/067071 US2017067071W WO2018125641A1 WO 2018125641 A1 WO2018125641 A1 WO 2018125641A1 US 2017067071 W US2017067071 W US 2017067071W WO 2018125641 A1 WO2018125641 A1 WO 2018125641A1
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Prior art keywords
electrode
lithium
alkali metal
battery
graphene
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PCT/US2017/067071
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English (en)
Inventor
Aruna Zhamu
Hui He
Baofei Pan
Yu-Sheng Su
Bor Z. Jang
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Nanotek Instruments, Inc.
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Priority claimed from US15/392,127 external-priority patent/US10008747B1/en
Priority claimed from US15/392,120 external-priority patent/US10535880B2/en
Application filed by Nanotek Instruments, Inc. filed Critical Nanotek Instruments, Inc.
Publication of WO2018125641A1 publication Critical patent/WO2018125641A1/fr

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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/102—Primary casings, jackets or wrappings of a single cell or a single battery characterised by their shape or physical structure
    • H01M50/103—Primary casings, jackets or wrappings of a single cell or a single battery characterised by their shape or physical structure prismatic or rectangular
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/102—Primary casings, jackets or wrappings of a single cell or a single battery characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/102—Primary casings, jackets or wrappings of a single cell or a single battery characterised by their shape or physical structure
    • H01M50/107—Primary casings, jackets or wrappings of a single cell or a single battery characterised by their shape or physical structure having curved cross-section, e.g. round or elliptic
    • 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 invention relates generally to the field of lithium batteries, sodium batteries, and potassium batteries, including rope-type primary (non-rechargeable) and secondary
  • Lithium ion battery is a prime candidate energy storage device for electric vehicle (EV) and mobile device applications.
  • EV electric vehicle
  • the past two decades have witnessed a continuous improvement in Li-ion batteries in terms of energy density, rate capability, and safety, and somehow the significantly higher energy density Li metal batteries have been largely overlooked.
  • the use of graphite-based anodes in Li-ion batteries has several significant drawbacks: low specific capacity (theoretical capacity of 372 mAh/g as opposed to 3,860 mAh/g for Li metal), long Li intercalation time (e.g. low solid-state diffusion coefficients of Li in and out of graphite and inorganic oxide particles) requiring long recharge times (e.g.
  • the insertion and extraction of lithium in and out of these commonly used cathodes rely upon extremely slow solid-state diffusion of Li in solid particles having very low diffusion coefficients (typically 10 "8 to 10 "14 cm 2 /s), leading to a very low power density (another long-standing problem of today's lithium -ion batteries).
  • the current cathode materials are electrically and thermally insulating, not capable of effectively and efficiently transporting electrons and heat.
  • the low electrical conductivity means high internal resistance and the necessity to add a large amount of conductive additives, effectively reducing the proportion of electrochemically active material in the cathode that already has a low capacity.
  • the low thermal conductivity also implies a higher tendency to undergo thermal runaway, a major safety issue in lithium battery industry.
  • sodium batteries have been considered an attractive alternative to lithium batteries since sodium is abundant and the production of sodium is significantly more environmentally benign compared to the production of lithium.
  • the high cost of lithium is a major issue and Na batteries potentially can be of significantly lower cost.
  • Sodium ion batteries using a hard carbon-based anode active material (a Na intercalation compound) and a sodium transition metal phosphate as a cathode have been described by several research groups; e.g. J. Barker, et al. "Sodium Ion Batteries," US Patent No. 7,759,008 (July 20, 2010).
  • the anode active materials for Na intercalation and the cathode active materials for Na intercalation have lower Na storage capacities as compared with their Li storage capacities.
  • hard carbon particles are capable of storing Li ions up to 300- 360 mAh/g, but the same materials can store Na ions up to 150-250 mAh/g and less than 100 mAh/g for K ion storage.
  • sodium metal may be used as the anode active material in a sodium metal cell.
  • metallic sodium as the anode active material is normally considered undesirable and dangerous due to the dendrite formation, interface aging, and electrolyte incompatibility problems.
  • the cathode active material amount is typically 1.5-2.5 times higher than the anode active material.
  • the weight proportion of the anode active material (e.g. graphite or carbon) in a lithium-ion battery is typically from 12% to 17%, and that of the cathode active material (e.g. LiMn 2 0 4 ) from 17% to 35% (mostly ⁇ 30%).
  • the weight fraction of the cathode and anode active materials combined is typically from 30% to 45% of the cell weight
  • the low active material mass loading is primarily due to the inability to obtain thicker electrodes (thicker than 100-200 ⁇ ) using the conventional slurry coating procedure. This is not a trivial task as one might think, and in reality the electrode thickness is not a design parameter that can be arbitrarily and freely varied for the purpose of optimizing the cell performance. This is manufacturing limited. Furthermore, thicker samples tend to become extremely brittle or of poor structural integrity and would also require the use of large amounts of binder resin.
  • the low areal densities and low volume densities result in a relatively low volumetric capacity and low volumetric energy density of the battery cells. Sodium-ion batteries and potassium-ion batteries have similar problems.
  • thick electrodes in conventional batteries are also mechanically rigid, not flexible, not bendable, and not conformal to a desired shape.
  • high volumetric/gravimetric energy density and mechanical flexibility appear to be mutually exclusive.
  • alkali metal batteries that have high active material mass loading (high areal density), active materials with a high apparent density (high tap density), high electrode thickness without significantly decreasing the electron and ion transport rates (e.g. without a high electron transport resistance or long lithium or sodium ion diffusion path), high gravimetric energy density, and high volumetric energy density.
  • the present invention provides a rope-shape alkali metal battery containing filamentary or rod-like anode and cathode electrodes that are combined to form a braid or twist yarn shape (e.g. twist 2-ply, 3 -ply, 4-ply, 5-ply yarn or braid, etc.), wherein the alkali metal is selected from Li, Na, K, or a combination thereof.
  • the battery can be a Li metal battery, Li-ion battery, sodium metal battery, Na-ion battery, potassium metal battery, potassium-ion battery, hybrid Li/Na, Li/K, Na/K, and Li/Na/K batteries.
  • the battery comprises: (a) a first electrode comprising a first electrically conductive porous rod (or filament) having pores and a first mixture of a first electrode active material and a first electrolyte, wherein the first mixture resides in pores of the first porous rod (e.g. foam of a filamentary shape); (b) a porous separator wrapping around or encasing the first electrode to form a separator-protected first electrode; (c) a second electrode comprising a second electrically conductive porous rod (e.g.
  • the invented alkali metal battery may further comprise a porous separator wrapping around or encasing the second electrode to form a separator-protected second electrode.
  • both the first and second electrodes are encased by a porous separator prior to being braided or interlaced together to form a braid or twist yarn.
  • the two electrodes are as closely packed as possible to maximize the contact or interfacial areas between the electrodes.
  • the rope-shape alkali metal battery further comprises a third electrolyte disposed between the braid or yarn and the protective sheath.
  • the third electrolyte may be the same as or different than the first electrolyte or the second electrolyte.
  • the first electrode can be a negative electrode (or anode) and the second electrode a positive electrode (or cathode).
  • the second electrode is a negative electrode or anode and the first electrode is a positive electrode or cathode.
  • the battery can comprise a plurality of the first electrodes and/or a plurality of the second electrodes.
  • the battery can have multiple anode and/or multiple cathode filaments combined together to form a braid or twist yarn structure.
  • At least one of the electrodes is an anode and at least one of the electrodes is a cathode.
  • the first electrode contains Li, Na, and/or K metal as an anode active material. Additionally or separately, an intercalation compound may be used as an anode active material.
  • the rope-shaped alkali metal battery has a length and a diameter or thickness with a length-to-diameter or length-to-thickness aspect ratio being at least 5, preferably at least 10, and more preferably at least 20.
  • the battery comprises: (a) a first electrode comprising a first electrically conductive rod (not a porous foam) and a first mixture of a first electrode active material and a first electrolyte, wherein the first mixture is deposited on or in the first rod; (b) a porous separator wrapping around or encasing the first electrode to form a separator-protected first electrode; (c) a second electrode comprising a second electrically conductive rod that is porous and has pores and a second mixture of a second electrode active material and a second electrolyte, wherein the second mixture resides in the pores of the second rod that is porous; wherein the separator-protected first electrode and the second electrode are interlaced or combined in a spiral or twist manner to form a braid or yarn; and (d) a protective casing or sheath wrapping around or encasing the yarn or braid.
  • the invented alkali metal battery may further comprise a porous separator wrapping around or encasing the second electrode to form a separator-protected second electrode.
  • the alkali metal battery further comprises a third electrolyte disposed between the braid or yarn and the protective sheath.
  • the third electrolyte may be the same as or different than the first electrolyte or the second electrolyte.
  • the first or second electrode (but not both) comprises a conductive rod (not a foam) and the first or second mixture is coated or deposited on the surface of this conductive rod.
  • This rod can be as simple as a metal wire, a conductive polymer fiber or yarn, a carbon or graphite fiber or yarn, or multiple wires, fibers, or yarns.
  • the rope-shaped battery has a first end and a second end and the first electrode contains a first terminal connector comprising at least one metallic wire, conductive carbon/graphite fiber, or conductive polymer fiber that is embedded in, connected to, or integral with the first electrode.
  • the at least one metallic wire, conductive carbon/graphite fiber, or conductive polymer fiber runs approximately from the first end to the second end. This wire or fiber preferably is protruded out of the first end or second end to become a terminal tab for connecting to an electronic device or external circuit or load.
  • the rope-shaped battery has a first end and a second end and the second electrode contains a second terminal connector comprising at least one metallic wire, conductive carbon/graphite fiber, or conductive polymer fiber that is embedded in, connected to, or integral with the second electrode.
  • at least one metallic wire, conductive carbon/graphite fiber, or conductive polymer fiber runs approximately from the first end to the second end. This wire or fiber preferably is protruded out of the first end or second end to become a terminal tab for connecting to an electronic device or external circuit or load.
  • the first or second electrically conductive porous rod may contain a porous foam selected from a metal foam, metal web, metal fiber mat, metal nanowire mat, metal wire braid, conductive polymer fiber mat, conductive polymer foam, conductive polymer fiber braid, conductive polymer-coated fiber foam, carbon foam, graphite foam, carbon aerogel, graphene aerogel, carbon xerogel, graphene foam, graphene oxide foam, reduced graphene oxide foam, carbon fiber foam, graphite fiber foam, exfoliated graphite foam, or a combination thereof.
  • a porous foam selected from a metal foam, metal web, metal fiber mat, metal nanowire mat, metal wire braid, conductive polymer fiber mat, conductive polymer foam, conductive polymer fiber braid, conductive polymer-coated fiber foam, carbon foam, graphite foam, carbon aerogel, graphene aerogel, carbon xerogel, graphene foam, graphene oxide foam, reduced graphene oxide foam, carbon fiber foam, graphite fiber foam, exfoliated
  • foam structures can be readily made into a porosity level > 50%, typically and desirably > 70%, more typically and preferably > 80%, still more typically and preferably > 90%), and most preferably > 95% (graphene aerogel can exceed a 99% porosity level).
  • the skeleton structure (pore walls) in these foams forms a 3D network of electron-conducting pathways while the pores can accommodate a large proportion of an electrode active material (anode active material in the anode or cathode active material in the cathode) without using any conductive additive or a binder resin.
  • the foam can have a cross-section that is circular, elliptic, rectangular, square, hexagon, hollow, or irregular in shape.
  • the battery has a rope shape that has a length and a diameter or thickness and an aspect ratio (length/thickness or length/diameter ratio) greater than 10, preferably greater than 15, more preferably greater than 20, further preferably greater than 30, even more preferably greater than 50 or 100.
  • the thickness or diameter is typically and preferably from 100 nm to 10 cm, more preferably and typically from 1 ⁇ to 1 cm, and most typically from 10 ⁇ to 1 mm.
  • the length can run from 1 ⁇ to tens of meters or even hundreds of meters (if so desired).
  • the first electrode or second electrode contains particles, foil, or coating of Li, Na, K, or a combination thereof as an electrode active material.
  • the alkali metal battery is a lithium-ion battery and the first or second electrode active material is selected from the group consisting of: (a) Particles of natural graphite, artificial graphite, meso-carbon microbeads (MCMB), and carbon; (b) Silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), nickel (Ni), cobalt (Co), manganese (Mn), titanium (Ti), iron (Fe), and cadmium (Cd); (c) Alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, or Cd with other elements, wherein said alloys or compounds are stoichiometric or non-stoichiometric; (d) Oxides, carbides, nitrides, sulfides, phosphides, selenides,
  • the pre-lithiated graphene sheets may be selected from pre-lithiated versions of pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, boron- doped graphene, nitrogen-doped graphene, chemically functionalized graphene, a physically or chemically activated or etched version thereof, or a combination thereof.
  • an alkali intercalation compound selected from petroleum coke, carbon black, amorphous carbon, activated carbon, hard carbon,
  • the alkali metal battery is a sodium-ion battery and the first or second electrode active material contains an alkali intercalation compound selected from the following groups of materials: (a) Sodium- or potassium-doped silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), cobalt (Co), nickel (Ni), manganese (Mn), cadmium (Cd), and mixtures thereof; (b) Sodium- or potassium-containing alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd, and their mixtures; (c) Sodium- or potassium-containing oxides, carbides, nitrides, sulfides, phosphides, selenides, tellurides, or antimonides of Si, Ge, Sn, Pb, Sb, Bi,
  • the second or first electrode active material contains a lithium intercalation compound or lithium absorbing compound selected from the group consisting of lithium cobalt oxide, doped lithium cobalt oxide, lithium nickel oxide, doped lithium nickel oxide, lithium manganese oxide, doped lithium manganese oxide, lithium vanadium oxide, doped lithium vanadium oxide, lithium mixed-metal oxides, lithium iron phosphate, lithium vanadium phosphate, lithium manganese phosphate, lithium mixed-metal phosphates, metal sulfides, lithium selenide, lithium polysulfide, and combinations thereof.
  • a lithium intercalation compound or lithium absorbing compound selected from the group consisting of lithium cobalt oxide, doped lithium cobalt oxide, lithium nickel oxide, doped lithium nickel oxide, lithium manganese oxide, doped lithium manganese oxide, lithium vanadium oxide, doped lithium vanadium oxide, lithium mixed-metal oxides, lithium iron phosphate, lithium vanadium phosphate, lithium manganese phosphate, lithium mixed-metal phosphates
  • the second or first electrode active material contains a sodium intercalation compound or a potassium intercalation compound selected from NaFeP0 , Na ( i. X )K x P0 4 , KFeP0 4 , Na 0 7 FeP0 4 , Nai 5 VOPO 4 F 0 5 , Na 3 V 2 (P0 4 ) 3 , Na 3 V 2 (P0 4 ) 2 F 3 , Na 2 FeP0 4 F, NaFeF 3 , NaVP0 4 F, KVP0 4 F, Na 3 V 2 (P0 4 ) 2 F 3 , Nai 5 VOPO 4 F 0 5 , Na 3 V 2 (P0 4 ) 3 , NaV 6 0i 5 , Na x V0 2 , Na 0.33 V 2 O 5 , Na x Co0 2 , Na 2/3 [Nii /3 Mn 2/3 ]0 2 , Na x (Fei /2 Mni /2 )0 2 , Na
  • Nii /3 Mni /3 Coi /3 0 2 , Cu 0.56 Ni 0 . HCF, NiHCF, Na x Mn0 2 , NaCr0 2 , KCr0 2 , Na 3 Ti 2 (P0 4 ) 3 , C02O4, Ni 3 S 2 /FeS 2 , Sb 2 0 4 , Na 4 Fe(CN) 6 /C, NaVi -x Cr x P0 4 F, Se z S y , y/z 0.01 to 100, Se, sodium polysulfide, sulfur, Alluaudites, or a combination thereof, wherein x is from 0.1 to 1.0.
  • the first electrolyte and/or the second electrolyte may contain a lithium salt or sodium salt dissolved in a liquid solvent and wherein the liquid solvent is water, an organic solvent, an ionic liquid, or a mixture of an organic solvent and an ionic liquid.
  • the liquid solvent may be mixed with a polymer to form a polymer gel.
  • the first electrolyte and/or second electrolyte preferably contains a lithium salt or sodium salt dissolved in a liquid solvent having a salt concentration greater than 2.5 M (preferably > 3.0 M, further preferably > 3.5 M, even more preferably > 5.0 M, still more preferably > 7.0 M, and most preferably > 10 M, up to 15 M).
  • the first or second electrically conductive porous rod has at least 90% by volume of pores
  • the first or second electrode has a diameter or thickness no less than 200 ⁇ or has an active mass loading (anode or cathode active material) occupying at least 30%) by weight or by volume of the entire battery cell
  • the first and second electrode active materials combined occupies at least 50 % by weight or by volume of the entire battery cell.
  • the first or second electrically conductive porous rod has at least 95% by volume of pores
  • the first or second electrode has a diameter or thickness no less than 300 ⁇ or has an active mass loading occupying at least 35% by weight or by volume of the entire battery cell, or the first and second electrode active materials combined occupies at least 60 % by weight or by volume of the entire battery cell.
  • the first or second electrode active material comprises an alkali metal intercalation compound or alkali metal-absorbing compound selected from an inorganic material, an organic or polymeric material, a metal oxide/phosphate/sulfide, or a combination thereof.
  • the metal oxide/phosphate/sulfide is selected from a lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium vanadium oxide, lithium-mixed metal oxide, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, lithium mixed metal phosphate, transition metal sulfide, or a combination thereof.
  • the inorganic material may be selected from sulfur, sulfur compound, lithium polysulfide, 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 metal oxide/phosphate/sulfide contains a vanadium oxide selected from the group consisting of V0 2 , Li x V0 2 , V 2 0 5 , Li x V 2 0 5 , V 3 0 8 , Li x V 3 0 8 , Li x V 3 0 7 , V 4 0 9 , Li x V 4 0 9 , V 6 0i 3 , Li x V 6 0i 3 , their doped versions, their derivatives, and combinations thereof, wherein 0.1 ⁇ x ⁇ 5.
  • the metal oxide/phosphate/sulfide is 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 combination thereof, wherein 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 first or second electrode is a cathode that contains 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, Tetracyanoquino-dimethane (TCNQ), tetracyanoethylene (TCNE),
  • PAQS Poly(anthraquinonyl sulfide)
  • PTCDA 10-perylenetetracarboxylic dianhydride
  • PYT poly(anthraquinonyl sulfide), pyrene 4,5,9, 10-tetraone
  • PYT polymer-bound PYT
  • HMTP 11-hexamethoxytriphenylene
  • PADAQ poly(5 -amino- 1,4-dyhydroxy anthraquinone)
  • PADAQ poly(5 -amino- 1,4-dyhydroxy anthraquinone)
  • phosphazene disulfide polymer [( PS 2 ) 3 ] «)
  • lithiated 1,4,5,8-naphthalenetetraol formaldehyde polymer Hexaazatrinaphtylene (HATN), Hexaazatriphenylene hexacarbonitrile (HAT(CN) 6 ), 5-Benzylidene hydantoin, Isatine lithium salt, Pyromellitic diimide lithium salt, tetrahydroxy-p-benzoquinone derivatives (THQLi 4 ), N,N'-diphenyl-2,3,5,6-tetraketopiperazine (PHP), N,N'-diallyl-2,3,
  • the thioether polymer is selected from Poly[methanetetryl-tetra(thiomethylene)] (PMTTM), Poly(2,4-dithiopentanylene) (PDTP), a polymer containing Poly(ethene-l, 1,2,2- tetrathiol) (PETT) as a main-chain thioether polymers, a side-chain thioether polymer having a main-chain consisting of conjugating aromatic moieties, and having a thioether side chain as a pendant, Poly(2-phenyl-l,3-dithiolane) (PPDT), Poly(l,4-di(l,3-dithiolan-2-yl)benzene) (PDDTB), poly(tetrahydrobenzodithiophene) (PTHBDT), poly [1,2,4, 5- tetrakis(propylthio)benzene] (PTKPTB, or poly[3,4(ethylenedithio)thioph
  • the organic material contains a phthalocyanine compound selected from 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 selected from copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, iron phthalocyanine, lead phthalocyanine, nickel phthalocyanine, vanadyl phthalocyanine, fluorochromium phthalocyanine, magnesium phthalo
  • the cathode contains an alkali metal intercalation compound or alkali metal- absorbing compound selected from a metal carbide, metal nitride, metal boride, metal dichalcogenide, or a combination thereof. Further preferably, the cathode contains an alkali metal intercalation compound or alkali metal-absorbing compound selected from an oxide, dichalcogenide, trichalcogenide, sulfide, selenide, or telluride of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, vanadium, chromium, cobalt, manganese, iron, or nickel in a nanowire, nano-disc, nano-ribbon, or nano platelet form.
  • an alkali metal intercalation compound or alkali metal- absorbing compound selected from a metal carbide, metal nitride, metal boride, metal dichalcogenide, or a combination thereof.
  • the cathode contains an alkal
  • the cathode active material contains nano discs, nano platelets, nano-coating, or nano sheets of an inorganic material 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; wherein said discs, platelets, or sheets have a thickness less than 100 nm.
  • an inorganic material selected from: (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) sulfide, selenide, or telluride of niobium, zirconium, molyb
  • FIG.1(A) Schematic of a prior art lithium -ion battery cell (as an example of an alkali metal battery) composed of an anode current collector (e.g. Cu foil), an anode electrode
  • a cathode electrode e.g. LiMn 2 0 4 layer
  • a cathode current collector e.g. Al foil
  • FIG.1(B) Schematic of a prior art lithium-ion battery, wherein the electrode layer is composed of discrete particles of an active material (e.g. graphite or tin oxide particles in the anode layer or LiCo0 2 in the cathode layer);
  • an active material e.g. graphite or tin oxide particles in the anode layer or LiCo0 2 in the cathode layer
  • FIG.1(C) Schematic of a process for producing a rope-shaped, flexible and shape-conformable alkali metal battery
  • FIG.1(D) Four examples of the procedure for producing an electrode (rod-shaped anode or cathode) in a continuous and automated manner
  • FIG.1(E) Schematic of a presently invented process for continuously producing an alkali metal- ion battery electrode.
  • FIG.2 An electron microscopic image of isolated graphene sheets.
  • FIG.3 Examples of conductive porous layers: metal grid/mesh and carbon nano-fiber mat.
  • FIG.3(B) Examples of conductive porous layers: graphene foam and carbon foam.
  • FIG.3(C) Examples of conductive porous layers: graphite foam and Ni foam.
  • FIG.3(D) Examples of conductive porous layers: Cu foam and stainless steel foam.
  • FIG.4(A) Schematic of a commonly used process for producing exfoliated graphite, expanded graphite flakes (thickness > 100 nm), and graphene sheets (thickness ⁇ 100 nm, more typically ⁇ 10 nm, and can be as thin as 0.34 nm).
  • FIG.4 (B) Schematic drawing to illustrate the processes for producing exfoliated graphite
  • FIG.5 Ragone plots (gravimetric and volumetric power density vs. energy density) of lithium- ion battery cells containing graphite particles as the anode active material and carbon- coated LFP particles as the cathode active materials.
  • Two of the 4 data curves are for the rope-shaped cells prepared according to an embodiment of instant invention and the other two the conventional cells prepared by the conventional slurry coating of electrodes (roll- coating).
  • FIG.6 Ragone plots (both gravimetric and volumetric power density vs. gravimetric and
  • FIG.7 Ragone plots of lithium metal batteries containing a lithium foil as the anode active
  • FIG.8 The cell-level gravimetric (Wh/kg) and volumetric energy densities (Wh/L) of lithium metal cells plotted over the achievable cathode thickness range of the Mn0 2 /RGO cathode prepared via the conventional method without delamination and cracking and those rope-shape cells by the presently invented method.
  • FIG.9 The cell-level gravimetric and volumetric energy densities of the rope-shaped
  • FIG.10 Ragone plots (gravimetric and volumetric power density vs. energy density) of Na-ion battery cells containing hard carbon particles as the anode active material and carbon- coated Na 3 V 2 (P0 4 ) 2 F 3 particles as the cathode active materials.
  • Two of the 4 data curves are for the rope-shape cells prepared according to an embodiment of instant invention and the other two by the conventional slurry coating of electrodes (roll- coating).
  • FIG.11 Ragone plots (both gravimetric and volumetric power density vs. gravimetric and
  • volumetric energy density of two cells, both containing graphene-embraced Sn nano particles as the anode active material and NaFeP0 4 nano particles as the cathode active material.
  • the data are for both rope-shape sodium-ion cells prepared by the presently invented method and those by the conventional slurry coating of electrodes.
  • FIG.12 Ragone plots of sodium metal batteries containing a graphene-supported sodium foil as the anode active material, disodium rhodizonate (Na 2 C 6 0 6 ) as the cathode active material, and sodium salt (NaPF 6 )-PC/DEC as organic liquid electrolyte.
  • the data are for both the rope-shaped sodium metal cells prepared by the presently invented method and those by the conventional slurry coating of electrodes.
  • FIG.13 Ragone plot of a series of K-ion cells prepared by the conventional slurry coating
  • This invention is directed at a flexible and shape-conformable rope-like alkali metal battery exhibiting an exceptionally high volumetric energy density and high gravimetric energy density.
  • This alkali metal battery can be a primary battery, but is preferably a secondary battery selected from a lithium-ion battery or a lithium metal secondary battery (e.g. using lithium metal as an anode active material), a sodium-ion battery, a sodium metal battery, a potassium-ion battery, or a potassium metal battery.
  • the battery is based on an aqueous electrolyte, a nonaqueous or organic electrolyte, a gel electrolyte, an ionic liquid electrolyte, or a mixture of organic and ionic liquid.
  • Li iron phosphate LFP
  • vanadium oxide V x O y
  • lithium nickel manganese cobalt oxide NMC
  • dilithium rhodizonate Li 2 C 6 0 6
  • copper phthalocyanine CuPc
  • graphite, SnO, Co 3 0 4 , and Si particles examples of the anode active material.
  • a lithium -ion battery cell is typically composed of an anode current collector (e.g.
  • the anode layer is composed of particles of an anode active material (e.g. graphite or Si), a conductive additive (e.g. carbon black particles), and a resin binder (e.g. SBR or PVDF).
  • the cathode layer is composed of particles of a cathode active material (e.g. LFP particles), a conductive additive (e.g. carbon black particles), and a resin binder (e.g. PVDF). Both the anode and the cathode layers are typically up to 100-200 ⁇ thick to give rise to a presumably sufficient amount of current per unit electrode area.
  • This thickness range is considered an industry-accepted constraint under which a battery designer normally works under.
  • This thickness constraint is due to several reasons: (a) the existing battery electrode coating machines are not equipped to coat excessively thin or excessively thick electrode layers; (b) a thinner layer is preferred based on the consideration of reduced lithium ion diffusion path lengths; but, too thin a layer (e.g. ⁇ 100 ⁇ ) does not contain a sufficient amount of an active lithium storage material (hence, insufficient current output); (c) thicker electrodes are prone to delaminate or crack upon drying or handling after roll-coating and the production of thick electrodes requires a coating line that runs for > 100 meters long
  • conventional lithium-ion batteries are such that they are rigid (non-flexible) and cannot be bent or twisted. It is also difficult to implement these conventional batteries in the body of an electric vehicle (e.g. e-bike and battery- driven car). For instance, some confined spaces inside a car door structure are not conducive to accommodating rigid rectangular or cylindrical batteries.
  • either the anode active material (e.g. Si) or the cathode active material (e.g. lithium transition metal oxide) is deposited in a thin film form directly onto a current collector, such as a sheet of copper foil or Al foil.
  • a current collector such as a sheet of copper foil or Al foil.
  • an extremely small thickness-direction dimension typically much smaller than 500 nm, often necessarily thinner than 100 nm implies that only a small amount of active material can be incorporated in an electrode (given the same electrode or current collector surface area), providing a low total lithium storage capacity and low lithium storage capacity per unit electrode surface area.
  • Such a thin film must have a thickness less than 100 nm to be more resistant to cycling-induced cracking (for the anode) or to facilitate a full utilization of the cathode active material. Such a constraint further diminishes the total lithium storage capacity and the lithium storage capacity per unit electrode surface area.
  • Such a thin-film battery has very limited scope of application.
  • a Si layer thicker than 100 nm has been found to exhibit poor cracking resistance during battery charge/discharge cycles. It takes but a few cycles to get fragmented.
  • a sputtered layer of lithium metal oxide thicker than 100 nm does not allow lithium ions to fully penetrate and reach full body of the cathode layer, resulting in a poor cathode active material utilization rate.
  • a desirable electrode thickness is at least 100 ⁇ , with individual active material coating or particle having a dimension desirably less than 100 nm.
  • these thin-film electrodes (with a thickness ⁇ 100 nm) directly deposited on a current collector fall short of the required thickness by three (3) orders of magnitude.
  • all of the cathode active materials are not conductive to both electrons and lithium ions.
  • a large layer thickness implies an excessively high internal resistance and a poor active material utilization rate.
  • the prior art lithium battery cell is typically made by a process that includes the following steps: (a) The first step includes mixing particles of the anode active material (e.g.
  • the second step includes coating the anode slurry onto one or both primary surfaces of an anode current collector (e.g.
  • the coated layer by vaporizing the solvent (e.g. NMP) to form a dried anode electrode coated on Cu foil.
  • the cathode slurry is coated and dried to form a dried cathode electrode coated on Al foil.
  • the third step includes laminating an anode/Cu foil sheet, a porous separator layer, and a cathode/ Al foil sheet together to form a 3-layer or 5-layer assembly, which is cut and slit into desired sizes and stacked to form a rectangular structure (as an example of shape) or rolled into a cylindrical cell structure, (d) The rectangular or cylindrical laminated structure is then encased in an aluminum-plastic laminated envelope or steel casing, (e) A liquid electrolyte is then injected into the laminated structure to make a lithium battery cell.
  • an electrode layer (anode layer or cathode layer) that is thicker than 200 ⁇ (100 ⁇ on each side of a solid current collector, such as Al foil).
  • An electrode of 100-200 ⁇ in thickness typically requires a heating zone of 30-50 meters long in a slurry coating facility, which is too time consuming, too energy intensive, and not cost-effective.
  • electrode active materials such as metal oxide particles
  • the resulting electrodes are very fragile and brittle. Thicker electrodes have a high tendency to delaminate and crack.
  • the actual mass loadings of the electrodes and the apparent densities for the active materials are too low to achieve a gravimetric energy density of > 200 Wh/kg.
  • the anode active material mass loading of the electrodes is significantly lower than 25 mg/cm 2 and the apparent volume density or tap density of the active material is typically less than 1.2 g/cm 3 even for relatively large particles of graphite.
  • the cathode active material mass loading of the electrodes is significantly lower than 45 mg/cm 2 for lithium metal oxide-type inorganic materials and lower than 15 mg/cm 2 for organic or polymer materials.
  • non-active materials e.g. conductive additive and resin binder
  • conductive additive and resin binder add additional weights and volumes to the electrode without contributing to the cell capacity.
  • These low areal densities and low volume densities result in relatively low gravimetric energy density and low volumetric energy density.
  • the conventional process requires dispersing electrode active materials (anode active material or cathode active material) in a liquid solvent (e.g. MP) to make a slurry and, upon coating on a current collector surface, the liquid solvent has to be removed to dry the electrode layer.
  • a liquid solvent e.g. MP
  • the anode and cathode layers, along with a separator layer, are laminated together and packaged in a housing to make a battery cell, one then injects a liquid electrolyte into the cell. In actuality, one makes the two electrodes wet, then makes the electrodes dry, and finally makes them wet again. Such a wet-dry-wet process does not sound like a good process at all.
  • the energy density data reported based on either the active material weight alone or the electrode weight cannot directly translate into the energy densities of a practical battery cell or device.
  • the "overhead weight” or weights of other device components must also be taken into account.
  • the convention production process results in the weight proportion of the anode active material (e.g. graphite or carbon) in a lithium- ion battery being typically from 12% to 17%, and that of the cathode active material (e.g. LiMn 2 0 4 ) from 20% to 35%.
  • the present invention provides a process for producing a flexible, shape-conformable, and non-flammable alkali metal battery cell having a rope shape, high active material mass loading, low overhead weight and volume, high gravimetric energy density, and high volumetric energy density.
  • the manufacturing costs of the alkali metal batteries produced by the presently invented process can be significantly lower than those by conventional processes.
  • the present rope- shaped alkali metal battery containing braid- or yarn-shape electrodes
  • a conductive additive or a resin binder may be optionally added into the mixture, but this is not required or even desired.
  • This first electrode 11 can optionally contain an active material-free and electrolyte-free end section 13 that can serve as a terminal tab for connecting to an external load.
  • This first electrode can assume a cross- section that is of any shape; e.g. circular, rectangular, elliptic, square, hexagonal, hollow, or irregular in shape.
  • the first electrode comprises a conductive rod (not a porous foam) and the first mixture is coated or deposited on the surface of this conductive rod.
  • This rod can be as simple as a metal wire, conductive polymer fiber or yarn, carbon or graphite fiber or yarn, or multiple thin wires, fibers, or yarns.
  • the second electrode must contain a porous foam structure.
  • the second step involves wrapping around or encasing the first electrode 11 with a thin layer of porous separator 15 (e.g. porous plastic film, paper, fiber mat, non-woven, glass fiber cloth, etc.) that is permeable to Li + , Na + , or K + ions.
  • porous separator 15 e.g. porous plastic film, paper, fiber mat, non-woven, glass fiber cloth, etc.
  • This step can be as simple as wrapping the first electrode with a thin, porous plastic tape in one full circle or slightly more than one full circle, or in a spiral manner.
  • the main purpose is to electronically separate the anode and the cathode to prevent internal shorting.
  • the porous separator layer can be simply deposited all around the first electrode by spraying, printing, coating, dip casting, etc.
  • the third step involves preparing a second electrode 17 that comprises a mixture of second active material and second electrolyte and, optionally, a conductive additive or resin binder (although not necessary and not desirable).
  • This second electrode 17 can optionally contain an active material-free and electrolyte-free end section that can serve as a terminal tab for connecting to an external load.
  • the second electrode may be optionally but desirably encased or wrapped around by a porous separator layer 18.
  • This second electrode, with or without an encasing porous separator layer is then combined with the first electrode using a braiding or yarn -making procedure to make a 2-ply twist yarn or braid.
  • the first electrode is an anode
  • the second electrode is a cathode; or vice versa.
  • a yarn or braid can contain multiple anodes (i.e. multiple filaments or rods each containing an anode active material and an electrolyte) combined with one single cathode or multiple cathodes.
  • a yarn or braid can contain multiple cathodes (i.e. multiple filaments or rods each containing a cathode active material and an electrolyte) combined with one single anode or multiple anode filaments.
  • this braid or yarn structure is encased or protected by a protective casing or sheath 19 that is electrically insulating (e.g. a plastic sheath or rubber shell).
  • n-ply braid/yarn n > 2
  • the protective sheath it may be noted that some additional electrolyte may be incorporated between the n-ply braid/yarn (n > 2) and the protective sheath. However, this is not a requirement since all the electrode rods or filaments already contain an active material and an electrolyte in their pores.
  • one of the electrodes comprises a porous rod having pores to accommodate an active material-electrolyte mixture and at least one of the electrodes is a non- porous rod (filament, fiber, wire, etc.) having an active material-electrolyte mixture coated on its surface.
  • one preferred method comprises continuously feeding one or a plurality of electrically conductive porous rods or filaments (e.g. 304, 310, 322, or 330; only one foam rod shown), from a feeder roller (not shown), into an active material/electrolyte impregnation zone where a wet active material mixture (e.g.
  • slurry, suspension, or gel-like mass such as 306a, 306b, 312a, 312b) of an electrode active material, an electrolyte and an optional conductive additive is delivered to at least a porous surface of the porous rod (e.g. 304 or 310 in Schematic A and schematic B, respectively, of FIG. 1(D)).
  • the wet active material/electrolyte mixture (306a, 306b) is forced to impregnate into the porous rod from both sides using one or two pairs of rollers (302a, 302b, 302c, and 302d) to form an impregnated active electrode 308 (an anode or cathode).
  • the conductive porous foam rod contains interconnected network of electron-conducting pathways and preferably at least 70% by volume of pores (preferably > 80%, more preferably > 90%, and further more preferably > 95%).
  • two feeder rollers 316a, 316b are used to continuously pay out two protective films 314a, 314b that support wet active material/electrolyte mixture rods 312a, 312b.
  • These wet active material/electrolyte mixture rods 312a, 312b can be delivered to the protective (supporting) films 314a, 314b using a broad array of procedures (e.g. printing, spraying, casting, coating, etc., which are well known in the art).
  • the wet active mixture material/electrolyte is impregnated into the pores of the porous rod 310 to form an active material electrode 320 (an anode or cathode electrode) covered by two protective films 314a, 314b. These protective films can be later removed.
  • two spraying devices 324a, 324b were used to dispense the wet active material/electrolyte mixture (325a, 325b) to the two opposed porous surfaces of the conductive rectangular porous rod 322.
  • the wet active material mixture is forced to impregnate into the porous rod from both sides using one or two pairs of rollers to form an impregnated active electrode 326 (an anode or cathode).
  • two spraying devices 332a, 332b were used to dispense the wet active material mixture (333a, 333b) to the two opposed porous foam surfaces of the conductive porous rod 330.
  • the wet active material- electrolyte mixture is forced to impregnate into the porous rod from both sides using one or two pairs of rollers to form an impregnated active electrode 338 (an anode or cathode).
  • the electrode production process begins by continuously feeding a conductive porous foam filament 356 of any cross- sectional shape from a feeder roller 340.
  • the porous filament 356 is directed by a roller 342 to get immersed into a wet active material mixture mass 346 (slurry, suspension, gel, etc.) in a container 344.
  • the active material mixture begins to impregnate into pores of the porous rod 356 as it travels toward roller 342b and emerges from the container to feed into the gap between two rollers 348a, 348b.
  • Two protective films 350a, 350b are concurrently fed from two respective rollers 352a, 352b to cover the impregnated porous rod 354, which may be continuously collected on a rotating drum (a winding roller 355).
  • the process is applicable to both the anode and the cathode electrodes.
  • the resulting electrode rod can have a thickness or diameter from 100 nm to several centimeters (or thicker, if so desired).
  • the electrode thickness or diameter is from 100 nm to 100 ⁇ , more typically from 1 ⁇ to 50 ⁇ , and most typically from 10 ⁇ to 30 ⁇ .
  • the electrode typically and desirably has a thickness no less than 100 ⁇
  • the electrically conductive porous rods may be selected from metal foam, metal web or screen, perforated metal sheet-based structure, metal fiber mat, metal nanowire mat, conductive polymer nano-fiber mat, conductive polymer foam, conductive polymer-coated fiber foam, carbon foam, graphite foam, carbon aerogel, carbon xerogel, graphene aerogel, graphene foam, graphene oxide foam, reduced graphene oxide foam, carbon fiber foam, graphite fiber foam, exfoliated graphite foam, or a combination thereof.
  • the porous rods must be made of an electrically conductive material, such as a carbon, graphite, metal, metal-coated fiber, conductive polymer, or conductive polymer-coated fiber, which is in a form of highly porous mat, screen/grid, non-woven, foam, etc. Examples of conductive porous rods are presented in FIG. 3(A), FIG. 3(B), FIG. 3(C), and FIG. 3(D).
  • the porosity level is preferably at least 70% by volume, preferably greater than 80%, further preferably greater than 90%, and most preferably greater than 95% by volume.
  • the backbone or foam walls form a network of electron-conducting pathways. These foam structures can be readily made into any cross-sectional shape.
  • the resulting rope-shape battery can be very flexible and can be made to conform to essentially any odd shape. Even when the salt concentration in a liquid solvent is high (e.g. from 2.5 M to 15 M), the foam containing electrolyte inside its pores remains deformable, bendable, twistable, and conformable to even odd shapes.
  • substantially all of the pores in the original conductive porous rods are filled with the electrode active material (anode or cathode), electrolyte, and optional conductive additive (no binder resin needed). Since there are great amounts of pores (70-99%) relative to the pore walls or conductive pathways (1-30%), very little space is wasted ("being wasted” means not being occupied by the electrode active material and electrolyte), resulting in high proportion of electrode active material -electrolyte mixture (high active material loading mass).
  • the electrons only have to travel a short distance (half of the pore size, on average; e.g. nanometers or a few micrometers) before they are collected by the pore walls since pore walls are present everywhere throughout the entire electrode structure (the conductive foam serving as a current collector). These pore walls form a 3-D network of interconnected electron-transporting pathways with minimal resistance.
  • all electrode active material particles are pre-dispersed in a liquid electrolyte (no wettability issue), eliminating the possibility of dry pockets commonly present in an electrode prepared by the conventional process of wet coating, drying, packing, and electrolyte injection.
  • the presently invented process has a totally unexpected advantage over the conventional battery cell production process.
  • the anode active material contains a prelithiated or pre- sodiated version of graphene sheets selected from pristine graphene (e.g. FIG. 2), graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, chemically functionalized graphene, or a combination thereof.
  • the starting graphitic material for producing any one of the above graphene materials may be selected from natural graphite, artificial graphite, meso-phase carbon, meso-phase pitch, meso-carbon micro-bead, soft carbon, hard carbon, coke, carbon fiber, carbon nano-fiber, carbon nano-tube, or a combination thereof.
  • Graphene materials are also a good conductive additive for both the anode and cathode active materials of an alkali metal battery.
  • the constituent graphene planes of a graphite crystallite in a natural or artificial graphite particle can be exfoliated and extracted or isolated to obtain individual graphene sheets of hexagonal carbon atoms, which are single-atom thick, provided the inter-planar van der Waals forces can be overcome.
  • An isolated, individual graphene plane of carbon atoms is commonly referred to as single-layer graphene.
  • a stack of multiple graphene planes bonded through van der Waals forces in the thickness direction with an inter-graphene plane spacing of approximately 0.3354 nm is commonly referred to as a multi-layer graphene.
  • a multi-layer graphene platelet has up to 300 layers of graphene planes ( ⁇ 100 nm in thickness), but more typically up to 30 graphene planes ( ⁇ 10 nm in thickness), even more typically up to 20 graphene planes ( ⁇ 7 nm in thickness), and most typically up to 10 graphene planes (commonly referred to as few-layer graphene in scientific community).
  • Single-layer graphene and multi-layer graphene sheets are collectively called “nano graphene platelets" (NGPs).
  • Graphene sheets/platelets are a new class of carbon nano material (a 2-D nano carbon) that is distinct from the 0-D fullerene, the 1-D CNT or CNF, and the 3-D graphite.
  • a graphene material isolated graphene sheets
  • CNT carbon nanotube
  • CNF carbon nano-fiber
  • graphene materials are obtained by intercalating natural graphite particles with a strong acid and/or an oxidizing agent to obtain a graphite intercalation compound (GIC) or graphite oxide (GO), as illustrated in FIG. 4(A) and FIG.
  • the presence of chemical species or functional groups in the interstitial spaces between graphene planes in a GIC or GO serves to increase the inter-graphene spacing (d 02 , as determined by X- ray diffraction), thereby significantly reducing the van der Waals forces that otherwise hold graphene planes together along the c-axis direction.
  • the GIC or GO is most often produced by immersing natural graphite powder (100 in FIG. 4(B)) in a mixture of sulfuric acid, nitric acid (an oxidizing agent), and another oxidizing agent (e.g. potassium permanganate or sodium perchlorate).
  • the resulting GIC (102) is actually some type of graphite oxide (GO) particles if an oxidizing agent is present during the intercalation procedure.
  • This GIC or GO is then repeatedly washed and rinsed in water to remove excess acids, resulting in a graphite oxide suspension or dispersion, which contains discrete and visually discernible graphite oxide particles dispersed in water.
  • a graphite oxide suspension or dispersion which contains discrete and visually discernible graphite oxide particles dispersed in water.
  • Route 1 involves removing water from the suspension to obtain "expandable graphite,” which is essentially a mass of dried GIC or dried graphite oxide particles.
  • expandable graphite essentially a mass of dried GIC or dried graphite oxide particles.
  • the GIC undergoes a rapid volume expansion by a factor of 30-300 to form “graphite worms” (104), which are each a collection of exfoliated, but largely un-separated graphite flakes that remain interconnected.
  • these graphite worms can be re-compressed to obtain flexible graphite sheets or foils (106) that typically have a thickness in the range of 0.1 mm (100 ⁇ ) - 0.5 mm (500 ⁇ ).
  • the exfoliated graphite is subjected to high-intensity mechanical shearing (e.g. using an ultrasonicator, high-shear mixer, high-intensity air jet mill, or high-energy ball mill) to form separated single-layer and multi-layer graphene sheets (collectively called NGPs, 112), as disclosed in our US Application No.
  • high-intensity mechanical shearing e.g. using an ultrasonicator, high-shear mixer, high-intensity air jet mill, or high-energy ball mill
  • Single-layer graphene can be as thin as 0.34 nm, while multi -layer graphene can have a thickness up to 100 nm, but more typically less than 10 nm (commonly referred to as few-layer graphene).
  • Multiple graphene sheets or platelets may be made into a sheet of NGP paper using a paper-making process. This sheet of NGP paper is an example of the porous graphene structure layer utilized in the presently invented process.
  • Route 2 entails ultrasonicating the graphite oxide suspension (e.g. graphite oxide particles dispersed in water) for the purpose of separating/isolating individual graphene oxide sheets from graphite oxide particles.
  • NGPs or graphene materials include discrete sheets/platelets of single-layer and multi-layer (typically less than 10 layers) pristine graphene, graphene oxide, reduced graphene oxide (RGO), graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, chemically functionalized graphene, doped graphene (e.g. doped by B or N).
  • Pristine graphene has essentially 0% oxygen.
  • RGO typically has an oxygen content of 0.001%-5% by weight.
  • Graphene oxide (including RGO) can have 0.001%-50% by weight of oxygen.
  • pristine graphene all the graphene materials have 0.001%-50% by weight of non-carbon elements (e.g. O, H, N, B, F, CI, Br, I, etc.). These materials are herein referred to as non-pristine graphene materials.
  • Pristine graphene in smaller discrete graphene sheets (typically 0.3 ⁇ to 10 ⁇ ), may be produced by direct ultrasonication (also known as liquid phase exfoliation or production) or supercritical fluid exfoliation of graphite particles. These processes are well-known in the art.
  • the graphene oxide (GO) may be obtained by immersing powders or filaments of a starting graphitic material (e.g. natural graphite powder) in an oxidizing liquid medium (e.g. a mixture of sulfuric acid, nitric acid, and potassium permanganate) in a reaction vessel at a desired temperature for a period of time (typically from 0.5 to 96 hours, depending upon the nature of the starting material and the type of oxidizing agent used).
  • an oxidizing liquid medium e.g. a mixture of sulfuric acid, nitric acid, and potassium permanganate
  • the resulting graphite oxide particles may then be subjected to thermal exfoliation or ultrasonic wave-induced exfoliation to produce isolated GO sheets.
  • These GO sheets can then be converted into various graphene materials by substituting -OH groups with other chemical groups (e.g. -Br, H 2 , etc.).
  • 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.
  • the process of liquid phase exfoliation includes ultrasonic treatment of a graphite fluoride in a liquid medium.
  • 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 150-250°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 150-250°C.
  • Other methods to synthesize nitrogen doped graphene include nitrogen plasma treatment on graphene,
  • a graphite particle (e.g. 100) is typically composed of multiple graphite crystallites or grains.
  • a graphite crystallite is made up of layer planes of hexagonal networks of carbon atoms. These layer planes of hexagonally arranged carbon atoms are substantially flat and are oriented or ordered so as to be substantially parallel and equidistant to one another in a particular crystallite.
  • These layers of hexagonal-structured carbon atoms commonly referred to as graphene layers or basal planes, are weakly bonded together in their thickness direction (crystallographic c-axis direction) by weak van der Waals forces and groups of these graphene layers are arranged in crystallites.
  • the graphite crystallite structure is usually characterized in terms of two axes or directions: the c-axis direction and the a-axis (or b-axis) direction.
  • the c- axis is the direction perpendicular to the basal planes.
  • the a- or ⁇ -axes are the directions parallel to the basal planes (perpendicular to the c-axis direction). Due to the weak van der Waals forces holding the parallel graphene layers, natural graphite can be treated so that the spacing between the graphene layers can be appreciably opened up so as to provide a marked expansion in the c-axis direction, and thus form an expanded graphite structure in which the laminar character of the carbon layers is substantially retained.
  • flakes of natural graphite are intercalated in an acid solution to produce graphite intercalation compounds (GICs, 102).
  • GICs graphite intercalation compounds
  • the GICs are washed, dried, and then exfoliated by exposure to a high temperature for a short period of time. This causes the flakes to expand or exfoliate in the c-axis direction of the graphite up to 80-300 times of their original dimensions.
  • the exfoliated graphite flakes are vermiform in appearance and, hence, are commonly referred to as graphite worms 104.
  • worms of graphite flakes which have been greatly expanded can be formed without the use of a binder into cohesive or integrated sheets of expanded graphite, e.g. webs, papers, strips, tapes, foils, mats or the like (typically referred to as "flexible graphite” 106) having a typical density of about 0.04-2.0 g/cm 3 for most applications.
  • Acids, such as sulfuric acid, are not the only type of intercalating agent (intercalant) that penetrate into spaces between graphene planes to obtain GICs.
  • stage n implies one intercalant layer for every n graphene planes.
  • a stage-1 potassium-intercalated GIC means there is one layer of K for every graphene plane; or, one can find one layer of K atoms inserted between two adjacent graphene planes in a G/K/G/K/G/KG .... sequence, where G is a graphene plane and K is a potassium atom plane.
  • a stage-2 GIC will have a sequence of GG/K/GG/K/GG/K/GG ....
  • stage-3 GIC will have a sequence of GGG/K/GGG/K/GGG ...., etc. These GICs can then be brought in contact with water or water-alcohol mixture to produce exfoliated graphite and/or separated/isolated graphene sheets.
  • Exfoliated graphite worms may be subjected to high -intensity mechanical
  • NGPs nano graphene platelets
  • An NGP is composed of a graphene sheet or a plurality of graphene sheets with each sheet being a two-dimensional, hexagonal structure of carbon atoms.
  • a mass of multiple NGPs including discrete sheets/platelets of single-layer and/or few-layer graphene or graphene oxide may be made into a porous graphene film (114 in FIG.
  • graphite worms tend to be separated into the so-called expanded graphite flakes (108 in FIG. 4(B) having a thickness > 100 nm.
  • expanded graphite flakes can be formed into graphite mat or nonwoven 106 using mat- making process, with or without a resin binder, to form an expanded graphite foam.
  • Graphite foams can be made by graphitization of carbon foams as well.
  • the anode active material absorbs alkali ions (e.g.
  • lithium ions at an electrochemical potential of less than 1.0 volt (preferably less than 0.7 volts) above the Li/Li + (i.e. relative to Li ⁇ Li + + e " as the standard potential) the Na/Na + reference when the battery is charged.
  • the anode active material is selected from the group consisting of: (a) Particles of natural graphite, artificial graphite, meso-carbon microbeads (MCMB), and carbon (including soft carbon, hard carbon, carbon nano-fiber, and carbon nano-tube); (b) Silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), nickel (Ni), cobalt (Co), manganese (Mn), titanium (Ti), iron (Fe), and cadmium (Cd); (Si, Ge, Al, and Sn are most desirable due to their high specific capacities.) (c) Alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, or Cd with other elements, wherein the alloys or compounds are stoichiometric or non-stoichiometric (e.g.
  • SiAl, SiSn SiAl, SiSn
  • Pre-lithiated versions thereof e.g. pre-lithiated Ti0 2 , which is lithium titanate
  • Pre-lithiated graphene sheets Pre-lithiated graphene sheets; and combinations thereof.
  • the first electrode or second electrode contains particles, foil, or coating of Li, Na, K, or a combination thereof as an electrode active material.
  • the anode active material is a pre-sodiated or pre- potassiated version of graphene sheets selected from pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, chemically functionalized graphene, or a combination thereof.
  • the starting graphitic material for producing any one of the above graphene materials may be selected from natural graphite, artificial graphite, meso-phase carbon, meso- phase pitch, meso-carbon micro-bead, soft carbon, hard carbon, coke, carbon fiber, carbon nano- fiber, carbon nano-tube, or a combination thereof.
  • Graphene materials are also a good conductive additive for both the anode and cathode active materials of an alkali metal battery.
  • the anode may contain an alkali ion source selected from an alkali metal, an alkali metal alloy, a mixture of alkali metal or alkali metal alloy with an alkali intercalation compound, an alkali element-containing compound, or a combination thereof.
  • an anode active material that contains an alkali intercalation compound selected from petroleum coke, carbon black, amorphous carbon, hard carbon, templated carbon, hollow carbon nanowires, hollow carbon sphere, titanates, NaTi 2 (P0 4 )3, Na 2 Ti 3 0 7 (Sodium titanate), Na 2 C 8 H 4 0 4 (Disodium Terephthalate), Na 2 TP (Sodium
  • the anode may contain a mixture of 2 or 3 types of anode active materials (e.g. mixed particles of activated carbon + NaTi 2 (P0 4 ) 3 ) and the cathode can be a sodium intercalation compound alone (e.g. Na x Mn0 2 ), an electric double layer capacitor-type cathode active material alone (e.g. activated carbon), a redox pair of -Mn0 2 /activated carbon for pseudo-capacitance.
  • anode active materials e.g. mixed particles of activated carbon + NaTi 2 (P0 4 ) 3
  • the cathode can be a sodium intercalation compound alone (e.g. Na x Mn0 2 ), an electric double layer capacitor-type cathode active material alone (e.g. activated carbon), a redox pair of -Mn0 2 /activated carbon for pseudo-capacitance.
  • the cathode active material typically is an alkali metal intercalation compound or alkali metal-absorbing compound that is capable of storing alkali metal ions when the battery is discharged and releasing alkali metal ions into the electrolyte when rec-charged.
  • the cathode active material may be selected from an inorganic material, an organic or polymeric material, a metal oxide/phosphate/sulfide (most desired types of inorganic cathode materials), or a combination thereof.
  • the group of metal oxide, metal phosphate, and metal sulfides consisting of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium vanadium oxide, lithium transition metal oxide, lithium-mixed metal oxide, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, lithium mixed metal phosphates, transition metal sulfides, and combinations thereof.
  • the lithium vanadium oxide may be selected from the group consisting of V0 2 , Li x V0 2 , V 2 0 5 , Li x V 2 0 5 , V 3 0 8 , Li x V 3 0 8 , Li x V 3 0 7 , V 4 0 9 , Li x V 4 09, V 6 0i 3 , Li x V 6 0i 3 , their doped versions, their derivatives, and combinations thereof, wherein 0.1 ⁇ x ⁇ 5.
  • Lithium transition metal oxide may be 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 combination thereof, wherein M is a transition metal or a mixture of multiple transition metals.
  • the cathode active material may contain a sodium intercalation compound (or their potassium counterparts) selected from NaFeP0 4 (Sodium iron phosphate), Na 0 7 FeP0 4 , Nai .5 VOPO 4 F 0 5 , Na 3 V 2 (P0 4 ) 3 , Na 3 V2(P0 4 ) 2 F 3 , Na 2 FeP0 4 F, NaFeF 3 , NaVP0 4 F, Na 3 V 2 (P0 4 ) 2 F 3 , Nai 5 VOPO 4 F 0 5 , Na 3 V 2 (P0 4 ) 3 , NaV 6 0i 5 , Na x V0 2 , Na 0 .
  • NaFeP0 4 Sodium iron phosphate
  • Na 0 7 FeP0 4 Nai .5 VOPO 4 F 0 5
  • Na 3 V 2 (P0 4 ) 3 Na 3 V2(P0 4 ) 2 F 3
  • Na x Co0 2 (Sodium cobalt oxide), Na 2/3 [Nii /3 Mn 2/3 ]0 2 , Na x (Fei /2 Mni /2 )0 2 , Na x Mn0 2 (Sodium manganese bronze), ⁇ - ⁇ 0 2 , Na 0 44 MnO 2 , Na 0 . 44 MnO 2 /C, Na 4 Mn 9 0i 8 , NaFe 2 Mn(P0 4 ) 3 , Na 2 Ti 3 0 7 , Nii /3 Mni /3 Coi /3 0 2 , Cu 0.56 Ni 0 . HCF (Copper and nickel), Copper and nickel
  • NiHCF nickel hexacyanoferrate
  • inorganic materials for use as a cathode active material may be selected from sulfur, sulfur compound, lithium polysulfide, 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 inorganic material may be 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 may be selected from a functional material or nano-structured material having an alkali metal ion-capturing functional group or alkali metal ion-storing surface in direct contact with the electrolyte.
  • the functional group reversibly reacts with an alkali metal ion, forms a redox pair with an alkali metal ion, or forms a chemical complex with an alkali metal ion.
  • the functional material or nano-structured material may be selected from the group consisting of (a) a nano-structured or porous disordered carbon material selected from a soft carbon, hard carbon, polymeric carbon or carbonized resin, meso- phase carbon, coke, carbonized pitch, carbon black, activated carbon, nano-cellular carbon foam or partially graphitized carbon; (b) a nano graphene platelet selected from a single-layer graphene sheet or multi-layer graphene platelet; (c) a carbon nanotube selected from a single- walled carbon nanotube or multi -walled carbon nanotube; (d) a carbon nano-fiber, nano-wire, metal oxide nano-wire or fiber, conductive polymer nano-fiber, or a combination thereof; (e) a carbonyl-containing organic or polymeric molecule; (f) a functional material containing a carbonyl, carboxylic, or amine group; and combinations thereof.
  • a nano-structured or porous disordered carbon material selected from a soft carbon, hard carbon
  • PTCDA perylenetetracarboxylicacid-dianhydride
  • NTCDA 1,4,5,8- naphthalene-tetracarboxylicacid-dianhydride
  • Benzene-l,2,4,5-tetracarboxylic dianhydride 1,4,5,8-tetrahydroxy anthraquinon, Tetrahydroxy-p-benzoquinone
  • the organic material or polymeric material may be 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),
  • PAQS Poly(anthraquinonyl sulfide)
  • PTCDA 10-perylenetetracarboxylic dianhydride
  • PYT pyrene-4,5,9,10-tetraone
  • TCNQ Tetracyanoquinodimethane
  • TCNE tetracyanoethylene
  • HMTP 2,3,6,7,10, 11-hexamethoxytriphenylene
  • PADAQ poly(5-amino- 1,4-dyhydroxy anthraquinone)
  • phosphazene disulfide polymer [( PS 2 ) 3 ] «)
  • lithiated 1,4,5,8-naphthalenetetraol formaldehyde polymer Hexaazatrinaphtylene (HATN)
  • anthraquinone ADDAQ
  • 5-amino-l,4-dyhydroxy anthraquinone ADAQ
  • calixquinone Li 4 C 6 0 6 , Li 2 C 6 0 6 , Li 6 C 6 0 6 , or a combination thereof.
  • the thioether polymer is selected from Poly[methanetetryl-tetra(thiomethylene)]
  • PMTTM Poly(2,4-dithiopentanylene)
  • PDTP Poly(2,4-dithiopentanylene)
  • PETT Poly(ethene- 1, 1,2,2- tetrathiol)
  • PETT Poly(ethene- 1, 1,2,2- tetrathiol)
  • PPDT Poly(2-phenyl-l,3-dithiolane)
  • PPDT Poly(l,4-di(l,3-dithiolan-2-yl)benzene)
  • the organic material may be selected from a phthalocyanine compound selected from copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, iron phthalocyanine, lead phthalocyanine, nickel phthalocyanine, vanadyl phthalocyanine, fluorochromium
  • phthalocyanine aluminum phthalocyanine chloride, cadmium phthalocyanine, chlorogallium phthalocyanine, cobalt phthalocyanine, silver phthalocyanine, a metal-free phthalocyanine, a chemical derivative thereof, or a combination thereof.
  • the lithium intercalation compound or lithium-absorbing compound may be selected from a metal carbide, metal nitride, metal boride, metal dichalcogenide, or a combination thereof.
  • the lithium intercalation compound or lithium-absorbing compound is selected from an oxide, dichalcogenide, trichalcogenide, sulfide, selenide, or telluride of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, vanadium, chromium, cobalt, manganese, iron, or nickel in a nanowire, nano-disc, nano-ribbon, or nano platelet form.
  • 2D inorganic materials can be used as a cathode active material in the presented invented lithium battery prepared by the invented direct active material-electrolyte injection process.
  • Layered materials represent a diverse source of 2D systems that can exhibit unexpected electronic properties and good affinity to lithium ions.
  • graphite is the best known layered material, transition metal dichalcogenides (TMDs), transition metal oxides (TMOs), and a broad array of other
  • the lithium intercalation compound or lithium-absorbing compound is selected from nano discs, nano platelets, nano-coating, or nano sheets of an inorganic material 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; wherein the discs, platelets, or sheets have a thickness less than 100 nm.
  • an inorganic material selected from: (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) sulfide, selenide, or telluride of niobium, zir
  • the lithium intercalation compound or lithium-absorbing compound may contain nano discs, nano platelets, nano-coating, or nano sheets of a compound selected from: (i) bismuth selenide or bismuth telluride, (ii) transition metal dichalcogenide or trichalcogenide, (iii) sulfide, selenide, or telluride of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, cobalt, manganese, iron, nickel, or a transition metal; (iv) boron nitride, or (v) a combination thereof, wherein the discs, platelets, coating, or sheets have a thickness less than 100 nm.
  • Non-graphene 2D nano materials single-layer or few-layer (up to 20 layers), can be produced by several methods: mechanical cleavage, laser ablation (e.g. using laser pulses to ablate TMDs down to a single layer), liquid phase exfoliation, and synthesis by thin film techniques, such as PVD (e.g. sputtering), evaporation, vapor phase epitaxy, liquid phase epitaxy, chemical vapor epitaxy, molecular beam epitaxy (MBE), atomic layer epitaxy (ALE), and their plasma-assisted versions.
  • PVD e.g. sputtering
  • evaporation vapor phase epitaxy
  • liquid phase epitaxy liquid phase epitaxy
  • chemical vapor epitaxy molecular beam epitaxy
  • ALE atomic layer epitaxy
  • a wide range of electrolytes can be used for practicing the instant invention. Most preferred are non-aqueous organic and/or ionic liquid electrolytes.
  • the non-aqueous electrolyte to be employed herein may be produced by dissolving an electrolytic salt in a non-aqueous solvent.
  • Any known non-aqueous solvent which has been employed as a solvent for a lithium secondary battery can be employed.
  • a non-aqueous solvent mainly consisting of a mixed solvent comprising ethylene carbonate (EC) and at least one kind of non-aqueous solvent whose melting point is lower than that of aforementioned ethylene carbonate and whose donor number is 18 or less (hereinafter referred to as a second solvent) may be preferably employed.
  • This non-aqueous solvent is advantageous in that it is (a) stable against a negative electrode containing a carbonaceous material well developed in graphite structure; (b) effective in suppressing the reductive or oxidative decomposition of electrolyte; and (c) high in conductivity.
  • a non-aqueous electrolyte solely composed of ethylene carbonate (EC) is advantageous in that it is relatively stable against decomposition through a reduction by a graphitized carbonaceous material.
  • the melting point of EC is relatively high, 39 to 40°C, and the viscosity thereof is relatively high, so that the conductivity thereof is low, thus making EC alone unsuited for use as a secondary battery electrolyte to be operated at room temperature or lower.
  • the second solvent to be used in a mixture with EC functions to make the viscosity of the solvent mixture lower than that of EC alone, thereby promoting the ion conductivity of the mixed solvent.
  • the second solvent having a donor number of 18 or less (the donor number of ethylene carbonate is 16.4)
  • the aforementioned ethylene carbonate can be easily and selectively solvated with lithium ion, so that the reduction reaction of the second solvent with the carbonaceous material well developed in graphitization is assumed to be suppressed.
  • the donor number of the second solvent is controlled to not more than 18, the oxidative decomposition potential to the lithium electrode can be easily increased to 4 V or more, so that it is possible to manufacture a lithium secondary battery of high voltage.
  • Preferable second solvents are dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), ethyl propionate, methyl propionate, propylene carbonate (PC), .gamma. -butyrolactone (.gamma.-BL), acetonitrile (AN), ethyl acetate (EA), propyl formate (PF), methyl formate (MF), toluene, xylene and methyl acetate (MA).
  • DMC dimethyl carbonate
  • MEC methylethyl carbonate
  • DEC diethyl carbonate
  • ethyl propionate methyl propionate
  • PC propylene carbonate
  • AN acetonitrile
  • EA ethyl acetate
  • PF propyl formate
  • MF methyl formate
  • MA toluene
  • MA methyl acetate
  • the mixing ratio of the aforementioned ethylene carbonate in the mixed solvent should preferably be 10 to 80% by volume. If the mixing ratio of the ethylene carbonate falls outside this range, the conductivity of the solvent may be lowered or the solvent tends to be more easily decomposed, thereby deteriorating the charge/discharge efficiency. More preferable mixing ratio of the ethylene carbonate is 20 to 75% by volume. When the mixing ratio of ethylene carbonate in a non-aqueous solvent is increased to 20% by volume or more, the solvating effect of ethylene carbonate to lithium ions will be facilitated and the solvent decomposition-inhibiting effect thereof can be improved.
  • Examples of preferred mixed solvent are a composition comprising EC and MEC;
  • volume ratio of MEC being controlled within the range of 30 to 80%.
  • the volume ratio of MEC from the range of 30 to 80%, more preferably 40 to 70%, the conductivity of the solvent can be improved.
  • an electrolyte having carbon dioxide dissolved therein may be employed, thereby effectively improving both the capacity and cycle life of the battery.
  • the electrolytic salts to be incorporated into a non-aqueous electrolyte may be selected from a lithium salt such as lithium perchlorate (L1CIO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (L1BF 4 ), lithium hexafluoroarsenide (LiAsF 6 ), lithium trifluoro- metasulfonate (LiCF 3 S0 3 ) and bis-trifluorom ethyl sulfonylimide lithium [LiN(CF 3 S0 2 ) 2 ].
  • a lithium salt such as lithium perchlorate (L1CIO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (L1BF 4 ), lithium hexafluoroarsenide (LiAsF 6 ), lithium trifluoro- metasulfonate (LiCF 3 S0 3 ) and bis-trifluorom e
  • LiPF 6 , L1BF4 and LiN(CF 3 S0 2 ) 2 are preferred.
  • the content of aforementioned electrolytic salts in the non-aqueous solvent is preferably greater than 2.5 M (mol/1), more preferably > 3.0 M, further more preferably > 5.0 M, still more preferably > 7.0 M, and most preferably > 10 M.
  • alkali metal salt makes it easier to form a cable-shape battery that does not have the tendency to leak during manufacturing or during bending or twisting of the cable battery.
  • the salt concentration exceeds 3.5M. Some becomes non-flammable at a salt concentration greater than 3.0 M or just > 2.5 M. Battery scientists and engineers would expect that higher concentration means higher viscosity and lower ion mobility and, hence, lower alkali ion conductivity. We have found that this trend is generally true of the salt concentration range of 0.01 M to 2.0 M.
  • the alkali ion conductivity decreases initially when the salt concentration increases, but begins to increase
  • the ionic liquid is composed of ions only.
  • Ionic liquids are low melting temperature salts that are in a molten or liquid state when above a desired temperature. For instance, a salt is considered as an ionic liquid if its melting point is below 100°C. If the melting temperature is equal to or lower than room temperature (25°C), the salt is referred to as a room temperature ionic liquid (RTIL).
  • RTIL room temperature ionic liquid
  • the IL salts are characterized by weak interactions, due to the combination of a large cation and a charge-delocalized anion. This results in a low tendency to crystallize due to flexibility (anion) and asymmetry (cation).
  • a typical and well-known ionic liquid is formed by the combination of a l-ethyl-3- methylimidazolium (EMI) cation and an N,N-bis(trifluoromethane)sulphonamide (TFSI) anion.
  • EMI l-ethyl-3- methylimidazolium
  • TFSI N,N-bis(trifluoromethane)sulphonamide
  • Ionic liquids are basically composed of organic ions that come in an essentially unlimited number of structural variations owing to the preparation ease of a large variety of their components.
  • various kinds of salts can be used to design the ionic liquid that has the desired properties for a given application. These include, among others, imidazolium, pyrrolidinium and quaternary ammonium salts as cations and bis(trifluoromethanesulphonyl) imide, bis(fluorosulphonyl)imide, and hexafluorophosphate as anions.
  • ionic liquids come in different classes that basically include aprotic, protic and zwitterionic types, each one suitable for a specific application.
  • RTILs room temperature ionic liquids
  • RTILs include, but not limited to, tetraalkylammonium, di-, tri-, and tetra-alkylimidazolium, alkylpyridinium, dialkyl- pyrrolidinium, dialkylpiperidinium, tetraalkylphosphonium, and trialkylsulfonium.
  • RTILs include, but not limited to, BF 4 " , B(CN) 4 “ , CH3BF3 “ , CH2CHBF 3 “ , CF 3 BF 3 “ , C 2 F 5 BF 3 " , «-C 3 F 7 BF 3 “ , «-C 4 F 9 BF 3 “ , PF 6 " , CF 3 C0 2 “ , CF 3 S0 3 “ , N(S0 2 CF 3 ) 2 " , N(COCF 3 )(S0 2 CF 3 ) “ , N(S0 2 F) 2 “ , N(CN) 2 “ , C(CN) 3 “ , SCN “ , SeCN “ , CuCl 2 “ , A1C1 4 “ , F(HF) 2.3 “ , etc.
  • RTILs can possess archetypical properties such as high intrinsic ionic conductivity, high thermal stability, low volatility, low (practically zero) vapor pressure, non-flammability, the ability to remain liquid at a wide range of temperatures above and below room temperature, high polarity, high viscosity, and wide electrochemical windows. These properties, except for the high viscosity, are desirable attributes when it comes to using an RTIL as an electrolyte ingredient (a salt and/or a solvent) in a battery.
  • a rope shape battery means a battery that contains at least a rod-shape or filament-shape anode and a rod-shape or filament-shape cathode combined into a braid or twist yarn.
  • the battery has a length and a diameter or thickness wherein the aspect ratio (length-to- diameter or length-to-thickness ratio) is at least 10 and preferably at least 20.
  • the rope-shaped alkali metal battery can have a length greater than 1 m, or even greater than 100 m. The length can be as short as 1 ⁇ , but typically from 10 ⁇ to 10 m and more typically from micrometers to a few meters.
  • the invented rope-shaped alkali metal battery is so flexible that the battery can be easily bent to have a radius of curvature greater than 10 cm.
  • the battery is bendable to substantially conform to the shape of a void or interior compartment in a vehicle.
  • the void or interior compartment may be a trunk, door, hatch, spare tire compartment, area under seat or area under dashboard.
  • the battery is removable from a vehicle and is bendable to conform to the shape of a different void or interior compartment.
  • One or more units of instant rope-shape battery can be incorporated into a garment, belt, luggage strap, weaponry strap, musical instrument strap, helmet, hat, boot, foot covering, glove, wrist covering, watch band, jewelry item, animal collar or animal harness.
  • One or more units of instant rope-shaped battery can be removably incorporated a garment, belt, luggage strap, weaponry strap, musical instrument strap, helmet, hat, boot, foot covering, glove, wrist covering, watch band, jewelry item, animal collar or animal harness.
  • the invented rope battery conforms to the interior radius of a hollow bicycle frame.
  • anode active materials e.g. graphite foam, graphene foam, and metal foam
  • conductive porous rods e.g. graphite foam, graphene foam, and metal foam
  • EXAMPLE 1 Illustrative examples of electronically conductive porous rods or filaments as a porous current collector to accommodate an active material-electrolyte mixture
  • conductive porous rods serving as a current collector
  • anode or cathode e.g. Ni foam, Cu foam, Al foam, Ti foam, Ni mesh/web, stainless steel fiber mesh, etc.
  • Metal -coated polymer foams and carbon foams are also used as current collectors.
  • the most desirable thickness/diameter ranges for these conductive porous rods are 50-1000 ⁇ , preferably 100-800 ⁇ , more preferably 200-600 ⁇ .
  • porous carbon fibers e.g. made by electro-spinning polymer fibers, carbonizing the polymer fibers, and activating the resulting carbon fibers
  • porous graphite fibers can be used to accommodate an electrode active material-electrolyte mixture.
  • EXAMPLE 2 Ni foam and CVD graphene foam -based porous rods supported on Ni foam templates
  • Ni frame was etched away.
  • a thin layer of poly (methyl methacrylate) (PMMA) was deposited on the surface of the graphene films as a support to prevent the graphene network from collapsing during nickel etching. After the PMMA layer was carefully removed by hot acetone, a fragile graphene foam sample was obtained. The use of the PMMA support layer was considered critical to preparing a free-standing film of graphene foam.
  • a conducting polymer was used as a binder resin to hold graphene together while Ni was etched away.
  • the graphene foam or Ni foam thickness/diameter range was from 35 ⁇ to 600 ⁇ .
  • the Ni foam or the CVD graphene foam used herein is intended as conductive porous rods (CPR) to accommodate the ingredients (anode or cathode active material + optional conductive additive + liquid electrolyte) for the anode or cathode or both.
  • CPR conductive porous rods
  • Si nano particles dispersed in an organic liquid electrolyte e.g. 1-5.5 M of LiPF 6 dissolved in PC-EC
  • Graphene-supported LFP nano particles dispersed in the same liquid electrolyte were made into cathode slurry, which was sprayed over porous surfaces of a continuous Ni foam layer to form a cathode electrode.
  • a porous foam rod containing Si nano particle-electrolyte mixture impregnated into the foam pores (the first electrode) was wrapped around by a porous separator layer (porous PE-PP copolymer).
  • a rod of a LFP-electrolyte mixture embedded in pores of a filamentary foam structure was also similarly made. The two electrodes were then combined into a twist yarn and then encased in a thin polymer sheath to obtain a rope-shape lithium-ion battery.
  • EXAMPLE 3 Graphitic foam -based conductive porous rods from pitch-based carbon foams Pitch powder, granules, or pellets are placed in a aluminum mold with the desired final shape of the foam. Mitsubishi ARA-24 meso-phase pitch was utilized. The sample is evacuated to less than 1 torr and then heated to a temperature approximately 300°C. At this point, the vacuum was released to a nitrogen blanket and then a pressure of up to 1,000 psi was applied. The temperature of the system was then raised to 800°C. This was performed at a rate of 2 degree C/min.
  • Natural graphite from Huadong Graphite Co. (Qingdao, China) was used as the starting material.
  • GO was obtained by following the well-known modified Hummers method, which involved two oxidation stages.
  • the first oxidation was achieved in the following conditions: 1100 mg of graphite was placed in a 1000 mL boiling flask. Then, 20 g of K 2 S 2 O 8 , 20 g of P 2 O 5 , and 400 mL of a concentrated aqueous solution of H 2 SO 4 (96%) were added in the flask. The mixture was heated under reflux for 6 hours and then let without disturbing for 20 hours at room temperature. Oxidized graphite was filtered and rinsed with abundant distilled water until neutral pH. A wet cake-like material was recovered at the end of this first oxidation.
  • the previously collected wet cake was placed in a boiling flask that contains 69 mL of a concentrated aqueous solution of H 2 SO 4 (96%).
  • the flask was kept in an ice bath as 9 g of KMn0 4 was slowly added. Care was taken to avoid overheating.
  • the resulting mixture was stirred at 35°C for 2 hours (the sample color turning dark green), followed by the addition of 140 mL of water. After 15 min, the reaction was halted by adding 420 mL of water and 15 mL of an aqueous solution of 30 wt % H 2 O 2 . The color of the sample at this stage turned bright yellow.
  • the mixture was filtered and rinsed with a 1 : 10 HC1 aqueous solution.
  • the collected material was gently centrifuged at 2700g and rinsed with deionized water.
  • the final product was a wet cake that contained 1.4 wt % of GO, as estimated from dry extracts. Subsequently, liquid dispersions of GO platelets were obtained by lightly sonicating wet-cake materials, which were diluted in deionized water.
  • RGO-BS Surfactant-stabilized RGO
  • Sonication was performed using a Branson Sonifier S-250A equipped with a 13 mm step disruptor horn and a 3 mm tapered micro-tip, operating at a 20 kHz frequency. For instance, 10 mL of aqueous solutions containing 0.1 wt.
  • % of GO was sonicated for 10 min and subsequently centrifuged at 2700g for 30 min to remove any non-dissolved large particles, aggregates, and impurities.
  • Chemical reduction of as-obtained GO to yield RGO was conducted by following the method, which involved placing 10 mL of a 0.1 wt. % GO aqueous solution in a boiling flask of 50 mL. Then, 10 ⁇ ⁇ of a 35 wt. % aqueous solution of N 2 H 4 (hydrazine) and 70 mL of a 28 wt. % of an aqueous solution of H 4 OH (ammonia) were added to the mixture, which was stabilized by surfactants. The solution was heated to 90°C and refluxed for 1 h. The pH value measured after the reaction was approximately 9. The color of the sample turned dark black during the reduction reaction.
  • RGO was used as a conductive additive in either or both of the anode and cathode active material in certain lithium batteries presently invented.
  • Pre-lithiated RGO e.g. RGO + lithium particles or RGO pre-deposited with lithium coating
  • RGO + lithium particles or RGO pre-deposited with lithium coating was also used as an anode active material that was mixed with a liquid electrolyte to form wet anode active material mixtures for use in selected lithium-ion cells.
  • Selected cathode active materials TiS 2 nano particles and LiCo0 2 particles, respectively
  • non-lithiated RGO sheets were dispersed in a liquid electrolyte to prepare wet cathode active material mixture.
  • the wet anode active mixture and cathode active mixtures were separately delivered to surfaces of graphite foams for forming an anode and a cathode, respectively.
  • a rope-shape battery was then fabricated, wherein one filamentary electrode (e.g. an anode) and one filamentary electrode (a cathode) were combined to form a braid, twist yarn, or the like.
  • Electrodes and a separator disposed between two dried electrodes were then assembled and encased in an Al-plastic laminated packaging envelop, followed by liquid electrolyte injection to form a conventional lithium battery cell.
  • pristine graphene sheets (non-oxidized and oxygen-free, non-halogenated and halogen-free, etc.) can lead to a conductive additive having a high electrical and thermal conductivity.
  • Pre-lithiated pristine graphene and pre-sodiated pristine graphene were also used as an anode active material for a lithium-ion battery and a sodium-ion battery, respectively.
  • Pristine graphene sheets were produced by using the direct ultrasoni cation or liquid-phase production process.
  • Pristine graphene sheets, as a conductive additive, along with an anode active material (or cathode active material in the cathode) were then incorporated in a battery using both the presently invented procedure and conventional procedure of slurry coating, drying and layer laminating. Both lithium-ion batteries and lithium metal batteries (impregnation into cathode only) were investigated. Sodium-ion cells were also prepared and studied.
  • EXAMPLE 6 Lithium iron phosphate (LFP) cathode of a lithium metal battery
  • LFP powder un-coated or carbon-coated, is commercially available from several sources.
  • a LFP target for sputtering was prepared by compacting and sintering LFP powders together. Sputtering of LFP was conducted on a graphene film and, separately, carbon nano-fiber (CNF) mat. The LFP-coated graphene film was then broken and pulverized to form LFP-coated graphene sheets.
  • CNF carbon nano-fiber
  • EXAMPLE 7 Preparation of disodium terephthalate (Na 2 C 8 H 4 0 4 ) as an anode active material of a sodium-ion battery
  • Disodium terephthalate was obtained by the recrystallization method.
  • An aqueous solution was prepared via the addition of terephthalic acid to an aqueous NaOH solution and then ethanol (EtOH) was added to the mixture to precipitate disodium terephthalate in a water/EtOH mixture.
  • EtOH ethanol
  • terephtalic acid has relatively low pKa values, which allow easy deprotonation by NaOH, affording disodium terephthalate (Na 2 TP) through the acid-base chemistry.
  • terephthalic acid (3.00 g, 18.06 mmol) was treated with sodium hydroxide (1.517 g, 37.93 mmol) in EtOH (60 mL) at room temperature. After 24 h, the suspended reaction mixture was centrifuged and the supernatant solution was decanted. The precipitate was re-dispersed in EtOH and then centrifuged again. This procedure was repeated twice to yield a white solid. The product was dried in vacuum at 150°C for 1 h. In a separate sample, GO was added to aqueous NaOH solution (5% by wt. of GO sheets) to prepare sheets of graphene-supported disodium terephthalate under comparable reaction conditions.
  • EXAMPLE 8 V 2 0 5 as an example of a transition metal oxide cathode active material of a lithium battery
  • V 2 0 5 powder alone is commercially available.
  • vanadium pentoxide gels were obtained by mixing V 2 0 5 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 180°C for 12 h.
  • 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 nano-belt sizes, and then spray-drying at 200°C to obtain graphene-embraced composite particulates.
  • V 2 0 5 powder (with a carbon black powder as a conductive additive) and graphene-supported V 2 0 5 powder, separately, along with a liquid electrolyte, were then incorporated in a battery using both the presently invented rope-making process and the conventional procedure of slurry coating, drying and layer laminating.
  • EXAMPLE 9 LiCo0 2 as an example of lithium transition metal oxide cathode active material for a lithium-ion battery
  • Commercially available L1C0O 2 powder and carbon black powder were dispersed in a liquid electrolyte to form cathode active material mixtures, which were impregnated into a rod- shape Ni foam-based cathode current collector to form a cathode electrode.
  • Graphite particle- liquid electrolyte i.e. the anode active mixture
  • a mixture of graphene embraced Si nano particles and liquid electrolyte was impregnated into pores of Cu foam to obtain a high-capacity anode electrode.
  • An anode electrode encased in a porous separator layer and a cathode electrode were twist- assembled, compacted, and encased in a plastic envelop to form a rope-shape battery cell. The cell was then hermetically sealed.
  • LiCo0 2 powder, carbon black powder, and PVDF resin binder were dispersed in NMP solvent to form a slurry, which was coated onto both sides of a AL foil current collector and then dried under vacuum to form a cathode layer.
  • Graphite particles and PVDF resin binder were dispersed in NMP solvent to form a slurry, which was coated onto both sides of a Cu foil current collector and then dried under vacuum to form an anode layer.
  • the anode layer, separator, and cathode layer were then laminated and encased in an Al-plastic housing, which was injected with a liquid electrolyte to form a conventional lithium -ion battery.
  • Nio .25 Mn 0.75 (OH) 2 cathode active material Na 2 C0 3 , and Li 2 C0 3 were used as starting
  • a sheet of aluminum foil was coated with N-methylpyrrolidinone (NMP) slurry of the cathode mixture.
  • the electrode mixture is composed of 82 wt% active oxide material, 8 wt% conductive carbon black (Timcal Super-P), and 10 wt. % PVDF binder (Kynar).
  • the electrode was initially dried at 70° C for 2 h, followed by dynamic vacuum drying at 80° C for at least 6 h.
  • the sodium metal foil was cut from sodium chunks (Aldrich, 99%) that were cleaned of any oil using hexane, then rolled and punched out.
  • NMP was replaced by a liquid electrolyte (propylene carbonate with 1 M of NaC10 4 ).
  • a slurry was directly impregnated into the pores of a porous filamentary cathode current collector rod.
  • the electrolyte was propylene carbonate with 1 M of NaC10 4 electrolyte salt (Aldrich, 99%). Pouch cells were galvanostatically cycled to a cutoff of 4.2 V vs. Na/Na + (15 mA/g) and then discharged at various current rates to a cutoff voltage of 2.0 V.
  • the specific discharge capacity herein referred to is the total charge inserted into the cathode during the discharge, per unit mass of the composite cathode (counting the weights of cathode active material, conductive additive or support, binder, and any optional additive combined, but excluding the current collector).
  • the specific charge capacity refers to the amount of charges per unit mass of the composite cathode.
  • the specific energy and specific power values presented in this section are based on the total cell weight for all pouch cells. The morphological or micro-structural changes of selected samples after a desired number of repeated charging and recharging cycles were observed using both
  • the Na 3 V 2 (P0 4 ) 3 /C sample was synthesized by a solid state reaction according to the following procedure: a stoichiometric mixture of NaH 2 P0 -2H 2 0 (99.9%, Alpha) and V 2 0 3 (99.9%), Alpha) powders was put in an agate j ar as a precursor and then the precursor was ball- milled in a planetary ball mill at 400 rpm in a stainless steel vessel for 8 h. During ball milling, for the carbon coated sample, sugar (99.9%, Alpha) was also added as the carbon precursor and the reductive agent, which prevents the oxidation of V 3+ . After ball milling, the mixture was pressed into a pellet and then heated at 900°C for 24 h in Ar atmosphere.
  • Na 3 V 2 (P0 4 ) 3 /Graphene cathode was prepared in a similar manner, but with sugar replaced by graphene oxide.
  • the cathode active materials were used in several Na metal cells containing 1-7.5 M of NaPF 6 salt in PC+DOL as the electrolyte. Both conventional NMP slurry coating process and the invented rope cell-making procedure were followed to produce Na metal cells.
  • EXAMPLE 12 Organic material (Li 2 C 6 0 6 ) as a cathode active material of a lithium metal battery
  • dilithium rhodizonate Li 2 C 6 06
  • the rhodizonic acid dihydrate (species 1 in the following scheme) was used as a precursor.
  • a basic lithium salt, Li 2 C0 3 can be used in aqueous media to neutralize both enediolic acid functions. Strictly stoichiometric quantities of both reactants, rhodizonic acid and lithium carbonate, were allowed to react for 10 hours to achieve a yield of 90%.
  • Dilithium rhodizonate (species 2) was readily soluble even in a small amount of water, implying that water molecules are present in species 2. Water was removed in a vacuum at 180°C for 3 hours to obtain the anhydrous version (species 3).
  • the electrolyte was 1M of lithium hexafluorophosphate (LiPF 6 ) in PC-EC.
  • the two Li atoms in the formula Li 2 C 6 06 are part of the fixed structure and they do not participate in reversible lithium ion storing and releasing. This implies that lithium ions must come from the anode side. Hence, there must be a lithium source (e.g. lithium metal or lithium metal alloy) at the anode.
  • the anode current collector a graphene aerogel foam rod
  • the anode current collector is deposited with a layer of lithium (e.g. via sputtering or electrochemical plating).
  • the lithium-coated rod (or simply a lithium rod), having a porous separator wrapped around the rod, and an impregnated cathode rod into a 2-ply yarn, which is then encased in a protective plastic sheath.
  • the corresponding conventional Li metal cell was also fabricated by the conventional procedures of slurry coating, drying, laminating, packaging, and electrolyte injection.
  • EXAMPLE 13 Organic material (Na 2 C 6 0 6 ) as a cathode active material of a sodium metal battery
  • disodium rhodizonate Na 2 C 6 06
  • the rhodizonic acid dihydrate (species 1 in the following scheme) was used as a precursor.
  • a basic sodium salt, Na 2 C0 3 can be used in aqueous media to neutralize both enediolic acid functions.
  • Disodium rhodizonate (species 2) was readily soluble even in a small amount of water, implying that water molecules are present in species 2. Water was removed in a vacuum at 180°C for 3 hours to obtain the anhydrous version (species 3).
  • the electrolyte was 1M of sodium hexafluorophosphate (NaPF 6 ) in PC-EC.
  • the two Na atoms in the formula Na 2 C 6 0 6 are part of the fixed structure and they do not participate in reversible lithium ion storing and releasing.
  • the sodium ions must come from the anode side. Hence, there must be a sodium source (e.g. sodium metal or sodium metal alloy) at the anode.
  • the anode current collector (a carbon foam rod or thin Cu wire) is deposited with a layer of sodium (e.g. via electrochemical plating). This can be done prior to assembling the sodium-coated layer or simply a sodium rod, covered by a porous separator, and a cathode active material/electrolyte-impregnated foam rod into a rope-shape battery.
  • the pores of the cathode current collector were pre-infiltrated with the suspension of the cathode active material and conductive additive (Na 2 C 6 06/C composite particles) dispersed in the liquid electrolyte.
  • conductive additive Na 2 C 6 06/C composite particles
  • the corresponding conventional Na metal cell was also fabricated by the conventional procedures of slurry coating, drying, laminating, packaging, and electrolyte injection.
  • EXAMPLE 14 Metal naphthalocyanine-RGO hybrid cathode of a lithium metal battery
  • CuPc-coated graphene sheets were obtained by vaporizing CuPc in a chamber along with a graphene film (5 nm) prepared from spin coating of RGO-water suspension. The resulting coated film was cut and milled to produce CuPc-coated graphene sheets, which were used as a cathode active material in a lithium metal battery.
  • This battery has a lithium metal rod as the anode active material and 1-3.7 M of LiC10 4 in propylene carbonate (PC) solution as the electrolyte.
  • EXAMPLE 15 Preparation of M0S 2 /RGO hybrid material as a cathode active material of a lithium metal battery
  • Product was collected by centrifugation at 8000 rpm for 5 min, washed with DI water and recollected by centrifugation. The washing step was repeated for at least 5 times to ensure that most DMF was removed. Finally, product was dried, mixed with liquid electrolyte to produce active cathode mixture slurry for impregnation.
  • EXAMPLE 16 Preparation of two-dimensional (2D) layered Bi 2 Se 3 chalcogenide nanoribbons
  • the preparation of (2D) layered Bi 2 Se 3 chalcogenide nanoribbons is well-known in the art.
  • Bi 2 Se 3 nanoribbons were grown using the vapor-liquid-solid (VLS) method.
  • Nanoribbons herein produced are, on average, 30-55 nm thick with widths and lengths ranging from hundreds of nanometers to several micrometers. Larger nanoribbons were subjected to ball- milling for reducing the lateral dimensions (length and width) to below 200 nm.
  • Nanoribbons prepared by these procedures (with or without the presence of graphene sheets or exfoliated graphite flakes) were used as a cathode active material of a lithium metal battery.
  • EXAMPLE 17 Graphene-enhanced nano silicon fabricated from TEOS as an anode active material of a lithium-ion battery
  • stirring was maintained for 24 hours to obtain a complete hydrolysis of TEOS.
  • 10% ⁇ 3 ⁇ 2 0 was added dropwise to the solution until a gel state was reached, which could be called as TP gel.
  • the TP gel was grinded to tiny particles, oven-dried at 120°C for 2 hours and at 150°C for 4 hours.
  • the dried TP particles were mixed with Mg in a ratio of 10:7. As high as 20 times amount of 7mm SS balls were added into a milling pot and the sample was ball milled under Argon protection.
  • the rotating speed was gradually increased to 250 rpm.
  • Some amount of TPM powders was placed in a Nickel crucible and heat treated at 680°C.
  • Some amount of 2M HCl solution was also prepared. Then, heat treated TPM powders were gradually added to the acid solution.
  • the reaction was maintained for 2-24 hours, and then the turbid liquid was added to the ultrasonic bath and ultrasonicated for 1 hour.
  • the suspension was poured out to a filtration system and the large particles at the bottom were discarded. DI water was used to rinse the sample three times.
  • the yellow paste was dried and ground to powders using a blender.
  • the as-prepared nano particle sample exhibits a specific surface area (SSA) value in the range of 30 m 2 /g to 200 m 2 /g due to different graphene contents.
  • SSA specific surface area
  • TPM particles were then put into muffle furnace and calcined at 400°C ⁇ 600°C for 2 hours under air purging to remove the carbon content from the nanocomposite, producing graphene-free yellow-color silicon nano powders.
  • Both Si nano powder and graphene-wrapped Si nano particles were used as a high-capacity anode active material.
  • EXAMPLE 18 Cobalt Oxide (Co 3 0 4 ) particulates as an anode active material
  • Co 3 0 4 is an anode active material of a lithium-ion battery since L1C0O 2 is at an electrochemical potential of approximately +4.0 volts relative to Li/Li + and C0 3 O 4 is at an electrochemical potential of approximately +0.8 volts relative to Li/Li + .
  • EXAMPLE 19 Graphene-enhanced Tin oxide particulates as an anode active material
  • Tin oxide (Sn0 2 ) nano particles an anode active material, were obtained by the controlled hydrolysis of SnCl 4 5H 2 0 with NaOH using the following procedure: SnCl 4 5H 2 0 (0.95 g, 2.7 m-mol) and NaOH (0.212 g, 5.3 m-mol) were dissolved in 50 mL of distilled water each. The NaOH solution was added drop-wise under vigorous stirring to the tin chloride solution at a rate of 1 mL/min. This solution was homogenized by sonication for 5 min.
  • EXAMPLE 20 Preparation of graphene-supported Mn0 2 and NaMn0 2 cathode active material
  • the Mn0 2 powder was synthesized by two methods (each with or without the presence of graphene sheets).
  • a 0.1 mol/L KMn0 4 aqueous solution was prepared by dissolving potassium permanganate in deionized water.
  • 13.32 g surfactant of high purity sodium bis(2-ethylhexyl) sulfosuccinate was added in 300mL iso-octane (oil) and stirred well to get an optically transparent solution.
  • NaMn0 2 and NaMn0 2 /graphene composite were synthesized by ball- milling mixtures ofNa 2 C0 3 and Mn0 2 (at a molar ratio of 1 :2), with or without graphene sheets, for 12 h followed by heating at 870°C for 10 h.
  • a sheet of potassium-coated graphene film was used as the anode active material while a layer of PVDF -bonded reduced graphene oxide (RGO) sheets, supplied from Angstron
  • the cathode active material was 1 M of KC10 4 salt dissolved in a mixture of propylene carbonate and DOL (1/1 ratio). Charge- discharge curves were obtained at several current densities (from 50 mA/g to 50 A/g), corresponding to different C rates, with the resulting energy density and power density data measured and calculated.
  • a typical anode composition includes 85 wt. % active material (e.g., Si- or Co 3 0 4 -coated graphene sheets), 7 wt. % acetylene black (Super-P), and 8 wt. % polyvinylidene fluoride binder (PVDF, 5 wt. % solid content) dissolved in N-methyl-2- pyrrolidinoe ( MP).
  • active material e.g., Si- or Co 3 0 4 -coated graphene sheets
  • Super-P acetylene black
  • PVDF polyvinylidene fluoride binder
  • MP N-methyl-2- pyrrolidinoe
  • Cathode layers are made in a similar manner (using Al foil as the cathode current collector) using the conventional slurry coating and drying procedures.
  • An anode layer, separator layer (e.g. Celgard 2400 membrane), and a cathode layer are then laminated together and housed in a plastic- Al envelop.
  • the cell is then injected with 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
  • ionic liquids were used as the liquid electrolyte.
  • the cell assemblies were made in an argon-filled glove-box.
  • electrochemical workstation at a typical scanning rate of 1 mV/s.
  • electrochemical performances of various cells were also evaluated by galvanostatic charge/discharge cycling at a current density of from 50 mA/g to 10 A/g.
  • galvanostatic charge/discharge cycling at a current density of from 50 mA/g to 10 A/g.
  • multi-channel battery testers manufactured by LAND were used.
  • cycle life of a battery In lithium-ion battery industry, it is a common practice to define the cycle life of a battery as the number of charge-discharge cycles that the battery suffers 20% decay in capacity based on the initial capacity measured after the required electrochemical formation.
  • the volumetric energy density is increased from 412.5 Wh/L to 723 Wh/L. This latter value of 723 Wh/L has never been previously achieved with a lithium-ion battery using a graphite anode and a lithium iron phosphate cathode.
  • the maximum power density is increased from 621 W/kg to 1255 W/kg. This might have been due to significantly reduced internal resistance against electron transport and lithium ion transport.
  • FIG. 6 shows the Ragone plots (both gravimetric and volumetric power density vs.
  • the data are for both lithium metal cells prepared by the presently invented method and those by the conventional slurry coating of electrodes. These data indicate that both the gravimetric and volumetric energy densities and power densities of the lithium metal cells prepared by the presently invented method are significantly higher than those of their counterparts prepared via the conventional method.
  • the gravimetric energy density of the presently invented lithium metal -organic cathode cell is as high as 494 Wh/kg, higher than those of all rechargeable lithium-metal or lithium-ion batteries ever reported (recall that current Li-ion batteries store 150-220 Wh/kg based on the total cell weight). Also quite astonishing is the observation that the volumetric energy density of such an organic cathode-based battery is as high as 988 Wh/L, an unprecedentedly high value that tops those of all lithium-ion and lithium metal batteries ever reported.
  • the present invention overcomes this long-standing, most serious problem in the art of lithium batteries.
  • the weight proportion of the anode active material (e.g. graphite or carbon) in a lithium-ion battery is typically from 12% to 17%, and that of the cathode active material (for inorganic material, such as LiMn 2 0 4 ) from 22% to 41%, or from 10% to 15% for organic or polymeric.
  • the electrode thickness of a lithium battery is a design parameter that can be freely adjusted for optimization of device performance. Contrary to this perception, in reality, the lithium battery electrode thickness is manufacturing-limited and one cannot produce electrodes of good structural integrity that exceed certain thickness level in a real industrial manufacturing environment (e.g. a roll-to-roll slurry coating facility).
  • a real industrial manufacturing environment e.g. a roll-to-roll slurry coating facility.
  • FIG. 8 Shown in FIG. 8 are the cell-level gravimetric (Wh/kg) and volumetric energy densities
  • Mn0 2 /RGO cathode prepared via the conventional method without delamination and cracking and those by the presently invented method.
  • the electrodes can be fabricated up to a thickness of 100-200 ⁇ using the conventional slurry coating process.
  • the electrode thickness or diameter there is no theoretical limit on the electrode thickness or diameter that can be achieved with the presently invented method.
  • the practical electrode thickness is from 1 ⁇ to 1000 ⁇ , more typically from 10 ⁇ to 800 ⁇ , and most typically from 100 ⁇ to 600 ⁇ .
  • EXAMPLE 25 Achievable active material weight percentage in a cell and its effect on electrochemical performance of lithium battery cells
  • the weight of the anode and cathode active materials combined accounts for up to about 30%-50% of the total mass of the packaged commercial lithium batteries, a factor of 30%-50% must be used to extrapolate the energy or power densities of the device from the performance data of the active materials alone.
  • the energy density of 500 Wh/kg of combined graphite and NMC (lithium nickel manganese cobalt oxide) weights will translate to about 150-250 Wh/kg of the packaged cell.
  • this extrapolation is only valid for electrodes with thicknesses and densities similar to those of commercial electrodes (150 ⁇ or about 15 mg/cm 2 of the graphite anode and 30 mg/cm 2 of NMC cathode).
  • An electrode of the same active material that is thinner or lighter will mean an even lower energy or power density based on the cell weight.
  • the instant invention makes it possible to elevate the active material proportion above 85% if so desired; but typically from 45% to 80%, more typically from 40% to 70%, and most typically from 40% to 65%.
  • FIG. 9 Shown in FIG. 9 are the cell-level gravimetric and volumetric energy densities of the graphite/NMC cells prepared by the presently invented method and the conventional roll-coating method. These data further demonstrate the implications of our ability to take the total active material mass beyond 50%, enabling the attainment of unexpectedly high gravimetric and volumetric energy densities that have not been previously possible given the same lithium battery system (e.g. elevated from 189 Wh/kg to 301 Wh/kg and from 510 Wh/L to 783 Wh/L).
  • EXAMPLE 26 Representative testing results of sodium metal and potassium metal cells
  • FIG. 10 Shown in FIG. 10 are Ragone plots (gravimetric and volumetric power density vs. energy density) of Na-ion battery cells containing hard carbon particles as the anode active material and carbon-coated Na 3 V 2 (P0 4 ) 2 F3 particles as the cathode active materials.
  • Two of the 4 data curves are for the rope-shape cells prepared according to an embodiment of instant invention and the other two by the conventional slurry coating of electrodes (roll-coating).
  • volumetric energy density is increased from 241 Wh/L to 483 Wh/L.
  • This latter value of 483 Wh/L is exceptional for a sodium-ion battery using a hard carbon anode and a sodium transition metal phosphate-type cathode.
  • FIG. 11 shows the Ragone plots (both gravimetric and volumetric power density vs. gravimetric and volumetric energy density) of two cells, both containing graphene-embraced Sn nano particles as the anode active material and NaFeP0 4 nano particles as the cathode active material.
  • the experimental data were obtained from the Na-ion battery cells that were prepared by the presently invented method and those by the conventional slurry coating of electrodes. These data indicate that both the gravimetric and volumetric energy densities and power densities of the rope-shape sodium battery cells prepared by the presently invented method are significantly higher than those of their counterparts prepared via the conventional method.
  • the conventionally made cells exhibit a gravimetric energy density of 185 Wh/kg and volumetric energy density of 388 Wh/L, but the presently invented rope-shape cells deliver 302 Wh/kg and 755 Wh/L, respectively.
  • the cell-level volumetric energy density of 755 Wh/L has never been previously achieved with any rechargeable sodium batteries.
  • Even the state-of-the-art lithium-ion battery rarely exhibits a volumetric energy density higher than 750 Wh/L.
  • the power densities as high as 1 198 W/kg and 3,474 W/L are also unprecedented for typically higher-energy lithium-ion batteries, let alone for sodium-ion batteries.
  • FIG. 12 Shown in FIG. 12 are Ragone plots of sodium metal batteries containing a sodium foil as the anode active material, disodium rhodizonate (Na 2 C 6 0 6 ) as the cathode active material, and lithium salt (NaPF 6 )-PC/DEC as organic liquid electrolyte.
  • the data are for both the rope-shape sodium metal cells prepared by the presently invented method and those by the conventional slurry coating of electrodes. These data indicate that both the gravimetric and volumetric energy densities and power densities of the presently invented rope-shape sodium metal cells are significantly higher than those of their conventional counterparts prepared via the conventional method.
  • the gravimetric energy density of the presently invented sodium metal-organic cathode cell is as high as 312 Wh/kg, higher than those of all rechargeable sodium metal or sodium-ion batteries ever reported (recall that current Na-ion batteries typically store 100-150 Wh/kg based on the total cell weight).
  • a gravimetric power density of 1,225 W/kg and volumetric power density of 3,552 W/L would have been un-thinkable.
  • the weight proportion of the anode active material (e.g. graphite or carbon) in a lithium-ion battery is typically from 12% to 17%, and that of the cathode active material (for inorganic material, such as LiMn 2 0 4 ) from 22% to 41%, or from 10% to 15% for organic or polymeric.
  • the anode active material e.g. graphite or carbon
  • the cathode active material for inorganic material, such as LiMn 2 0 4
  • the active material weight is typically from 5% to 10% of the total device weight, which implies that the actual cell (device) energy or power densities may be obtained by dividing the corresponding active material weight-based values by a factor of 10 to 20. After this factor is taken into account, the properties reported in these papers do not really look any better than those of commercial batteries. Thus, one must be very careful when it comes to read and interpret the performance data of batteries reported in the scientific papers and patent applications.
  • the Ragone plot of a series of K-ion cells prepared by the conventional slurry coating process and the Ragone plot of corresponding cable-shape K-ion cells prepared by the presently invented process are summarized and contrasted in FIG. 13. These data again confirm that the presently invented process works well for making both Na and K metal batteries having ultrahigh energy densities and power densities.

Abstract

La présente invention concerne une batterie en métal alcalin en forme de corde comprenant : (a) une première électrode comprenant une première tige poreuse conductrice ayant des pores et un premier mélange d'un premier matériau actif d'électrode et d'un premier électrolyte se trouvant dans les pores de la première tige poreuse ; (b) un séparateur poreux enveloppant ou enrobant la première électrode pour former une première électrode protégée par séparateur ; (c) une seconde électrode comprenant une seconde tige poreuse conductrice ayant des pores et un second mélange d'un second matériau actif d'électrode et d'un second électrolyte se trouvant dans les pores de la seconde tige poreuse ; la première électrode protégée par un séparateur et la seconde électrode étant combinées pour former une tresse ou un fil ayant une électrode torsadée ou en spirale ; et (d) un boîtier ou une enveloppe de protection enveloppant ou enrobant la tresse ou le fil.
PCT/US2017/067071 2016-12-28 2017-12-18 Batteries en métal alcalin en forme de corde souples et à forme conforme WO2018125641A1 (fr)

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CN109686961A (zh) * 2019-01-21 2019-04-26 莱西市冀工碳材料研究院 一种富氧缺陷钛酸钠/石墨烯复合负极材料的制备方法
CN109755543B (zh) * 2019-03-07 2020-12-11 肇庆市华师大光电产业研究院 一种钠离子电池负极材料及其制备方法
CN109755543A (zh) * 2019-03-07 2019-05-14 肇庆市华师大光电产业研究院 一种钠离子电池负极材料及其制备方法
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CN110729518A (zh) * 2019-09-08 2020-01-24 复旦大学 基于二氧化锰/石墨烯的水系锌离子电池及制备方法
CN110729518B (zh) * 2019-09-08 2022-12-20 复旦大学 基于二氧化锰/石墨烯的水系锌离子电池及制备方法
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CN111592045A (zh) * 2020-05-11 2020-08-28 三峡大学 锰酸钾钾离子电池正极材料
CN111834631B (zh) * 2020-07-13 2021-07-23 万华化学集团股份有限公司 一种锂离子电池高镍正极材料的制备方法
CN111834631A (zh) * 2020-07-13 2020-10-27 万华化学集团股份有限公司 一种锂离子电池高镍正极材料的制备方法
CN111925547A (zh) * 2020-10-16 2020-11-13 河南功能高分子膜材料创新中心有限公司 一种含氟聚合物复合涂层的聚乙烯膜及其制备方法
CN111925547B (zh) * 2020-10-16 2020-12-29 河南功能高分子膜材料创新中心有限公司 一种含氟聚合物复合涂层的聚乙烯膜及其制备方法
CN112226209A (zh) * 2020-11-11 2021-01-15 北京科技大学 中空管状导电聚合物复合纤维气凝胶材料的制备及应用
CN114023924A (zh) * 2021-11-01 2022-02-08 湖南立方新能源科技有限责任公司 一种无集流体硅基负极的制备方法及纤维锂离子电池
CN114023924B (zh) * 2021-11-01 2023-07-11 湖南立方新能源科技有限责任公司 一种无集流体硅基负极的制备方法及纤维锂离子电池

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