WO2018222348A1 - Batterie à métal alcalin de forme adaptable dotée d'une électrode polymère quasi-solide conductrice et déformable - Google Patents

Batterie à métal alcalin de forme adaptable dotée d'une électrode polymère quasi-solide conductrice et déformable Download PDF

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WO2018222348A1
WO2018222348A1 PCT/US2018/031519 US2018031519W WO2018222348A1 WO 2018222348 A1 WO2018222348 A1 WO 2018222348A1 US 2018031519 W US2018031519 W US 2018031519W WO 2018222348 A1 WO2018222348 A1 WO 2018222348A1
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lithium
sodium
sulfonated
oxide
poly
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PCT/US2018/031519
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English (en)
Inventor
Aruna Zhamu
Bor Z. Jang
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Nanotek Instruments, Inc.
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Priority claimed from US15/608,597 external-priority patent/US10535892B2/en
Priority claimed from US15/610,136 external-priority patent/US10170789B2/en
Application filed by Nanotek Instruments, Inc. filed Critical Nanotek Instruments, Inc.
Priority to CN201880035241.6A priority Critical patent/CN110679009B/zh
Priority to JP2019565836A priority patent/JP7353983B2/ja
Priority to KR1020197037722A priority patent/KR20200014335A/ko
Publication of WO2018222348A1 publication Critical patent/WO2018222348A1/fr

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    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M10/00—Secondary cells; Manufacture thereof
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    • H01M10/052—Li-accumulators
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    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H—ELECTRICITY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • H—ELECTRICITY
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • H—ELECTRICITY
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    • 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
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
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    • H01M2004/028—Positive electrodes
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    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • 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 alkali metal batteries, including rechargeable lithium metal batteries, sodium metal batteries, lithium-ion batteries, sodium-ion batteries, lithium-ion capacitors and sodium-ion capacitors.
  • Li metal is an ideal anode material due to its light weight (the lightest metal), high electronegativity (-3.04 V vs. the standard hydrogen electrode), and high theoretical capacity (3,860 mAh/g). Based on these outstanding properties, lithium metal batteries were proposed 40 years ago as an ideal system for high energy-density applications. During the mid-1980s, several prototypes of rechargeable Li metal batteries were developed.
  • a notable example was a battery composed of a Li metal anode and a molybdenum sulfide cathode, developed by MOLI Energy, Inc. (Canada). This and several other batteries from different manufacturers were abandoned due to a series of safety problems caused by sharply uneven Li growth (formation of Li dendrites) as the metal was re-plated during each subsequent recharge cycle. As the number of cycles increases, these dendritic or tree-like Li structures could eventually traverse the separator to reach the cathode, causing internal short-circuiting.
  • Li-ion battery Li-ion battery
  • Li -ion batteries are inherently safer than Li-metal batteries.
  • Lithium ion battery is a prime candidate energy storage device for electric vehicle (EV), renewable energy storage, and smart grid applications.
  • EV electric vehicle
  • EV renewable energy storage
  • smart grid applications 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.
  • phosphate and lithium transition metal oxides has been limited to the range of 150-250 mAh/g and, in most cases, less than 200 mAh/g.
  • 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.
  • 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.
  • sodium batteries have been considered as 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.
  • Sodium ion batteries using a hard carbon-based anode (Na-carbon intercalation compound) and a sodium transition metal phosphate as a cathode have been described by several research groups.
  • these sodium-based devices exhibit even lower specific energies and rate capabilities than Li-ion batteries.
  • These conventional sodium-ion batteries require sodium ions to diffuse in and out of a sodium intercalation compound at both the anode and the cathode.
  • the required solid-state diffusion processes for sodium ions in a sodium-ion battery are even slower than the Li diffusion processes in a Li-ion battery, leading to excessively low power densities.
  • 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 because of dendrite formation, interface aging, and electrolyte incompatibility problems.
  • the same flammable solvents previously used for lithium secondary batteries are also used in most of the sodium metal or sodium-ion batteries.
  • 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.
  • a high-energy density battery that is shape- conformable so that it can be fitted into some odd-shape or confined spaces in a device or vehicle.
  • a battery By implementing a battery in a space that otherwise would be an empty (unused or “wasted") space (e.g. part of a car door or roof top), one can make the device more compact or make the EV capable of storing more power.
  • the electrodes In order to make the battery shape-conformable, the electrodes must be deformable, flexible, and shape-conformable.
  • lithium and sodium batteries that have high active material mass loading (high areal density), high electrode thickness or volume without compromising conductivity, high-rate capability, high power density, and high energy density. These batteries must be produced in an environmentally benign manner. Further, the battery must be shape-conformable, being capable of forming any regular (e.g. rectangular or
  • the present invention provides an alkali metal battery that meets all these criteria.
  • the present invention provides a method of producing a flexible and shape-conformable lithium battery or sodium battery having a high active material mass loading, exceptionally low overhead weight and volume (relative to the active material mass and volume), high capacity, and unprecedentedly high energy density and power density.
  • This lithium or sodium battery can be a primary battery (non-rechargeable) or a secondary battery (rechargeable), including a rechargeable lithium or sodium metal battery (having a lithium or sodium metal anode) and a lithium-ion or sodium-ion battery (e.g. having a first lithium intercalation compound as an anode active material and a second lithium intercalation or absorbing compound, having a much higher electrochemical potential than the first one, as a cathode active material).
  • This alkali battery also includes lithium-ion capacitor and sodium-ion capacitor, wherein the anode is a lithium-ion or sodium-ion cell type of anode and the cathode is a supercapacitor cathode (e.g. activated carbon or graphene sheets as an active material for use in an electric double layer capacitor or a redox p seudo-cap acitor) .
  • the anode is a lithium-ion or sodium-ion cell type of anode
  • the cathode is a supercapacitor cathode (e.g. activated carbon or graphene sheets as an active material for use in an electric double layer capacitor or a redox p seudo-cap acitor) .
  • a supercapacitor cathode e.g. activated carbon or graphene sheets as an active material for use in an electric double layer capacitor or a redox p seudo-cap acitor
  • the invention provides an alkali metal cell comprising: (a) a quasi-solid cathode containing about 30% to about 95% by volume of a cathode active material, about 5% to about 40% by volume of a first electrolyte containing an alkali salt dissolved in a solvent and an ion-conducting polymer dissolved in, dispersed in, or impregnated by this solvent, and about 0.01% to about 30% by volume of a conductive additive wherein the conductive additive, containing conductive filaments, forms a 3D network of electron-conducting pathways such that the quasi-solid electrode has an electrical conductivity from about 10 "6 S/cm to about 300 S/cm; (b) an anode; and (c) an ion-conducting membrane or porous separator disposed between the anode and the quasi-solid cathode; wherein said quasi-solid cathode has a thickness no less than 200 ⁇ .
  • the quasi-solid cathode preferably contains a cathode active material mass loading no less than 10 mg/cm 2 , preferably no less than 15 mg/cm 2 , further preferably no less than 25 mg/cm 2 , more preferably no less than 35 mg/cm 2 , still more preferably no less than 45 mg/cm 2 , and most preferably greater than 65 mg/cm 2 .
  • the anode may contain a quasi-solid anode containing about 30% to about 95% by volume of an anode active material, about 5% to about 40% by volume of a second electrolyte containing an alkali salt dissolved in a solvent and an ion-conducting polymer dissolved in, dispersed in, or impregnated by this solvent, and about 0.01% to about 30% by volume of a conductive additive wherein said conductive additive, containing conductive filaments, forms a 3D network of electron-conducting pathways such that the quasi-solid electrode has an electrical conductivity from about 10 "6 S/cm to about 300 S/cm; wherein the quasi-solid anode has a thickness no less than 200 ⁇ and can be up to 100 cm or larger.
  • the quasi-solid anode preferably contains an anode active material mass loading no less than 10 mg/cm 2 , preferably no less than 15 mg/cm 2 , further preferably no less than 25 mg/cm 2 , more preferably no less than 35 mg/cm 2 , still more preferably no less than 45 mg/cm 2 , and most preferably greater than 65 mg/cm 2 .
  • the first electrolyte may be the same as or different from the second electrolyte in composition and structure.
  • the invention provides an alkali metal cell comprising: (A) a quasi-solid anode containing about 30% to about 95% by volume of an anode active material, about 5% to about 40% by volume of an electrolyte containing an alkali salt dissolved in a solvent an ion-conducting polymer dissolved in, dispersed in, or impregnated by this solvent, and about 0.01%) to about 30% by volume of a conductive additive wherein the conductive additive, containing conductive filaments, forms a 3D network of electron-conducting pathways such that the quasi-solid electrode has an electrical conductivity from about 10 "6 S/cm to about 300 S/cm; (B) a cathode; and (C) an ion-conducting membrane or porous separator disposed between the anode and the quasi-solid cathode; wherein said quasi-solid cathode has a thickness no less than 200 ⁇ .
  • the presently invented quasi-solid polymer electrodes are deformable
  • the present invention also provides a method of preparing an alkali metal cell having a quasi-solid electrode, the method comprising: (a) combining a quantity of an active material (an anode active material or a cathode active material), a quantity of an electrolyte containing an alkali salt dissolved in a solvent an ion-conducting polymer dissolved in, dispersed in, or impregnated by this solvent, and a conductive additive to form a deformable and electrically conductive electrode material, wherein the conductive additive, containing conductive filaments, forms a 3D network of electron-conducting pathways; (b) forming the electrode material into a quasi-solid electrode, wherein the forming step includes deforming the electrode material into an electrode shape without interrupting the 3D network of electron-conducting pathways such that the electrode maintains an electrical conductivity no less than 10 "6 S/cm (preferably no less than 10 "5 S/cm, more preferably no less than 10 "3 S/cm, further preferably
  • the second electrode may be a quasi-solid electrode as well
  • the electrolyte (including the first electrolyte or the second electrolyte) contains a lithium ion-conducting or sodium ion-conducting polymer selected from poly(ethylene oxide) (PEO, having a molecular weight lower than 1 x 10 6 g/mole),
  • PEO poly(ethylene oxide)
  • polypropylene oxide PPO
  • poly(acrylonitrile) PAN
  • poly(methyl methacrylate) PMMA
  • poly(vinylidene fluoride) PVDF
  • PVDF poly bis-methoxy ethoxyethoxide-phosphazene
  • polyvinyl chloride polydimethylsiloxane
  • PVDF-HFP poly(vinylidene fluoride)-hexafluoropropylene
  • Sulfonation is herein found to impart improved lithium ion conductivity to a polymer.
  • a PEO molecular weight higher than 1 x 10 6 g/mole typically makes PEO insoluble and non-dispersible in a solvent.
  • this ion-conducting polymer does not form a matrix
  • the ion-conducting polymer may be selected from the group consisting of poly(perfluoro sulfonic acid), sulfonated polytetrafluoroethylene, sulfonated perfluoroalkoxy derivatives of polytetrafluoroethylene, sulfonated polysulfone, sulfonated poly(ether ketone), sulfonated poly (ether ether ketone), sulfonated polystyrene, sulfonated polyimide, sulfonated styrene-butadiene copolymers, sulfonated poly chloro-trifluoroethylene (PCTFE), sulfonated perfluoroethylene- propylene copolymer (FEP), sulfonated ethylene-chlorotrifluoroethylene copolymer (ECTFE), sulfonated polyvinylidenefluoride (PVDF), sulfonated polyviny
  • a “filament” is a solid material object having a largest dimension (e.g. length) and a smallest dimension (e.g. diameter or thickness) and the largest dimension-to-smallest dimension ratio is greater than 3, preferably greater than 10, and further preferably greater than 100.
  • the conductive filaments are selected from carbon fibers, graphite fibers, carbon nanofibers, graphite nanofibers, carbon nanotubes, needle coke, carbon whiskers, conductive polymer fibers, conductive material-coated fibers, metal nanowires, metal fibers, metal wires, graphene sheets, expanded graphite platelets, a combination thereof, or a combination thereof with non-filamentary conductive particles.
  • the electrode maintains an electrical conductivity from 10 "5 S/cm to about 100 S/cm.
  • the deformable electrode material has an apparent viscosity of no less than about 10,000 Pa-s measured at an apparent shear rate of 1,000 s "1 . In certain embodiments, the deformable electrode material has an apparent viscosity of no less than about 100,000 Pa-s at an apparent shear rate of 1,000 s "1 .
  • the quasi-solid electrode is capable of conforming to practically any desired shape, regular or irregular. In the method, the quantity of the active material is typically from about 20% to about 95% by volume of the electrode material, more typically from about 35% to about 85% by volume of the electrode material, and most typically from about 50% to about 75% by volume of the electrode material.
  • the step of combining active material, conductive additive, and electrolyte (including dissolving a lithium or sodium salt in a liquid solvent) follows a specific sequence.
  • This step includes first dispersing the conductive filaments into a liquid solvent to form a homogeneous suspension, followed by adding the active material in the suspension and by dissolving a lithium salt or sodium salt in the liquid solvent and by dissolving or dispersing the ion-conducting polymer in the solvent.
  • the conductive filaments must be uniformly dispersed in the liquid solvent first prior to adding other ingredients, such as active material and the ion-conducting polymer, and prior to dissolving the lithium salt or sodium salt in the solvent.
  • This sequence is essential to achieving percolation of conducting filaments for forming a 3D network of electron-conducting pathways at a lower conductive filament volume fraction (lower threshold volume fraction). Without following such a sequence, the percolation of conducting filaments may not occur or occur only when an excessively large proportion of conducting filaments (e.g. > 10% by volume) is added, which would reduce the fraction of active material and thus reduce the energy density of the cell.
  • an excessively large proportion of conducting filaments e.g. > 10% by volume
  • the steps of combining and forming the electrode material into a quasi-solid electrode include dissolving a lithium salt (or sodium salt) and an ion-conducting polymer in a liquid solvent to form a polymer electrolyte having a first salt concentration and first polymer concentration and subsequently removing portion of the liquid solvent to increase the salt concentration to obtain a quasi-solid polymer electrolyte having a second salt
  • concentration and second polymer concentration which are higher than the first concentrations and preferably higher than 2.5 M of combined salt and polymer (and more preferably from 3.0 M to 14 M).
  • the step of removing portion of solvent may be conducted in such a manner that it does not cause precipitation or crystallization of the salt and polymer and that the electrolyte is in a supersaturated state.
  • the liquid solvent contains a mixture of at least a first liquid solvent and a second liquid solvent and the first liquid solvent is more volatile than the second liquid solvent, wherein the step of removing portion of the liquid solvent includes partially or fully removing the first liquid solvent.
  • the anode active material absorbs 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) when the battery is charged.
  • the alkali metal cell is a lithium metal battery, lithium- ion battery, or lithium-ion capacitor, wherein the anode active material is selected from the group consisting of: (a) Particles of lithium metal or a lithium metal alloy; (b) Natural graphite particles, artificial graphite particles, mesocarbon microbeads (MCMB), carbon particles (including soft carbon and hard carbon), needle coke, carbon nanotubes, carbon nanofibers, carbon fibers, and graphite fibers; (c) 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); (d) Alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, or Cd with other elements,
  • a sodium intercalation compound
  • the alkali metal cell is a sodium metal cell or sodium-ion cell and the active material is an anode active material selected from the group consisting of: (a) Particles of sodium metal or a sodium metal alloy; (b) Natural graphite particles, artificial graphite particles, mesocarbon microbeads (MCMB), carbon particles, needle coke, carbon nanotubes, carbon nanofibers, carbon fibers, and graphite fibers; (c) Sodium-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; (d) Sodium-containing alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd, and their mixtures thereof;
  • the alkali metal cell is a sodium metal cell or sodium-ion cell and the active material is a cathode active material containing a sodium intercalation compound or sodium-absorbing compound selected from an inorganic material, an organic or polymeric material, a metal oxide/phosphate/sulfide, or a combination thereof.
  • the metal is a cathode active material containing a sodium intercalation compound or sodium-absorbing compound selected from an inorganic material, an organic or polymeric material, a metal oxide/phosphate/sulfide, or a combination thereof.
  • oxide/phosphate/sulfide may be selected from a sodium cobalt oxide, sodium nickel oxide, sodium manganese oxide, sodium vanadium oxide, sodium-mixed metal oxide,
  • sodium/potassium-transition metal oxide sodium iron phosphate, sodium/potassium iron phosphate, sodium manganese phosphate, sodium/potassium manganese phosphate, sodium vanadium phosphate, sodium/potassium vanadium phosphate, sodium mixed metal phosphate, transition metal sulfide, or a combination thereof.
  • the inorganic material may be selected from sulfur, sulfur compound, lithium
  • 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 alkali metal cell is a sodium metal cell or sodium-ion cell and the active material is a cathode active material containing a sodium intercalation compound selected from NaFeP0 4 , Na ( i -x) K x P0 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 )2F3, 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 0i5, Na x V0 2 , Na 0 .
  • a sodium intercalation compound selected from NaFeP0 4 , Na ( i -x) K x P0 4 , Na 0 7 FeP0 4 , Nai 5 VOPO 4 F 0 5
  • the cathode active material contains a lithium
  • intercalation 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, and combinations thereof.
  • the electrolytes can contain water, organic liquid, ionic liquid (ionic salt having a melting temperature lower than 100°C, preferably lower than room temperature, 25°C), or a mixture of an ionic liquid and an organic liquid at a ratio from 1/100 to 100/1.
  • the organic liquid is desirable, but the ionic liquid is preferred.
  • the electrolyte typically and preferably contains a high solute concentration (concentration of lithium/sodium salt and polymer combined) that brings the solute to a saturated or supersaturated state in the resulting electrode (anode or cathode).
  • Such an electrolyte is essentially a polymer electrolyte that behaves like a deformable or conformable solid. This is fundamentally distinct from a liquid electrolyte or polymer gel electrolyte.
  • the quasi-solid electrode has a thickness from 200 ⁇ to 1 cm, preferably from 300 ⁇ to 0.5 cm (5 mm), further preferably from 400 ⁇ to 3 mm, and most preferably from 500 ⁇ to 2.5 mm (2,500 ⁇ ).
  • the active material is an anode active material
  • the anode active material has a mass loading no less than 25 mg/cm 2 (preferably no less than 30 mg/cm 2 , and more preferably no less than 35 mg/cm 2 ) and/or occupies at least 25% (preferably at least 30% and more preferably at least 35%) by weight or by volume of the entire battery cell.
  • the cathode active material preferably has a mass loading no less than 20 mg/cm 2 (preferably no less than 25 mg/cm 2 and more preferably no less than 30 mg/cm 2 ) for an organic or polymer material or no less than 45 mg/cm 2 (preferably no less than 50 mg/cm 2 and more preferably no less than 55 mg/cm 2 ) for an inorganic and non-polymer material in the cathode and/or occupies at least 45 % (preferably at least 50% and more preferably at least 55%) by weight or by volume of the entire battery cell.
  • the aforementioned requirements on electrode thickness, the anode active material areal mass loading or mass fraction relative to the entire battery cell, or the cathode active material areal mass loading or mass fraction relative to the entire battery cell have not been possible with conventional lithium or sodium batteries using the conventional slurry coating and drying process.
  • the anode active material is a prelithiated 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, boron-doped graphene, nitrogen-doped graphene, chemically functionalized graphene, a physically or chemically activated or etched version thereof, or a combination thereof.
  • the resulting lithium battery cell does not exhibit a satisfactory cycle life (i.e. capacity decays rapidly).
  • the cell is a lithium metal cell or lithium- ion cell containing a cathode active material selected from a lithium intercalation compound or lithium-absorbing compound is selected from an inorganic material, an organic or polymeric material, a metal oxide/phosphate/sulfide, or a combination thereof.
  • the metal oxide/phosphate/sulfide may be selected from a lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium vanadium oxide, lithium-mixed metal oxide, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, lithium mixed metal phosphate, transition metal sulfide, or a combination thereof.
  • the inorganic material is 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. These will be further discussed later.
  • the cathode active material contains a lithium intercalation compound selected from a metal carbide, metal nitride, metal boride, metal dichalcogenide, or a combination thereof.
  • the cathode active material contains a lithium intercalation 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, nanodisc, nanoribbon, or nanoplatelet form.
  • the cathode active material contains a lithium intercalation compound selected from nanodiscs, nanoplatelets, nanocoating, or nanosheets 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.
  • the cathode active material in this lithium metal battery is an organic material or polymeric material selected from poly(anthraquinonyl sulfide) (PAQS), a lithium oxocarbon, 3,4,9, 10-perylenetetracarboxylic dianhydride (PTCDA), poly(anthraquinonyl sulfide), pyrene-4,5,9, 10-tetraone (PYT), polymer-bound PYT, quino(triazene), redox-active organic material, tetracyanoquinodimethane (TCNQ), tetracyanoethylene (TCNE), 2,3,6,7, 10,11- hexamethoxytriphenylene (HMTP), poly(5 -amino- 1,4-dyhydroxy anthraquinone) (PADAQ), phosphazene disulfide polymer ([( PS 2 ) 3 ] «), lithiated 1,4,5, 8-naphthale
  • 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-l,l,2,2- tetrathiol)
  • PETT poly(ethene-l,l,2,2- tetrathiol)
  • PPDT poly(2-phenyl-l,3-dithiolane)
  • PPDT poly(l,4-di(l,3-dithiolan-2-yl)benzene)
  • PEDTT poly(tetrahydrobenzodithiophene)
  • PTHBDT poly(tetrahydrobenzodithiophene)
  • PEDTT poly[l,2,4,5-tetrakis (propylthio) benzene]
  • PEDTT poly[3,4(ethylenedithio)thiophene]
  • the cathode active material is an organic material containing 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
  • the cathode active material constitutes an electrode active material loading greater than 30 mg/cm 2 (preferably greater than 40 mg/cm 2 , more preferably greater than 45 mg/cm 2 , and most preferably greater than 50 mg/cm 2 ) and/or wherein the electrode has a thickness no less than 300 ⁇ (preferably no less than 400 ⁇ , more preferably no less than 500 ⁇ , can be up to or greater than 100 cm).
  • the electrode thickness of the presently invented alkali metal battery There is no theoretical limit on the electrode thickness of the presently invented alkali metal battery.
  • FIG.1(A) Schematic of a prior art lithium -ion battery cell composed of an anode current
  • anode active material layers e.g. thin Si coating layers coated on the two primary surfaces of the anode current collector, a porous separator and electrolyte, one or two cathode electrode layers (e.g. sulfur layers), and a cathode current collector;
  • 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), conductive additives (not shown), and resin binder (bot shown).
  • FIG. 1(C) Schematic of a presently invented lithium-ion battery cell, comprising a quasi-solid anode (consisting of anode active material particles and conductive filaments directly mixed or dispersed in an electrolyte), a porous separator, and a quasi-solid cathode (consisting of cathode active material particles and conductive filaments directly mixed or dispersed in an electrolyte). In this embodiment, no resin binder is required.
  • FIG. 1(D) Schematic of a presently invented lithium metal battery cell, comprising an anode
  • FIG. 2(A) Schematic of the closely packed, highly ordered structure of a solid electrolyte
  • FIG. 2(B) Schematic of a totally amorphous liquid electrolyte having large fractions of free volume through which cations (e.g. Na + ) can easily migrate;
  • cations e.g. Na +
  • FIG. 2(C) Schematic of the randomized or amorphous structure of a quasi-solid electrolyte
  • the ion-conducting polymer is also brought into a supersaturated state that remains substantially amorphous.
  • FIG. 3(A) The Na + ion transference numbers of electrolytes (e.g. (PEO+NaTFSI salt) in
  • FIG. 3(B) The Na + ion transference numbers of electrolytes (e.g. (PPO+NaTFSI salt) in
  • FIG. 4 Schematic of a commonly used process for producing exfoliated graphite, expanded
  • FIG. 5(A) The electrical conductivity (percolation behavior) of conducting filaments in a quasi- solid polymer electrode, plotted as a function of the volume fraction of conductive filaments (carbon nanofibers).
  • FIG. 5(B) The electrical conductivity (percolation behavior) of conducting filaments in a quasi- solid polymer electrode, plotted as a function of the volume fraction of conductive filaments (reduced graphene oxide sheets).
  • FIG. 6 Ragone plots (gravimetric 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. Three of the 4 data curves are for the cells prepared according to an embodiment of instant invention and the remaining one by the conventional slurry coating of electrodes (roll-coating).
  • FIG. 7 Ragone plots (gravimetric power density vs. gravimetric energy density) of three cells, each containing graphene-embraced Si nanoparticles as the anode active material and LiCo0 2 nanoparticles as the cathode active material.
  • the experimental data were obtained from the Li-ion battery cells that were prepared by the presently invented method (following sequences SI and S3) and that by the conventional slurry coating of electrodes.
  • FIG. 8 Ragone plots of lithium metal batteries containing a lithium foil as the anode active
  • the data are the lithium metal cells prepared by the presently invented method (sequences S2 and S3 with 2 different salt concentrations) and that by the conventional slurry coating of electrodes.
  • FIG. 9 Ragone plots of two sodium-ion capacitors each containing pre-sodiated hard carbon particles as the anode active material and graphene sheets as the cathode active material; one cell having an anode prepared by conventional slurry coating process and the other cell having a quasi-solid anode prepared according to a presently invented method.
  • This invention is directed at a lithium battery or sodium battery exhibiting an
  • This battery can be a primary battery, but is preferably a secondary battery selected from a lithium-ion battery, a lithium metal secondary battery (e.g. using lithium metal as an anode active material), a sodium-ion battery, a sodium metal battery, a lithium-ion capacitor, or a sodium-ion capacitor.
  • the battery is based on a quasi-solid polymer electrolyte, which contains a polymer and a lithium or sodium salt dissolved in water, an organic solvent, an ionic liquid, or a mixture of organic and ionic liquid.
  • the electrolyte is a "quasi-solid polymer electrolyte" containing a high concentration of solutes (a lithium salt or sodium salt and a polymer) in a solvent to the extent that it behaves like a solid, but remains deformable even when desirable amounts of conductive filaments and an active material are added into the electrolyte (hence, the term "deformable quasi-solid polymer electrode”).
  • the electrolyte is not a liquid electrolyte, nor a solid electrolyte.
  • the shape of a lithium battery can be cylindrical, square, button-like, etc. The present invention is not limited to any battery shape or configuration.
  • a prior art lithium or sodium battery cell is typically composed of an anode current collector (e.g. Cu foil), an anode electrode or anode active material layer (e.g.
  • the anode layer is composed of particles of an anode active material (e.g. graphite, hard carbon, 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 (d) all non-active material layers in a battery cell (e.g. current collectors and separator) must be kept to a minimum in order to obtain a minimum overhead weight and a maximum lithium storage capability and, hence, a maximized energy density (Wk/kg or Wh/L of cell).
  • either the anode active material e.g. Si coating
  • the cathode active material e.g. lithium transition metal oxide
  • a thin film form directly onto a current collector, such as a sheet of copper foil or Al foil.
  • a thin film structure with 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 for the Si layer 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.
  • Sodium batteries have similar issues.
  • the prior art lithium battery cell is typically made by a process that includes the following steps: (a) The first step is mixing particles of the anode active material (e.g. Si nanoparticles or mesocarbon microbeads, MCMBs), a conductive filler (e.g.
  • the second step includes coating the anode slurry onto one or both primary surfaces of an anode current collector (e.g. Cu foil), drying the coated layer by vaporizing the solvent (e.g.
  • 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.
  • 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 and 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 dry-wet-dry-wet process is not 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 from 20% to 35% (for inorganic such as LiMn 2 0 4 ) or from 7-15% (for organic or polymer cathode materials).
  • the present invention provides a lithium battery or sodium battery cell having a high electrode thickness, high active material mass loading, low overhead weight and volume, high capacity, and high energy density.
  • the invention provides an alkali metal cell comprising: (a) a quasi-solid polymer cathode containing about 30% to about 95% by volume of a cathode active material, about 5% to about 40% by volume of a first electrolyte containing an alkali salt dissolved in a solvent and an ion-conducting polymer dissolved in, dispersed in, or impregnated by this solvent, and about 0.01% to about 30% by volume of a conductive additive wherein the conductive additive, containing conductive filaments, forms a 3D network of electron-conducting pathways such that the quasi-solid electrode has an electrical conductivity from about 10 "6 S/cm to about 300 S/cm (may be higher); (b) an anode (may be a conventional anode or a quasi-solid polymer electrode); and (c) an
  • the quasi-solid polymer cathode preferably contains a cathode active material mass loading no less than 10 mg/cm 2 , preferably no less than 15 mg/cm 2 , further preferably no less than 25 mg/cm 2 , more preferably no less than 35 mg/cm 2 , still more preferably no less than 45 mg/cm 2 , and most preferably greater than 65 mg/cm 2 .
  • the anode may also contain a quasi-solid polymer anode containing about 30% to about 95% by volume of an anode active material, about 5% to about 40% by volume of a second electrolyte containing an alkali salt dissolved in a solvent and an ion-conducting polymer dissolved in, dispersed in, or impregnated by this solvent, and about 0.01%> to about 30%) by volume of a conductive additive wherein said conductive additive, containing conductive filaments, forms a 3D network of electron-conducting pathways such that the quasi- solid electrode has an electrical conductivity from about 10 "6 S/cm to about 300 S/cm; wherein said quasi-solid anode has a thickness no less than 200 ⁇ .
  • the quasi-solid anode preferably contains an anode active material mass loading no less than 10 mg/cm 2 , preferably no less than 15 mg/cm 2 , further preferably no less than 25 mg/cm 2 , more preferably no less than 35 mg/cm 2 , still more preferably no less than 45 mg/cm 2 , and most preferably greater than 65 mg/cm 2 .
  • the first electrolyte may be the same as or different from the second electrolyte in composition and structure.
  • the alkali metal battery contains a quasi-solid polymer anode, but a conventional cathode.
  • the present invention also provides a method of producing an alkali metal battery.
  • the method comprises:
  • the forming step includes deforming the electrode material into an electrode shape without interrupting the 3D network of electron-conducting pathways such that the electrode maintains an electrical conductivity no less than 10 "6 S/cm (preferably no less than 10 "5 S/cm, more preferably no less than 10 "4 S/cm, further preferably no less than 10 "3 S/cm, still more preferably and typically no less than 10 "2 S/cm, even more typically and preferably no less than 10 "1 S/cm, and further more typically and preferably no less than 1 S/cm; up to 300 S/cm was observed);
  • 10 "6 S/cm preferably no less than 10 "5 S/cm, more preferably no less than 10 "4 S/cm, further preferably no less than 10 "3 S/cm, still more preferably and typically no less than 10 "2 S/cm, even more typically and preferably no less than 10 "1 S/cm, and further more typically and preferably no less than 1 S/cm; up to 300 S/
  • the second electrode may be a quasi-solid polymer electrode or a conventional electrode
  • the step of forming a second electrode includes (A) combining a quantity of a second active material (e.g. an anode active material if the first electrode is a cathode), a quantity of an electrolyte, and a conductive additive to form a second deformable and electrically conductive electrode material, wherein the conductive additive, containing conductive filaments, forms a 3D network of electron-conducting pathways and the electrolyte contains an alkali salt and an ion-conducting polymer dissolved or dispersed in a solvent; and (B) forming the second deformable and conductive electrode material into a second quasi-solid electrode, wherein the forming operation includes deforming the second deformable and conductive electrode material into an electrode shape without interrupting said 3D network of electron-conducting pathways such that the second electrode maintains an electrical conductivity no less than 10 "6 S/cm
  • a second active material e.g. an anode active material if the first electrode is a cathode
  • one preferred embodiment of the present invention is an alkali metal-ion cell having a conductive quasi-solid polymer anode 236, a conductive quasi-solid polymer cathode 238, and a porous separator 240 (or ion-permeable membrane) that
  • the quasi-solid polymer anode 236 contains an anode active material (e.g. particles of Si or hard carbon, not shown in FIG.
  • an electrolyte phase typically containing a lithium salt or sodium salt dissolved in a solvent and an ion-conducting polymer dissolved in, dispersed in, or impregnated by this solvent; also not shown in FIG.1(C)
  • a conductive additive containing conductive filaments
  • the quasi-solid polymer cathode contains a cathode active material, an electrolyte, and a conductive additive (containing conductive filaments) that forms a 3D network of electron-conducting pathways 242.
  • FIG. 1(D) Another preferred embodiment of the present invention, as illustrated in FIG. 1(D), is an alkali metal cell having an anode composed of a lithium or sodium metal coating/foil 282 deposited/attached to a current collector 280 (e.g. Cu foil), a quasi-solid cathode 284, and a separator or ion-conducting membrane 282.
  • the quasi-solid polymer cathode 284 contains a cathode active material 272 (e.g.
  • the present invention also includes a lithium-ion capacitor and a sodium-ion capacitor.
  • the electrolyte is preferably a quasi-solid polymer electrolyte containing a lithium salt or sodium salt and a polymer dissolved in a solvent with a combined salt/polymer concentration no less than 1.5 M, preferably greater than 2.5 M, more preferably greater than 3.5 M, further preferably greater than 5 M, still more preferably greater than 7 M, and even more preferably greater than 10 M.
  • the electrolyte is a quasi-solid polymer electrolyte containing a polymer and a lithium salt or sodium salt dissolved in a liquid solvent with a combined salt/polymer concentration from 3.0 M to 14 M.
  • the choices of lithium salt or sodium salt and the solvent are further discussed in later sections.
  • the electrolyte contains a lithium ion-conducting or sodium ion- conducting polymer selected from poly(ethylene oxide) (PEO, having a molecular weight lower than 1 x 10 6 g/mole), polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly(m ethyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVDF), poly bis-methoxy ethoxyethoxide- phosphazene, polyvinyl chloride, polydimethylsiloxane, poly(vinylidene fluoride)- hexafluoropropylene (PVDF-HFP), a sulfonated derivative thereof, a sulfonated polymer, or a combination thereof. Sulfonation is herein found to impart improved lithium ion conductivity to a polymer.
  • a PEO molecular weight higher than 1 x 10 6 g/mole typically
  • this ion-conducting polymer does not form a matrix (continuous phase) in the electrode. Rather, the polymer is dissolved in a solvent as a solution phase or dispersed as a discrete phase in a solvent matrix.
  • the resulting electrolyte is a quasi-solid polymer electrolyte; it is not a liquid electrolyte and not a solid electrolyte.
  • the ion-conducting polymer may be selected from the group consisting of poly(perfluoro sulfonic acid), sulfonated polytetrafluoroethylene, sulfonated perfluoroalkoxy derivatives of polytetrafluoroethylene, sulfonated polysulfone, sulfonated poly(ether ketone), sulfonated poly (ether ether ketone), sulfonated polystyrene, sulfonated polyimide, sulfonated styrene-butadiene copolymers, sulfonated poly chloro-trifluoroethylene (PCTFE), sulfonated perfluoroethylene- propylene copolymer (FEP), sulfonated ethylene-chlorotrifluoroethylene copolymer (ECTFE), sulfonated polyvinylidenefluoride (PVDF), sulfonated copoly
  • Both the quasi-solid anode and the quasi-solid cathode preferably have a thickness greater than 200 ⁇ (preferably greater than 300 ⁇ , more preferably greater than 400 ⁇ , further preferably greater than 500 ⁇ , still more preferably greater than 800 ⁇ , further preferably greater than 1 mm, and can be greater than 5 mm, 1 cm, or thicker.
  • the anode active material typically constitutes an electrode active material loading no less than 20 mg/cm 2 (more typically and preferably no less than 25 mg/cm 2 and more preferably no less than 30 mg/cm 2 ) in the anode.
  • the cathode active material constitutes an electrode active material mass loading no less than 45 mg/cm 2 (typically and preferably greater than 50 mg/cm 2 and more preferably greater than 60 mg/cm 2 ) for an inorganic material as the cathode active material (no less than 25 mg/cm 2 for an organic or polymeric cathode active material).
  • the electrons only have to travel a short distance (e.g. a few micrometers or less) before they are collected by the conductive filaments that constitute the 3D network of electron-conducting pathways and are present everywhere throughout the entire quasi-solid polymer electrode (an anode or cathode).
  • Electrode active material particles are pre-dispersed in an electrolyte solvent (no wettability issue), eliminating the existence of dry pockets commonly present in an electrode prepared by the conventional process of wet coating, drying, packing, and electrolyte injection.
  • electrolyte solvent no wettability issue
  • the presently invented process or method has a totally unexpected advantage over the conventional battery cell production process.
  • These conductive filaments (such as carbon nanotubes and graphene sheets), as supplied, are originally a mass of randomly aggregated filaments prior to being mixed with particles of an active material and an electrolyte. The mixing procedure involves dispersing these conductive filaments in a highly viscous, solid-like electrolyte containing particles of an active material. This is not a trivial task as one might think.
  • nanomaterials particularly nanofilament materials, such as carbon nanotubes, carbon nanofibers, and graphene sheets
  • a highly flowable (non-viscous) liquid has been known to be notoriously difficult, let alone in a highly viscous quasi-solid, such as an electrolyte containing a high loading of an active material (e.g. solid particles, such as Si nanoparticles for the anode and lithium cobalt oxide for the cathode).
  • an active material e.g. solid particles, such as Si nanoparticles for the anode and lithium cobalt oxide for the cathode.
  • the electrolyte itself is a quasi-solid polymer electrolyte, containing a high concentration of lithium salt or sodium salt and a polymer in a solvent.
  • the electrolyte contains a polymer and an alkali metal salt (lithium salt and/or sodium salt) dissolved in an organic or ionic liquid solvent with a combined alkali metal salt/polymer concentration sufficiently high so that the electrolyte exhibits a vapor pressure less than 0.01 kPa or less than 0.6 (60%) of the vapor pressure of the solvent alone (when measured at 20°C), a flash point at least 20 degrees Celsius higher than a flash point of the first organic liquid solvent alone (when no lithium salt is present), a flash point higher than 150°C, or no detectable flash point at all.
  • an alkali metal salt lithium salt and/or sodium salt
  • any volatile organic solvent can be effectively suppressed provided that a sufficiently high amount of an alkali metal salt and a polymer is added to and dissolved in this organic solvent to form a solid-like or quasi-solid polymer electrolyte.
  • a quasi-solid polymer electrolyte exhibits a vapor pressure less than 0.01 kPa and often less than 0.001 kPa (when measured at 20°C) and less than 0.1 kPa and often less than 0.01 kPa (when measured at 100°C).
  • the flash point of the quasi-solid polymer electrolyte is typically at least 20 degrees (often > 50 or > 100 degrees) higher than the flash point of the neat organic solvent alone. In most of the cases, either the flash point is higher than 150°C or no flash point can be detected. The electrolyte just would not catch on fire.
  • any accidentally initiated flame does not sustain for longer than a few seconds.
  • concentration battery electrolytes (with a high molecular fraction, e.g. > 0.2 or > 0.3, of alkali metal salt/polymer chain segments or combined concentration approximately > 2.5 M or 3.5 M) for safety considerations. This is truly unexpected and of utmost technological and scientific significance.
  • Another surprising element of the present invention is the notion that we are able to dissolve a high concentration of an alkali metal salt and a select ion-conducting polymer in just about every type of commonly used battery-grade organic solvent to form a quasi-solid polymer electrolyte suitable for use in a rechargeable alkali metal battery.
  • this concentration is typically greater than 2.5 M (mole/liter), more typically and preferably greater than 3.5 M, still more typically and preferably greater than 5 M, further more preferably greater than 7 M, and most preferably greater than 10 M.
  • the electrolyte is no longer a liquid electrolyte; instead, it is a quasi-solid electrolyte.
  • the quasi-solid polymer electrolyte when implemented at least in the anode, can significantly enhance cyclic and safety performance of rechargeable alkali metal batteries through effective suppression of dendrite growth. It is generally accepted that dendrites start to grow in the non-aqueous liquid electrolyte when the anion is depleted in the vicinity of the electrode where plating occurs. In the ultrahigh concentration electrolyte, there is a mass of anions to keep the balance of cations (Li + or Na + ) and anions near metallic lithium or sodium anode.
  • the space charge created by anion depletion is minimal, which is not conducive to dendrite growth.
  • the quasi- solid polymer electrolyte provides a large amount of available lithium-ion or sodium-ion flux and raises the lithium or sodium ionic mass transfer rate between the electrolyte and the lithium or sodium electrode, thereby enhancing the lithium or sodium deposition uniformity and dissolution during charge/discharge processes.
  • the local high viscosity induced by a high concentration will increase the pressure from the electrolyte to inhibit dendrite growth, potentially resulting in a more uniform deposition on the surface of the anode.
  • the high viscosity could also limit anion convection near the deposition area, promoting more uniform deposition of sodium ions. Same reasoning is applicable to lithium metal batteries. These reasons, separately or in combination, are believed to be responsible for the notion that no dendrite-like feature has been observed with any of the large number of rechargeable alkali metal cells that we have investigated thus far. Furthermore, a skilled artisan in the field of chemistry or materials science would have anticipated that such a high salt/polymer concentration should make the electrolyte behave like a solid with an extremely high viscosity and, hence, this electrolyte should not be amenable to fast diffusion of alkali metal ions therein.
  • an alkali metal battery containing such a solid-like polymer electrolyte would not and could not exhibit a high capacity at a high charge-discharge rate or under a high current density condition (i.e. the battery should have a poor rate capability).
  • all the alkali metal cells containing such a quasi-solid polymer electrolyte deliver high energy density and high power density for a long cycle life. It appears that the quasi-solid polymer electrolytes as herein invented and disclosed are conducive to facile alkali metal ion transport. This surprising observation is likely due to two major factors: one related to the internal structure of the electrolyte and the other related to a high Na + or Li + ion transference number (TN).
  • FIG. 2(A) schematically shows the closely packed, highly ordered structure of a typical solid electrolyte, wherein there is little free volume for diffusion of alkali metal ions. Migration of any ions in such a crystal structure is very difficult, leading to an extremely low diffusion coefficient (10 "16 to 10 "12 cm 2 /sec) and extremely low ion conductivity (typically from 10 "7 S/cm to 10 "4 S/cm). In contrast, as schematically shown in FIG.
  • liquid electrolyte is totally amorphous, having large fractions of free volume through which cations (e.g. or Li or Na ) can easily migrate, leading to a high diffusion coefficient (10 "8 to 10 "6 cm 2 /sec) and high ion conductivity (typically from 10 "3 S/cm tolO "2 S/cm).
  • cations e.g. or Li or Na
  • high diffusion coefficient typically from 10 "3 S/cm tolO "2 S/cm
  • liquid electrolyte containing a low concentration of alkali metal salt is flammable and prone to dendrite formation, posing fire and explosion danger. Schematically shown in FIG.
  • 2(C) is the randomized or amorphous structure of a quasi-solid polymer electrolyte having solvent molecules separating salt species and polymer chain segments to produce amorphous zones for easy migration of free (un-clustered) cations.
  • Such a structure is amenable to achieving a high ion conductivity value (typically 10 "4 S/cm to 8xl0 "3 S/cm), yet still maintaining non-flammability. There are relatively few solvent molecules and these molecules are being retained (prevented from vaporizing) by
  • the anode active material is a prelithiated or pre-sodiated 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, mesophase carbon, mesophase pitch, mesocarbon microbead, soft carbon, hard carbon, coke, carbon fiber, carbon nanofiber, carbon nanotube, or a combination thereof.
  • Graphene materials are also a good conductive additive for both the anode and cathode active materials of a lithium 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.
  • a typical process is shown in FIG. 4.
  • 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 “nanographene platelets” (NGPs).
  • NGPs Graphene sheets/platelets (collectively, NGPs) are a new class of carbon nanomaterial (a 2-D nanocarbon) that is distinct from the 0-D fullerene, the 1-D CNT or CNF, and the 3-D graphite.
  • a graphene material is not (and does not include) a carbon nanotube (CNT) or a carbon nanofiber (CNF).
  • CNT carbon nanotube
  • CNF carbon nanofiber
  • 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. 5(A) and FIG. 5(B).
  • GIC graphite intercalation compound
  • GO graphite oxide
  • 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 ( ⁇ 002 , 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 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 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", 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 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), as disclosed in our US Application No. 10/858,814 (06/03/2004).
  • 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.
  • the inter-graphene plane separation bas been increased from 0.3354 nm in natural graphite to 0.6-1.1 nm in highly oxidized graphite oxide, significantly weakening the van der Waals forces that hold neighboring planes together.
  • Ultrasonic power can be sufficient to further separate graphene plane sheets to form fully separated, isolated, or discrete graphene oxide (GO) sheets.
  • RGO reduced graphene oxides
  • 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.
  • 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.
  • non-carbon elements e.g. O, H, N, B, F, CI, Br, I, etc.
  • 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,
  • the anode active material absorbs 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) when the battery is charged.
  • the anode active material of a lithium battery is selected from the group consisting of: (a) particles of lithium metal or a lithium metal alloy; (b) natural graphite particles, artificial graphite particles, mesocarbon microbeads (MCMB), carbon particles (including soft carbon and hard carbon), needle coke, carbon nanotubes, carbon nanofibers, carbon fibers, and graphite fibers; (c) 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); (d) 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; (e) silicon (S
  • a sodium intercalation compound selected
  • the alkali metal cell is a sodium metal cell or sodium-ion cell and the active material is an anode active material selected from the group consisting of: (a) particles of sodium metal or a sodium metal alloy; (b) natural graphite particles, artificial graphite particles, mesocarbon microbeads (MCMB), carbon particles, needle coke, carbon nanotubes, carbon nanofibers, carbon fibers, and graphite fibers; (c) sodium-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; (d) sodium-containing alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd, and their mixtures; (e
  • the cathode active material typically is a lithium intercalation compound or lithium- absorbing compound that is capable of storing lithium ions when the lithium battery is discharged and releasing lithium 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 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.
  • 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.
  • 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 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,
  • PAQS poly(anthraquinonyl sulfide)
  • PTCDA 10-perylenetetracarboxylic dianhydride
  • PYT pyrene-4,5,9,10-tetraone
  • PYT polymer-bound PYT
  • 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)
  • HAT(CN) 6 hexaazatriphenylene hexacarbonitrile
  • HAT(CN) 6 5-benzylidene hydantoin
  • isatine lithium salt pyromellitic diimide lithium salt
  • tetrahydroxy-p-benzoquinone derivatives TQLi 4
  • PPP ⁇ , ⁇ '- diphenyl-2,3,5,6-tetraketopiperazine
  • AP N,N'-diallyl-2,3,5,6-tetraketopiperazine
  • PvP a thioether polymer
  • a quinone compound 1,4- benzoquinone, 5,7, 12,14-pentacenetetrone (PT), 5-amino-2,3-dihydro-l,4-dyhydroxy
  • 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-l,l,2,2- tetrathiol)
  • PETT poly(ethene-l,l,2,2- tetrathiol)
  • PPDT poly(2-phenyl-l,3-dithiolane)
  • PPDT poly(l,4-di(l,3-dithiolan-2-yl)benzene)
  • PTDTB poly(tetrahydrobenzodithiophene)
  • PTHBDT poly(tetrahydrobenzodithiophene)
  • 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, nanodisc, nanoribbon, or nanoplatelet 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 nanodiscs, nanoplatelets, nanocoating, or nanosheets 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 nanodiscs, nanoplatelets, nanocoating, or nanosheets 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.
  • the cathode active material may contain a sodium intercalation compound selected from NaFeP0 4 (sodium iron phosphate), Nao 7 FePC"4, Na 1-5 VOPO4F0 5, Na 3 V 2 (P04)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 VOP0 4 Fo.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 (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), Na 0.44 MnO 2 , Na 0 .
  • NaFeP0 4
  • HCF copper and nickel hexacyanoferrate
  • NiHCF nickel hexacyanoferrate
  • the cathode active material may be selected from a functional material or nanostructured 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 nanostructured material may be selected from the group consisting of (a) a nanostructured or porous disordered carbon material selected from a soft carbon, hard carbon, polymeric carbon or carbonized resin, mesophase carbon, coke, carbonized pitch, carbon black, activated carbon, nanocellular carbon foam or partially graphitized carbon; (b) a nanographene 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 nanofiber, nanowire, metal oxide nanowire or fiber, conductive polymer nanofiber, 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 nanostructured or porous disordered carbon material selected from a soft carbon, hard carbon, polymeric carbon or carbonized resin, me
  • the functional material or nanostructured material has a functional group selected from -CO
  • Non-graphene 2D nanomaterials 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
  • DMC dimethyl carbonate
  • MEC methylethyl carbonate
  • DEC diethyl carbonate
  • ethyl propionate methyl propionate
  • PC ⁇ -butyrolactone
  • AN acetonitrile
  • EA ethyl acetate
  • PF propyl formate
  • MF methyl formate
  • 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 (LiC10 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), lithium hexafluoroarsenide (LiAsF 6 ), lithium trifluoro- metasulfonate (LiCF 3 S0 3 ) and bis-trifluoromethyl sulfonylimide lithium (LiN(CF 3 S0 2 ) 2 ).
  • LiPF 6 , LiBF 4 and LiN(CF 3 S0 2 ) 2 are preferred.
  • the content of aforementioned electrolytic salts in the non-aqueous solvent is preferably 0.5 to 2.0 mol/1.
  • the electrolyte may contain a sodium salt preferably selected from sodium perchlorate (NaC10 4 ), sodium
  • 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)sulfonamide (TFSI) anion.
  • EMI l-ethyl-3- methylimidazolium
  • TFSI N,N-bis(trifluoromethane)sulfonamide
  • 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(trifluoromethanesulfonyl) imide, bis(fluorosulfonyl)imide, and hexafluorophosphate as anions. Based on their
  • ionic liquids come in different classes that basically include aprotic, protic and zwitterionic types, each one suitable for a specific application.
  • Common cations of room temperature ionic liquids 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 “ , CH 3 BF 3 “ , 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 with good working conductivities.
  • 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 supercapacitor.
  • 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 0 8 , 20 g of P 2 0 5 , and 400 mL of a concentrated aqueous solution of H 2 S0 (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 % ⁇ 2 0 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 ⁇ L 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.
  • RGO was used as a conductive additive in either or both of the anode and cathode active material in certain lithium batteries presently invented.
  • Prelithiated RGO e.g. RGO + lithium particles or RGO pre-deposited with lithium coating
  • 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 of slurry injection into foam pores and conventional procedure of slurry coating, drying and layer laminating. Both lithium-ion batteries and lithium metal batteries (injection into cathode only) were investigated.
  • EXAMPLE 3 Preparation of prelithiated graphene fluoride sheets as an anode active material of a lithium-ion battery
  • HEG highly exfoliated graphite
  • FHEG fluorinated highly exfoliated graphite
  • Pre-cooled Teflon reactor was filled with 20-30 mL of liquid pre-cooled C1F 3 , the reactor was closed and cooled to liquid nitrogen temperature. Then, no more than 1 g of HEG was put in a container with holes for C1F 3 gas to access and situated inside the reactor. In 7-10 days a gray -beige product with approximate formula C 2 F was formed.
  • Preferred sodium metal salts include: sodium perchl orate (NaC10 4 ), sodium
  • NaPF 6 sodium borofluoride
  • NaBF 4 sodium hexafluoroarsenide
  • potassium hexafluoroarsenide sodium trifluoro-metasulfonate
  • NaN(CF 3 S0 2 ) 2 bis- trifluoromethyl sulfonylimide sodium
  • lithium salts that tend to be dissolved well in selected organic or ionic liquid solvents: lithium borofluoride (LiBF 4 ), lithium trifluoro-metasulfonate (LiCF 3 S0 3 ), lithium bis-trifluorom ethyl sulfonylimide (LiN(CF 3 S0 2 ) 2 or LITFSI), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF 2 C 2 0 4 ), and lithium bisperfluoroethy-sulfonylimide (LiBETI).
  • LiN0 3 lithium bis(trifluoro methanesulfonyl)imide
  • LiTFSI lithium bis(trifluoro methanesulfonyl)imide
  • Preferred organic liquid solvents include: ethylene carbonate (EC), dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), propylene carbonate (PC), acetonitrile (AN), vinylene carbonate (VC), allyl ethyl carbonate (AEC), 1,3-dioxolane (DOL), 1,2-dimethoxyethane (DME), tetraethylene glycol dimethyl ether (TEGDME), poly(ethylene glycol) dimethyl ether (PEGDME), diethylene glycol dibutyl ether (DEGDBE), 2-ethoxyethyl ether (EEE), hydrofloroether (e.g. TPTP), sulfone, and sulfolane.
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • MEC methylethyl carbonate
  • DEC diethyl carbonate
  • PC propylene carbonate
  • AN acetonitrile
  • Preferred ionic liquid solvents may be selected from a room temperature ionic liquid (RTIL) having a cation selected from tetraalkyl ammonium, di-alkylimidazolium,
  • RTIL room temperature ionic liquid
  • alkylpyridinium, dialkyl-pyrrolidinium, or dialkylpiperidinium is preferably selected from BF 4 " , B(CN) 4 " , CF 3 C0 2 " , CF 3 S0 3 " , N(S0 2 CF 3 ) 2 " , N(COCF 3 )(S0 2 CF 3 ) " , or
  • Particularly useful ionic liquid-based solvents include N-n-buty ⁇ -N- ethylpyrrolidinium bis(trifluoromethane sulfonyl)imide (BEPyTFSI), N-methyl-iV- propylpiperidinium bis(trifluoromethyl sulfonyl)imide (PP 1 TFSI), and N ⁇ -di ethyl -N-methyl-JV- (2-m ethoxyethyl) ammonium bi s(tri fl uorom ethyl sul fony 1 )i mide.
  • BEPyTFSI N-n-buty ⁇ -N- ethylpyrrolidinium bis(trifluoromethane sulfonyl)imide
  • PP 1 TFSI N-methyl-iV- propylpiperidinium bis(trifluoromethyl sulfonyl)imide
  • Preferred lithium ion-conducting or sodium ion-conducting polymers include
  • PEO poly(ethylene oxide)
  • polypropylene oxide PPO
  • poly(acrylonitrile) PAN
  • poly(vinylidene fluoride)- hexafluoropropylene PVDF-FIFP
  • Preferred sulfonated polymers include poly(perfluoro sulfonic acid), sulfonated polytetrafluoroethylene, sulfonated polysulfone, sulfonated poly (ether ether ketone) (S-PEEK), and sulfonated polyvinylidenefluonde (S-PVDF).
  • EXAMPLE 5 Vapor Pressure of Some Solvents and Corresponding Quasi-solid Polymer Electrolytes with Various Sodium Salt Molecular Ratios.
  • Vapor pressures of several solvents (DOL, DME, PC, AN, with or without an ionic liquid-based co-solvent, PP 13 TFSI) before and after adding a wide molecular ratio range of sodium salts, such as sodium borofluoride (NaBF ), sodium perchlorate (NaC10 4 ), or sodium bis(trifluoro methanesulfonyl)imide (NaTFSI), along with PEO, were measured.
  • the vapor pressure drops at a very high rate when the combined salt/polymer concentration exceeds 2.3 M, and rapidly approaches a minimal or essentially zero when the combined concentration exceeds 3.0 M.
  • EXAMPLE 6 Flash Points and Vapor Pressure of Some Solvents and Corresponding Quasi- solid Polymer Electrolytes with a Combined Sodium or Lithium Salt/Polymer Concentration of 3.0M.
  • Table 1 The flash points and vapor pressures of select solvents and their electrolytes.
  • Na + ions travel in a low salt concentration electrolyte (e.g. x ⁇ 0.2), a Na + ion can drag multiple solvating molecules along with it. The coordinated migration of such a cluster of charged species can be further impeded if the fluid viscosity is increased due to more salt and polymer dissolved in the solvent.
  • Na + ions could significantly out-number the available solvating molecules that otherwise could cluster the sodium ions, forming multi-ion complex species and slowing down their diffusion process.
  • This high Na + ion concentration makes it possible to have more "free Na + ions" (non-clustered), thereby providing a higher Na + transference number (hence, a facile Na + transport).
  • the sodium ion transport mechanism changes from a multi-ion complex- dominating one (with an overall larger hydrodynamic radius) to single ion-dominating one (with a smaller hydrodynamic radius) having a large number of available free Na + ions.
  • This observation has further asserted that an adequate number of Na + ions can quickly move through or from the quasi-solid electrolytes to make themselves readily available to interact or react with a cathode (during discharge) or an anode (during charge), thereby ensuring a good rate capability of a sodium secondary cell.
  • these highly concentrated electrolytes are nonflammable and safe. Combined safety, facile sodium ion transport, and electrochemical performance characteristics have been thus far difficult to come by for all types of sodium and lithium secondary batteries.
  • EXAMPLE 8 Lithium iron phosphate (LFP) cathode of a lithium metal battery
  • LFP powder un-coated or carbon-coated
  • graphene sheets RGO
  • carbon nanofiber CNF
  • the lithium salt used in this example includes lithium borofluoride (LiBF 4 ), and the organic solvents are PC, DOL, DEC, and their mixtures.
  • LiBF 4 lithium borofluoride
  • the organic solvents are PC, DOL, DEC, and their mixtures.
  • Sequence 1 LiBF 4 salt and PEO were dissolved in a mixture of PC and DOL first to form an electrolyte having a combined salt/polymer concentration of 1.0 M, 2.5 M, and 3.5 M, respectively. (With a concentration of 2.3 M or higher, the resulting electrolyte was no longer a liquid electrolyte. It actually behaves more like a solid and, hence, the term "quasi-solid".) Then, RGO or CNT filaments were dispersed in the electrolyte to form a filament-electrolyte suspension. Mechanical shearing was used to help forming uniform dispersion. (This filament- electrolyte suspension, even with a low salt concentration of 1.0 M, was also quite viscous). LFP particles, the cathode active material, were then dispersed in the filament-electrolyte suspension to form a quasi-solid polymer electrode material.
  • Sequence 2 LiBF 4 salt and PEO were dissolved in a mixture of PC and DOL first to form an electrolyte having a combined salt/polymer concentration of 1.0 M, 2.5 M, and 3.5 M, respectively. Then, LFP particles, the cathode active material, were dispersed in the electrolyte to form an active particle-electrolyte suspension. Mechanical shearing was used to help forming uniform dispersion. (This active particle-electrolyte suspension, even with a low salt concentration of 1.0 M, was also quite viscous). RGO or CNT filaments were then dispersed in the active particle-electrolyte suspension to form a quasi-solid polymer electrode material.
  • Sequence 3 First, a desired amount of RGO or CNT filaments was dispersed in the liquid solvent mixture (PC + DOL) containing no lithium salt or polymer dissolved therein. Mechanical shearing was used to help forming uniform suspension of conducting filaments in the solvent. The LiBF 4 salt, PEO, and LFP particles were then added into the suspension, allowing LiBF 4 salt and PEO to get dissolved in the solvent mixture of the suspension to form an electrolyte having a combined salt/polymer concentration of 1.0 M, 2.5 M, and 3.5 M, respectively.
  • LFP particles were dispersed in the electrolyte to form a deformable quasi-solid electrode material, which is composed of active material particles and conducting filaments dispersed in a quasi-solid polymer electrolyte (not a liquid electrolyte and not a solid electrolyte).
  • the conducting filaments percolate to form a 3D network of electron-conducting pathways. This 3D conducting network is maintained when the electrode material is shaped into an electrode of a battery.
  • the electrical conductivity of the electrode was measured using a four-point probe method.
  • the results are summarized in FIG. 5(A) and FIG. 5(B).
  • CNFs or RGO conductive filaments
  • S3 Sequence 3
  • the step of dispersing conductive filaments in a liquid solvent must be conducted before the lithium salt, sodium salt, or the ion-conducting polymer is dissolved in the liquid solvent and before active material particles are dispersed in the solvent.
  • a quasi-solid cathode, a porous separator, and a quasi-solid anode were then assembled together to form a unit cell, which was then encased in a protective housing (a laminated aluminum-plastic pouch), having two terminals protruding out, to make a battery.
  • Batteries containing a liquid or polymer gel electrolyte (1 M) and quasi-solid polymer electrolytes (2.5 M and 3.5 M) were fabricated and tested.
  • Example 19 For comparison purposes, slurry coating and drying procedures were conducted to produce conventional electrodes. One anode and one cathode, and a separator disposed between the two electrodes, were then assembled and encased in an Al-plastic laminated packaging envelop, followed by liquid electrolyte injection to form a prior art lithium battery cell. Battery testing results are summarized in Example 19.
  • 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.
  • V 2 0 5 powder and graphene-supported V 2 0 5 powder were then incorporated in a battery using both the presently invented method and the conventional procedure of slurry coating, drying and layer laminating.
  • CNTs conductive additive
  • EXAMPLE 10 LiCo0 2 as an example of lithium transition metal oxide cathode active material for a lithium-ion battery
  • Commercially available L1C0O 2 powder and multi-walled carbon nanotubes (MW-CNTs) were dispersed in a quasi-solid polymer electrolyte to form a quasi-solid electrode.
  • Two types of quasi-solid anode were prepared to couple with the cathode.
  • the electrolyte solvent used was EC-VC (80/20 ratio) and LiBOB+PEO were dissolved in this organic solvent to form the quasi-solid polymer electrolyte.
  • Each cell contains a quasi- solid anode, a separator layer, and a quasi-solid cathode assembled together and then
  • LiCo0 2 powder, MW-CNTs, 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, 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.
  • EXAMPLE 11 Organic material (Li 2 C 6 0 6 ) as a cathode active material of a lithium metal battery
  • dilithium rhodizonate Li 2 C 6 0 6
  • 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 2.5 M of lithium hexafluorophosphate (LiPF 6 ) and PPO in PC-EC.
  • the two Li atoms in the formula Li 2 C 6 0 6 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 (Cu foil) is deposited with a layer of lithium (e.g. via sputtering or electrochemical plating, or by using a lithium foil). This was followed by assembling the lithium-coated layer, a porous separator, and a quasi-solid cathode into a cell.
  • the cathode active material and conductive additive (Li 2 C 6 0 6 /C composite particles + C Fs) were dispersed in the liquid electrolyte.
  • the corresponding conventional Li metal cell was also fabricated by the conventional procedures of slurry coating, drying, laminating, packaging, and electrolyte injection.
  • EXAMPLE 12 Metal naphthalocyanine-RGO hybrid cathode of a lithium metal battery
  • Copper naphthalocyanine (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 having a lithium metal foil as the anode active material and 1.0 M and 3.0 M of LiC10 4 and PEO in propylene carbonate (PC) solution as the electrolyte.
  • PC propylene carbonate
  • EXAMPLE 13 Preparation of MoS 2 /RGO hybrid material as a cathode active material of a lithium metal battery
  • MXenes were produced by partially etching out certain elements from layered structures of metal carbides such as Ti 3 AlC 2 . For instance, an aqueous 1 M NH 4 FIF 2 was used at room temperature as the etchant for Ti 3 AlC 2 .
  • the MXene materials investigated include Ti 2 CT x , Nb 2 CT x , V 2 CT X , Ti 3 CNT x , and Ta 4 C 3 T x .
  • 2-35% graphene sheets were mixed in a solvent, followed by adding 35-95% MXene, some Li/Na salt, and a polymer to form a quasi-solid electrolyte-based cathode that is deformable, conformable, and conductive.
  • 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.
  • 32.4mL of 0.1 mol/L KMn0 4 solution and selected amounts of GO solution were added in the solution, which was ultrasonicated for 30 min to prepare a dark brown precipitate.
  • the product was separated, washed several times with distilled water and ethanol, and dried at 80°C for 12 h.
  • the sample is graphene-supported Mn0 2 in a powder form, which, along with a lithium salt and PEO, was dispersed in a CNT-containing electrolyte to form a quasi-solid polymer electrolyte-based cathode electrode.
  • EXAMPLE 17 Graphene-enhanced nano silicon as an anode active material of a lithium-ion battery
  • Graphene-wrapped Si particles were available from Angstron Energy Co., Dayton, Ohio).
  • Quasi-solid anode electrodes were prepared by dispersing pristine graphene sheets (as conductive filaments) in a PC-DOL (50/50 ratio) mixture, followed by dispersing graphene- wrapped Si particles (anode active material), and by dissolving 3.5 M of lithium
  • LiPF 6 hexafluorophosphate
  • EXAMPLE 18 Cobalt Oxide (Co 3 0 4 ) particulates as an anode active material
  • LiCo0 2 is a cathode active material
  • Co 3 0 4 is an anode active material of a lithium-ion battery since LiCo0 2 is at an electrochemical potential of approximately +4.0 volts relative to Li/Li + and Co 3 0 4 is at an electrochemical potential of approximately +0.8 volts relative to Li/Li + .
  • Tin oxide (Sn0 2 ) nanoparticles 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. Subsequently, the resulting hydrosol was reacted with the GO dispersion for 3 hours. To this mixed solution, few drops of 0.1 M of H 2 S0 4 were added to flocculate the product. The precipitated solid was collected by
  • 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 (NMP).
  • NMP 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 1M LiPF 6 electrolyte solution dissolved in a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC) (EC-DEC, 1 : 1 v/v).
  • EC-DEC ethylene carbonate
  • DEC-DEC diethyl carbonate
  • ionic liquids were used as the liquid electrolyte.
  • the cell assemblies were made in an argon-filled glove-box.
  • a quasi-solid anode, a porous separator, and a quasi-solid cathode are assembled in a protective housing.
  • the pouch was then sealed.
  • the cyclic voltammetry (CV) measurements were carried out using an Arbin electrochemical workstation at a typical scanning rate of 1 mV/s.
  • the 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. For long-term cycling tests, multi-channel battery testers manufactured by LAND were used.
  • the gravimetric energy densities and power densities of the lithium-ion battery cells prepared by the presently invented method are significantly higher than those of their
  • FIG. 7 shows the Ragone plots (gravimetric power density vs. gravimetric energy density) of two cells, both containing graphene-embraced Si nanoparticles as the anode active material and LiCo0 2 nanoparticles as the cathode active material.
  • the experimental data were obtained from the Li-ion battery cells that were prepared by the presently invented method and those by the conventional slurry coating of electrodes.
  • FIG. 8 Shown in FIG. 8 are Ragone plots of lithium metal batteries containing a lithium foil as the anode active material, dilithium rhodizonate (Li 2 C 6 0 6 ) as the cathode active material, and lithium salt (LiPF 6 )-PC/DEC as organic electrolyte (both 1.5 M and 5.0 M).
  • the quasi-solid electrodes were prepared according to the sequences S2 and S3 as described in Example 8.
  • the data are for the three lithium metal cells prepared by the presently invented method and those by the conventional slurry coating of electrodes. These data indicate that the gravimetric 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. Again, the differences are huge and are likely due to the significantly higher active material mass loading (not just mass loading) and higher conductivity associated with the presently invented electrodes, reduced proportion of overhead (non-active) components relative to the active material weight/volume, and
  • the gravimetric energy density of the presently invented lithium metal -organic cathode cell is as high as 502 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).
  • a gravimetric power density of 1,578 W/kg and would have been un-thinkable.
  • the cells containing a quasi-solid electrode prepared according to Sequence 3 exhibit significantly higher energy densities and power densities as compared to those of the conventional sequence S2.
  • higher concentration electrolytes are surprisingly more conducive to achieving higher energy densities and power densities.
  • FIG.9 indicates Ragone plots of two sodium -ion capacitors each containing pre-sodiated hard carbon particles as the anode active material and graphene sheets as a cathode active material; one cell having an anode prepared by the conventional slurry coating process and the other cell having a quasi-solid anode prepared according to a presently invented method.
  • the quasi-solid electrode-based cell delivers significantly higher energy density and higher power density. Lithium-ion capacitors were found to follow similar trend.
  • 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 cathode active material for inorganic material, such as LiMn 2 0 4
  • a factor of 3 to 4 is frequently used to extrapolate the energy or power densities of the device (cell) from the properties based on the active material weight alone.
  • the properties reported are typically based on the active material weight alone and the electrodes are typically very thin ( « 100 ⁇ , and mostly « 50 ⁇ ).
  • 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.

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Abstract

L'invention concerne un procédé de préparation d'une cellule à métal alcalin, le procédé comprenant : (a) la combinaison d'une certaine quantité d'un matériau actif, d'une certaine quantité d'un électrolyte et d'un additif conducteur pour former un matériau d'électrode déformable et conducteur, l'additif conducteur, contenant des filaments conducteurs, formant un réseau 3D de voies conductrices d'électrons et l'électrolyte contenant un sel alcalin et un polymère conducteur d'ions dissous ou dispersé dans un solvant ; (b) le façonnage du matériau d'électrode en une électrode polymère quasi-solide, le façonnage comprenant la déformation du matériau d'électrode pour lui donner une forme d'électrode sans rupture du réseau 3D des voies conductrices d'électrons de telle sorte que l'électrode conserve une conductivité électrique supérieure ou égale à 10-6 S/cm ; (c) la formation d'une seconde électrode ; et (d) la formation d'une cellule à métal alcalin par combinaison de l'électrode quasi-solide et de la seconde électrode. La seconde électrode peut également être une électrode polymère quasi-solide.
PCT/US2018/031519 2017-05-30 2018-05-08 Batterie à métal alcalin de forme adaptable dotée d'une électrode polymère quasi-solide conductrice et déformable WO2018222348A1 (fr)

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CN111908457A (zh) * 2020-09-23 2020-11-10 广西师范大学 一种电化学剥离制备石墨烯的对电极装置
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